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RELATED APPLICATION INFORMATION
[0001] This application is a continuation of U.S. patent application Ser. No. 14/795,867, filed Jul. 9, 2015, which is a continuation of U.S. patent application Ser. No. 14/019,119, filed Sep. 5, 2013, which is a continuation of U.S. patent application Ser. No. 13/709,586, filed Dec. 10, 2012, which is a continuation of U.S. patent application Ser. No. 12/408,058, filed Mar. 20, 2009, and claims priority to U.S. Provisional Application Ser. No. 61/045,465, filed Apr. 16, 2008. The entire disclosures of the prior applications are considered part of, and are incorporated by reference in their entireties in, the disclosure of this application.
BACKGROUND
[0002] Glatiramer acetate (also known as copolymer-1 and marketed as the active ingredient in COPAXONE® by Teva Pharmaceutical Industries Ltd., Israel) is used in the treatment of the relapsing-remitting form of multiple sclerosis (RRMS). According to the COPAXONE® product label, glatiramer acetate (GA) consists of the acetate salts of synthetic polypeptides, containing four naturally occurring amino acids: L-glutamic acid, L-alanine, L-tyrosine, and L-lysine with a reported average molar fraction of 0.141, 0.427, 0.095, and 0.338, respectively. Chemically, glatiramer acetate is designated L-glutamic acid polymer with L-alanine, L-lysine and L-tyrosine, acetate (salt). Its structural formula is:
[0000] (Glu, Ala, Lys, Tyr) x .xCH 3 COOH (C 5 H 9 NO 4 lC 3 H 7 NO 2 .C 6 H 14 N 2 O 2 .C 9 H 11 NO 3 ) x .xC H 4 O 2 CAS-147245-92-9
SUMMARY OF THE INVENTION
[0003] The invention is based, at least in part, on the identification and characterization of L-pyroGlutamic Acid (pyro-Glu) as a structural signature of glatiramer acetate (GA). Analysis of this signature component of GA is useful to assess product and process quality in the manufacture of GA.
[0004] Described herein is a method of selecting a batch of a composition comprising an amino acid copolymer (e.g., GA), the method comprising: providing a batch of a composition comprising an amino acid copolymer; measuring the amount of gyro-glutamate (pyro-Glu) in the batch; and selecting the batch if the amount of pyro-Glu in the batch is within a predetermined range. In this method, as in the other methods described herein, the measuring step can employ any suitable method and the units used to express the measured amount of pyro-Glu can be any suitable units (e.g., ppm or mole percent of chains). In measuring the amount of pyro-Glu, one can, e.g., measure the concentration of pyroGlu in a sample or the total amount of pyro-Glu in sample. However an amount of pyro-Glu is measured and whatever units are used to express the measured amount, the concentration of pyro-Glu in the selected batch is between 2000 and 7000 ppm (in some cases between 2500 and 6500 ppm) on a dry weight/dry weight basis.
[0005] Also described is a method for preparing a pharmaceutical composition comprising: providing a batch of a composition comprising an amino acid copolymer, measuring the amount of pyro-Glu in the batch; and preparing a pharmaceutical composition comprising at least a portion of the batch if the amount of pyro-Glu in the batch is within a predetermined range. Here too, the measuring step can employ any suitable method and units used to express the measured amount of pyro-Glu can be any suitable units (e.g., ppm or mole percent of chains). However the pyro-Glu is measured and whatever units are used to express the measured amount, the concentration of pyro-Glu in the selected batch is between 2000 and 7000 ppm (in some cases between 2500 and 6500 ppm) on a dry weight/dry weight basis.
[0006] A batch of a composition comprising an amino acid copolymer can be all or part of the product of a copolymer manufacturing process (e.g., all or part of a single manufacturing run). In some cases, one batch is analyzed. In some cases two or more batches are analyzed. In some cases, multiple samples taken from a single batch are analyzed. The composition containing a copolymer can be a drug substance (DS) (also known as an active pharmaceutical ingredient (API)), a drug product (DP), or a process intermediate. The copolymer can be glatiramer acetate.
[0007] Also described is a method for preparing a pharmaceutical composition comprising glatiramer acetate, comprising: polymerizing N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine to generate a protected copolymer; treating the protected copolymer to partially depolymerize the protected copolymer, deprotect benzyl protected groups and deprotect TFA-protected lysines to generate glatiramer acetate; and purifying the glatiramer acetate, wherein the improvement comprises: measuring the amount of pyro-glutamate (pyro-Glu) in the purified glatiramer acetate. In other embodiments the improvement further comprises selecting the purified glatiramer acetate for use in the preparation of a pharmaceutical composition if the amount of pyro-Glu in the purified glatiramer acetate is within a predetermined range. In some embodiments the concentration of pyro-Glu in the selected purified glatiramer acetate 2000-7000 ppm or 2500-6500 ppm.
[0008] Also described is a method for preparing a pharmaceutical composition comprising glatiramer acetate, the method comprising: polymerizing N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine to generate a protected copolymer; treating the protected copolymer to partially depolymerize the protected copolymer and deprotect benzyl protected groups and deprotecting TFA-protected lysines to generate glatiramer acetate; and purifying the glatiramer acetate, wherein the improvement comprises: measuring the amount of pyro-glutamate (pyro-Glu) during or after the polymerizing step.
[0009] Described herein is a method for preparing a pharmaceutical composition comprising glatiramer acetate, the method comprising: polymerizing N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine to generate a protected copolymer; treating the protected copolymer to partially depolymerize the protected copolymer and deprotect benzyl protected groups and deprotecting TFA-protected lysines to generate glatiramer acetate; and purifying the glatiramer acetate, wherein the improvement comprises: measuring the amount of pyro-glutamate (pyro-Glu) during or after the partial depolymerization step.
[0010] In the aforementioned methods for preparing a pharmaceutical composition the improvement can further comprise: measuring the amount of pyro-glutamate (pyro-Glu) in the purified glatiramer acetate; selecting the purified glatiramer acetate for use in the preparation of a pharmaceutical composition if the amount of pyro-Glu in the purified glatiramer acetate is within a predetermined range; and preparing a pharmaceutical composition comprising at least a portion of the selected purified glatiramer acetate. In various embodiments, concentration of pyro-Glu in the selected purified glatiramer acetate is, for example, 2000-7000 ppm or 2500-6500 ppm.
[0011] Also described is a method for preparing a pharmaceutical composition comprising glatiramer acetate, comprising: polymerizing N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine to generate a protected copolymer; treating the protected copolymer to partially depolymerize the protected copolymerand deprotect benzyl protected groups and deprotecting TFA-protected lysines to generate glatiramer acetate; and purifying the glatiramer acetate, wherein the improvement comprises: measuring the amount of benzyl alcohol during or after the polymerizing step, wherein the amount of benzyl alcohol is correlated to the amount of pyro-Glu.
[0012] Described herein is a method for preparing a pharmaceutical composition comprising glatiramer acetate, comprising: polymerizing N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine to generate a protected copolymer; treating the protected copolymer to partially depolymerize the protected copolymer and deprotect benzyl protected groups and deprotecting TFA-protected lysines to generate glatiramer acetate; and purifying the glatiramer acetate, wherein the improvement comprises: measuring the amount of benzyl alcohol during or after the partial depolymerization step, wherein the amount of benzyl alcohol is correlated to the amount of pyro-Glu.
[0013] In either of the methods entailing measuring the amount of benzyl alcohol, the improvement can further comprise: measuring the amount of pyro-glutamate (pyro-Glu) in the purified glatiramer acetate; selecting the purified glatiramer acetate for use in the preparation of a pharmaceutical composition if the amount of pyro-Glu in the purified glatiramer acetate is within a predetermined range; and preparing a pharmaceutical composition comprising at least a portion of the selected purified glatiramer acetate. In various embodiments, the concentration of pyro-Glu in the selected purified glatiramer acetate is, for example, 2000-7000 ppm or 2500-6500 ppm.
[0014] The step of measuring the amount of pyro-Glu in a batch or sample can include any method for measuring (qualitatively or quantitatively) the amount of pyro-Glu and can include multiple steps and processes. Thus, the measuring step can include, for example: direct measurement of the copolymer, size fractionating the copolymer, digesting the copolymer, or cleaving the copolymer. The measuring can be based on, for example, the total amount of pyro-Glu or on the concentration of pyro-Glu or on the percentage of copolymer peptides that include a pyro-Glu. The measured amount can be expressed in any convenient units, e.g., in weight, weight percent or ppm (all measured in dry weight, i.e., total dry weight pyro-Glu in the sample/total dry weight of the sample), or mole percent of peptide chains. It should be noted that as the mole percent of chains and weight percent of chains are related by the average molecular weight of the copolymer, it is possible to interconvert between these values if the average molecular weight is known, estimated or assumed. However, the precise value of the calculated mole percent of chains will depend on whether the average molecular weight value used is a number average molecular weight (Mn), weight average molecular weight (Mw) or peak average molecular weight (Mp). While Mw, Mp or Mn can be used in the calculations, it is preferable to use Mn. Whatever method is used to measure pyro-Glu in the batch or sample, and whatever units are used to express the measured pyro-Glu in the batch or sample, the concentration of pyro-Glu in the selected batch is between 2000 and 7000 ppm (mass pyro-Glu /mass total )×10 6 ).
[0015] The methods can also include selecting the batch or pharmaceutical preparation as suitable for sale or administration to a human when the concentration of pyro-Glu in the batch is within a predetermined range, e.g., 2000-7000 ppm.
[0016] The measuring step can comprise providing a value (e.g., in units such as ppm, percent of peptide chains) for the amount of pyro-Glu in the batch and optionally comparing the value to a reference value (e.g., a specification for commercial release of a copolymer product).
[0017] Where the value for the amount of pyro-Glu in a batch of glatiramer acetate has a preselected relationship with the reference value, the method can include classifying, selecting, accepting, discarding, releasing, or withholding a batch of glatiramer acetate; reprocessing a batch through a previous manufacturing step; processing a batch of glatiramer acetate into drug product, shipping the product from a batch of glatiramer acetate, moving the batch of glatiramer acetate to a new location; or formulating, labeling, packaging, selling, offering for sell, or releasing a batch of glatiramer acetate into commerce.
[0018] Also described herein is a method of analyzing a composition comprising glatiramer acetate for the presence or amount of pyro-Glu, the method comprising: digesting a sample of the composition with a peptidase or protease (e.g., pyroglutamate amino peptidase, an endopeptidase, and trypsin), comparing the digestion products to a pyro-Glu reference standard, and evaluating the amount of pyro-Glu in the sample relative to the reference standard, thereby analyzing a composition comprising glatiramer acetate. In some cases the digestion products are separated by a chromatographic process prior to comparing the digestion to a pyro-Glu reference standard. Thus, the comparison step can include a chromatographic method (e.g., liquid chromatography, particularly HPLC) to separate components and mass spectrometry (MS) analysis or UV absorbance analysis to detect the amount of various components.
[0019] In some cases the step of measuring pyro-Glu in the batch comprises: digesting a sample with a peptidase or a protease; isolating pyro-Glu present in the digested sample; and measuring the amount of isolated pyro-Glu. The isolating step can comprise a chromatographic method (e.g., liquid chromatography, particularly HPLC). The measuring step can comprise mass spectrometry (MS) analysis or UV absorbance analysis
[0020] The measuring step can comprise measuring UV absorbance (e.g., at 180-250 nm, 200 nm, or 210 nm). The isolating step can comprise a chromatographic method (e.g., liquid chromatography, particularly HPLC). The determining step can comprise mass spectrometry (MS) analysis. The isolating step can comprise HPLC and the measuring step can comprise UV absorbance analysis. The isolating step can comprise liquid chromatography and the measuring step can comprise mass spectrometry (MS) analysis.
[0021] In some cases, the pyro-Glu content of the copolymer or glatiramer acetate preparation is between 2000 to 7000 ppm, e.g., between 2500-6500 ppm, e.g., between 3000-6000 ppm, e.g., between 3300-4400 ppm. In some cases, the pyro-Glu content of the copolymer or glatiramer acetate preparation is less than 7000 ppm, e.g., less than 6000 ppm, less than 5000 ppm, less than 4000 ppm, less than 3000 ppm, or less than 2000 ppm.
[0022] As used herein, a “copolymer”, “amino acid copolymer” or “amino acid copolymer preparation” is a heterogeneous mixture of polypeptides comprising a defined plurality of different amino acids (typically between 2-10, e.g., between 3-6, different amino acids). A copolymer may be prepared from the polymerization of individual amino acids. The term “amino acid” is not limited to naturally occurring amino acids, but can include amino acid derivatives and/or amino acid analogs. For example, in an amino acid copolymer comprising tyrosine amino acids, one or more of the amino acids can be a homotyrosine. Further, an amino acid copolymer having one or more non-peptide or peptidomimetic bonds between two adjacent residues is included within this definition. A copolymer is non-uniform with respect to the molecular weight of each species of polypeptide within the mixture.
BRIEF DESCRIPTION OF THE FIGURES
[0023] FIG. 1 shows release of alanine from dipeptides upon HBr/acetic acid treatment. A=Ala=Alanine; E=Glutamic Acid; K=Lysine; Y=Tyrosine. All dipeptides were prepared at a concentration of 10 mM. Two dipeptides (A-A-NH2 and A-Y-NH2) were amidated at the C-terminus.
[0024] FIG. 2 is an LC-MS trace showing an unusual amino acid with residual mass of 111 Da (“X”) at the N-terminus of a peptide derived from trypsin-digested Copaxone®. Lys=Lysine; Ala=Alanine.
[0025] FIG. 3 shows the structure of L-pyro Glutamic Acid (pyro-Glu) Glatiramer Acetate (GA).
DETAILED DESCRIPTION OF THE INVENTION
[0026] Other than molecular weight and amino acid composition, which are specified in the approved label for the product, the label and other available literature for Copaxone® does not provide detailed information about the physiochemical characteristics of the product. Based on detailed characterization of the product and process kinetics, the inventors have unexpectedly found a signature component of GA, L-pyro-Glutamic Acid (pyro-Glu) GA, that can be evaluated to assess the GA manufacturing process and product quality. In particular, evaluation of pyro-Glu content can identify differences in materials that are not observed by looking at molar mass and amino acid composition alone. By evaluating the pyro-Glu content of a sample of a copolymer, e.g., GA, one can identify non-conforming copolymer compositions. Accordingly, pyro-Glu content can be used to evaluate product and process quality for GA.
[0027] The production of GA entails both polymerization of amino acids and partial depolymerization of the resulting peptides. It has now been found that depolymerization is highly specific and non-stochastic and occurs to a disproportionately high extent to the N-terminal side of glutamate residues. Indirectly, this results in pyro-Glu GA as a signature structural characteristic of GA, surprisingly occurring primarily as a consequence of depolymerization. Pyro-Glu is present in GA in a range of 2000-7000 ppm and can be assessed to identify or evaluate GA and its method of manufacture, and/or to evaluate the quality or suitability of a GA product for pharmaceutical use.
Methods for Manufacture of Glatiramer Acetate
[0028] Generally, the process for the manufacture of glatiramer acetate includes three steps:
Step (1): polymerization of N-carboxy anhydrides of L-alanine, benzyl-protected L-glutamic acid, trifluoroacetic acid (TFA) protected L-lysine and L-tyrosine (collectively referred to as NCAs) to result in a protected copolymer, Step (2): depolymerization and benzyl deprotection of the protected copolymer using hydrobromic acid in acetic acid, and Step (3): deprotection of the TFA-protected lysines on the product copolymers followed by purification and drying of the isolated drug substance.
[0032] In Step (1) of the manufacturing method, the NCAs are co-polymerized in a predetermined ratio using diethylamine as an initiator. Upon consumption of the NCA components, the reaction mixture is quenched in water. The resulting protected polymer (Intermediate-1) is isolated and dried. In Step (2), the protected polymer (Intermediate-1) is treated with anhydrous 33% HBr in acetic acid (HBr/AcOH). This results in the cleavage of the benzyl protecting group on the glutamic acid as well as cleavage of peptide bonds throughout the polymer, resulting in a partially depolymerized product (Intermediate-2) with a reduced molecular weight relative to the parent Intermediate-1 polymer. After the reaction is quenched with cold water, the product polymer is isolated by filtration and washed with water. The Intermediate-2 material is dried before proceeding to Step (3). In Step (3), Intermediate-2 is treated with aqueous piperidine to remove the trifluoroacetyl group on the lysine. The resulting copolymer (Intermediate-3) is subsequently purified using diafiltration/ultrafiltration and the resulting acetate salt dried to produce Glatiramer Acetate drug substance.
[0033] Methods for the manufacture of glatiramer acetate have been described in the following publications: U.S. Pat. No. 3,849,550; WO 95/031990 and US 2007-0021324.
Process Chemistry of Synthetic Method and Structural Characterization of GA
[0034] By studying the polymerization/depolymerization chemistry using model peptide compounds to model the synthetic process for producing GA, the inventors have found that there are certain rules associated with the chemistry. By developing an understanding of these rules, it is apparent that GA is not a stochastic, or random, mixture of peptides. Rather, there are certain attributes that are conserved from batch-to-batch and can be measured in order to monitor and evaluate process and batch quality.
[0035] Specifically, study of the kinetics of the depolymerization step of the GA manufacturing process using model peptide compounds revealed that Step 2 depolymerization occurs to disproportionately high levels on the N-terminal side of glutamate residues. In model compounds, the only appreciable cleavage was on the N-terminal side of glutamate residues ( FIG. 1 ). In the manufacturing process of Glatiramer Acetate, cleavage occurs at all residues, but with a bias towards the N-terminal side of glutamate residues. Further, a modified amino acid, identified as pyro-glutamic acid (pyro-Glu), was found in tryptic peptides of Copaxone® samples. Analysis of aliquots removed from the depolymerization step at various time points and then further processed to produce GA revealed that the amount of pyro-Glu at amino termini increases as the depolymerization time increases. Thus, the level of pyro-Glu in the final GA product is surprisingly primarily a consequence of the depolymerization kinetics and is not accounted for solely by the polymerization chemistry. From this understanding of the chemistry of GA synthesis, and from characterization of the resulting product, it has thus been discovered that pyro-Glu is a signature structural characteristic of glatiramer acetate. The formation of pyro-Glu results from: (1) parameters relating to the polymerization reaction, as well as, surprisingly and unexpectedly, (2) parameters related to the de-polymerization reaction. Accordingly, pyro-Glu can be evaluated and monitored in the manufacture of GA (including in the final drug substance or drug product) in order to, e.g., (i) identify GA, (ii) assess the quality of GA (e.g., of a GA batch), and/or (iii) assess or confirm the quality of the GA manufacturing process.
[0000] Methods of Measuring pyro-Glu
[0036] Because pyro-Glu is formed during the GA manufacturing process, its presence and level provide useful information regarding GA chemistry and product quality.
[0037] Certain methods are described herein for measuring pyro-Glu content in a composition that includes GA. However, it is understood that other methods to measure pyro-Glu can also be used.
[0038] One analytical method developed and described herein for the measurement of pyro-Glu content is based on enzymatic cleavage of an N-terminal pyroglutamate residue using pyroglutamate aminopeptidase (e.g., from thermophilic archaebacteria, Pyrococcus furiosus). The amount of pyro-Glu in the resulting enzymatic hydrolysate can be analyzed by a suitable technique, such as reverse phase liquid chromatography, to determine the ppm or w/w % of pyro-Glu in a GA sample. This method does not require knowing the mean chain length or average molecular weight of the GA in the composition. Accordingly, ppm or w/w% of pyro-Glu Glu is a preferred expression of the amount of pyro-Glu in a batch or a sample of copolymer, e.g., GA.
[0039] Various methods can be used to determine the percentage of peptide chains bearing pyro-Glu in a GA sample. A determination of mole % or percent of chains bearing pyro-Glu requires a determination of average molecular size or mean chain length. Molecular size can be evaluated e.g., by SEC MALLS (size exclusion chromatography with multiple angle laser light scattering). Mean chain length can be computed e.g., by labeling (e.g., with a radioactive or fluorescent label) the free amino termini with a molecule which can be directly quantified. One analytical method developed and described herein for measuring the percentage of peptide chains bearing pyro-Glu involves combining quantitative Edman degradation with enzymatic removal of pyro-Glu. Such an analysis can entail: 1) quantifying the N-terminal amino acids in a sample of GA before treatment to remove pyro-Glu; and 2) quantifying the N-terminal amino acids in a sample of GA after treatment to remove pyro-Glu.
EXAMPLES
Example 1
Depolymerization Kinetics of Glatiramer Acetate Method of Manufacture
[0040] To investigate the depolymerization kinetics, the reaction of various dipeptide model compounds with HBr/AcOH was investigated. FIG. 1 shows release of alanine from dipeptides upon HBr/acetic acid treatment as performed in Step 2 of the manufacturing process. All dipeptides were prepared at a concentration of 10 mM. Two dipeptides (A-A-NH2 and A-Y-NH2) were amidated at the C-terminus. As shown in FIG. 1 , release of alanine was only observed for A-E(OBn), indicating that dipeptides with Glu(OBn) in the C-terminal position demonstrate the most cleavage over the course of 24-48 h reaction times as compared to dipeptides without Glu in the C-terminal position. Thus, depolymerization occurs to an appreciable extent only on the N-terminal side of glutamate residues in these model systems. In the actual manufacturing process for Glatiramer Acetate, cleavage occurs at all residues, but still shows a strong bias for the N-terminal side of glutamate residues.
Example 2
Presence of N-Terminal Pyro-Glu Structures
[0041] Trypsin digestion of Copaxone® followed by LC-MS analysis identified expected peptides containing each of the amino acids A, E, K and Y. In addition, unexpected peptides were also found. An unusual amino acid (m/z 111) with residual mass of 111 Da was observed at the N-terminus of several such unexpected peptides derived from trypsin-digested Copaxone® (labeled as “X”, FIG. 2 ). From LC-MS/MS analysis it was determined that the unusual amino acid is pyro-Glu, formed by cycling of N-terminal glutamic acid to form pyro-glutamic acid losing a water molecule [111 Da=129 Da (Glutamic acid residue)−18 Da (H2O)]. FIG. 3 shows the structure of L-pyro Glutamic Acid (pyro-Glu) GA.
Example 3
Evaluation of Pyro-Glu Content on a Weight Basis
[0042] This example describes a method for evaluating pyro-Glu content in a copolymer composition.
[0043] An analytical method developed for the pyro-glutamate content assay is based on enzymatic cleavage of a N-terminal pyro-glutamate residue using pyro-glutamate aminopeptidase (from thermophilic archaebacteria, Pyrococcus furiosus). Pyro-glutamate in the resulting enzymatic hydrolysate is isolated by reverse phase liquid chromatography followed by detection at 200 nm using a reference standard curve prepared with known concentrations of L-Pyro-glutamate. Neurotensin (a commercially available polypeptide having 100% pyro-glutamate at the N-terminus) is assayed as a control to ensure the acceptability of the digestion and adequacy of the HPLC separation. The chromatographic analysis is performed using a Waters Atlantis C18 HPLC column and an isocratic mobile phase consisting of 100% Water, adjusted to pH 2.1 with phosphoric acid. Samples and Standards are held at 2-8° C. The peak corresponding to the pyro-glutamate moiety elutes at a retention time of approximately 12 minutes. The direct measure of pyro-glutamate content is on a w/w basis and the results are expressed as ppm (microgram/gram).
Example 4
Evaluation of Pyro-Glu Content on a Percentage of Peptide Chains Basis
[0044] The percentage of peptide chains in a sample of GA bearing pyro-Glu can be measured as an alternative to measuring the amount of pyro-Glu in a sample of GA. The percentage of peptide chains bearing pyro-Glu can be determined by combining quantitative Edman degradation with enzymatic removal of pyro-Glu. Thus, the analysis entails: 1) quantifying the N-terminal amino acids in a sample of GA before treatment to remove pyro-Glu; and 2) quantifying the N-terminal amino acids in a sample of GA after treatment to remove pyro-Glu.
[0045] An Edman degradation reaction was used to quantify the N-terminal amino acids in a sample of GA before and after treatment with pyroglutamate aminopeptidase (PA) to remove pyro-Glu. This reaction was performed manually to avoid quantitative limitations of automatic N-terminal peptide sequencers. The results of this analysis are presented in the table below.
[0000]
TABLE 1
N-terminal Amino Acid
nmol N-terminal amino acid
Before PA Treatment
After PA Treatment
Amino Acid
(st. dev)
(st. dev)
Ala
25.1
(0.6)
51.7
(0.5)
Glu
7.8
(0.3)
15.7
(0.1)
Lys
9.0
(0.2)
20.2
(0.8)
Tyr
6.5
(0.1)
10.5
(0.2)
Total
48.4
98.1
[0046] As can be seen in Table 1, above, the N-terminal amino acid concentration increased from 48.4 to 98.1 nmol after PA treatment. This is because removal of pyro-Glu permits detection of peptides that could not previously have been detected by Edman degradation. The percentage of chains bearing pyro-Glu can be calculated as follows: % chains capped by pyroglutamate=(Pafter−Pbefore)/Pafter×100%. In this calculation, Pbefore and Pafter are the concentrations of N-terminal amino acids with and without PA treatment, respectively. In this example, 51% of the polymer chains were capped by pyroglutamate.
Example 5
Pyro-Glu Ccontent can Distinguish Glatiramer Acetate
[0047] Using the method described in Example 3, the pyro-Glu content of commercial Copaxone® was compared to several other copolymer samples. A sample of glatiramer acetate (M-GA) prepared according to the method described in U.S. Pat. No. 3,849,550 was evaluated for pyro-Glu content. Table 2, below, provides the results of the analysis of a number of compositions, this sample conforms to the range found for pyro-Glu content from a sampling of Copaxone® lots, or between 2500-6500 ppm.
[0000]
TABLE 2
Analysis of Samples
Analysis of Samples
Molecular
weight (Mp)
Amino acid composition
P-Glu content
Sample
(Da)
(avg. molar fraction) 2
(ppm)
Copaxone ®
5,000-9,000 1
0.141 L-Glutamic acid
2500-6500 ppm 4
0.427 L-alanine
0.095 L-tyrosine
0.338 L-lysine
Glatiramer
8407
(conforms) 3
4900 ppm
acetate
(conforms)
(conforms)
sample
(M-GA)
Deviating
6579
(conforms) 3
8200 ppm
sample A
(conforms)
(fails)
Deviating
4808
(conforms) 3
7500 ppm
sample B
(fails)
(fails)
1 Molecular weight range specified in Copaxone ® product label and prescription information
2 Average molar fraction target specified in Copaxone ® product label and prescription information
3 Conforms relative to specification range based on label target plus allowance for manufacturing and measurement variability
4 Range is 75%/125% of Copaxone min/max for 30 commercial samples
[0048] To test the ability of pyro-Glu content to distinguish glatiramer acetate from non-conforming copolymers, two control copolymers were tested. The control copolymers were made with deliberate and specific deviations in the timing of NCA addition or in the duration of step 2. As shown in Table 1, both deviating samples A and B were outside of the range for pyro-Glu content determined for Copaxone®. Sample A was within the range for Copaxone® molar mass and amino acid composition while Sample B failed molar mass but conformed in amino acid composition. This data shows that evaluation of pyro-Glu content can identify differences in materials and process not observed by looking at molar mass and amino acid composition alone and illustrates the ability of pyro-Glu measurement to identify non-conforming copolymer. Accordingly, pyro-Glu content can be used to evaluate product and process quality for glatiramer acetate. | Methods for analyzing, selecting, characterizing or classifying compositions of a co-polymer, e.g., glatiramer acetate are described. The methods entail analysis of pyro-glutamate in the composition, and, in some methods, comparing the amount of pyro-glutamate present in a composition to a reference standard. | 2 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to a pultrusion die with removable and replaceable inserts and a process for making pultruded parts using the die that incorporates these inserts.
[0002] Processes are known for producing a fiber-reinforced composite by drawing fibers into a pultrusion die, impregnating the fibers with resin, and simultaneously forming and curing the structure in a heated die. (See Encyclopedia of Polymer Science and Engineering, 2 nd Edition, Vol. 4, John Wiley & Sons, New York, pp. 1-28 (1986).)
[0003] Thermoplastic pultrusions are known in the art. For example, Hawley in U.S. Pat. No. 4,439,387, incorporated herein by reference, teaches the extrusion of molten thermoplastic resin material through a die which imbeds the fibers. In U.S. Pat. No. 4,559,262, Cogswell et al., incorporated herein by reference, discloses a fiber-reinforced composition that is obtained by drawing a plurality of fibers continuously through an impregnation bath, which is a static melt of a thermoplastic polymer of sufficiently low molecular weight (resulting in lower melt viscosity) to adequately wet the fibers. In, U.S. Pat. No. 5,891,560, Edwards et al., incorporated herein by reference, discloses the use of a repolymerizable and depolymerizable thermoplastic polyurethane resin to achieve complete impregnation of a high molecular weight thermoplastic resin into a fiber bundle by pultrusion. Similarly, in U.S. Pat. No. 5,911,932 Dyksterhouse discloses a pultrusion process wherein the fiber bundle is preheated sufficiently above the temperature of the resin bath to create localized reduction in viscosity, thereby allowing more efficient impregnation of a variety of thermoplastic resins into the fiber bundle.
[0004] Pultrusion profiles are determined by the configuration of the pultrusion die. Every unique die forms a unique profile. Consequently, if a change in profile is desired, the die either needs to be replaced and the glass rovings restrung or entirely separate pultruders are required. The process of replacing the die and restringing the glass is time consuming and complicated, thereby adding significantly to the cost of making pultruded composites. It would therefore be an advantage to have a single die capable of making multiple profiles quickly and efficiently.
SUMMARY OF THE INVENTION
[0005] A modular pultrusion die comprising the following elements a-f communicating with each other in the order listed:
a) a fiber preheat station section containing inlets for the passage of fiber bundles; b) a fiber infeed section c) an resin infeed and impregnation section; d) a reduction section; e) a shaping and consolidation section that supports one or more removable and replaceable consolidation inserts; and f) a cooling section that supports one or more removable and replaceable consolidation inserts.
[0012] In a second the aspect the present invention is a modular pultrusion die comprising the following elements a-f communicating with each other in the order listed:
a) a fiber preheat station section containing inlets for the passage of fiber bundles; b) a fiber infeed section containing that supports one or more removable and replaceable fiber infeed inserts; c) an resin infeed and impregnation section; d) a reduction section; e) a shaping and consolidation section; and f) a cooling section.
[0019] In a third aspect, the present invention is a process of changing profiles in a modular pultrusion die comprising the steps of:
a) pultruding fiber through a pultrusion die containing any or all of the following removable and replaceable inserts: i) one or more consolidation inserts ii) one or more cooling inserts; and iii) one or more fiber infeed inserts; b) stopping the pultruding of fiber; c) removing any or all of the inserts and replacing the removed inserts with other inserts; and d) restarting the pultrusion process.
[0024] The present invention addresses a need in the art of pultrusion by providing a fast and cost-effective way of changing pultruded profiles of fiber architecture.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 illustrates a cut-out section of a modular pultrusion die.
[0026] FIG. 2 illustrates a cut-out section of a mandrel attached to the impregnation section.
DETAILED DESCRIPTION OF THE INVENTION
[0027] Referring now to FIG. 1 , which depicts a cut-out section of the preferred modular pultrusion die of the present invention, fiber bundle and/or other form of fibrous reinforcement such as continous strand mat or woven mat (hereinafter fibers) is pulled through a fiber preheat station ( 14 ), which contains a heater such as an infrared ceramic heater or heated pins. Fibers may be composed of any of a number of different types of materials including glass, carbon, aramid fibers, ceramics, and various metals. The preheat station ( 14 ) is at least sufficiently hot to remove any water present in the fibers. Depending on the nature of the resin used, it may be desirable to preheat the fiber at or above the processing temperature of the resin, preferably not more than about 200 K higher, more preferably not more than about 100 K higher, and most preferably not more than 50 K higher than the processing temperature of the resin.
[0028] The fibers are then pulled through a fiber infeed section ( 16 ) that is optionally adapted to contain interchangeable inserts to control and position the fibers and provide a way to feed different kinds of architecture (for example, rovings, continuous strand mat and woven mat) into the pultruded profile. The fibers are then fed through a resin infeed and impregnation section ( 18 ). In the resin infeed portion, resin melt is fed through a heated resin inlet port ( 30 ) then split through a series of resin feed ports ( 32 ) through slots onto the fiber bundles. The melt is preferably prepared by extruding the resin through a heated extruder, which melts the resin by way of shear and heat. The impregnation portion contains one or more series of undulating channels ( 18 a ) or impregnation pins to promote efficient wet out and impregnation of the fibers with the resin melt. The resin infeed and impregnation section ( 18 ) is preferably maintained above the melting point of the resin.
[0029] The impregnated fibers ( 10 a ) exit the resin infeed and impregnation section ( 18 ) then pass through a reduction section ( 20 ) to draw the multiple impregnated fibers ( 10 a ) close together, then through a consolidation die ( 22 ) that supports a removable and replaceable consolidation insert ( 24 ), which is preferably a split insert. The reduction section ( 20 ) optionally contains a removable and replaceable mandrel insert ( 26 ) supported by the resin infeed and impregnation section ( 18 ) as shown in FIG. 2 . The consolidated fiber ( 10 b ) then passes through a cooling section ( 24 ) containing an interchangeable cooling insert ( 28 ), which can be split.
[0030] The fibers preferably constitute at least about 30 volume percent, more preferably at least about 40 volume percent, and most preferably at least about 50 volume percent of the total volume of the completed fiber-reinforced composite article, and the reinforcing fibers extend substantially through the length of the composite. The pultruded sections can be cut to any desired length, from millimeters to kilometers, and further shaped, formed, or joined using techniques well known in the art, including thermoforming, hot stamping, and welding.
[0031] Examples of resins suitable to make pultruded composites using the modular pultrusion die of the present invention include thermoplastics such as polystyrene, polyvinyl chloride, ethylene vinyl acetate, ethylene vinyl alcohol, polybutylene terephthalate, polyethylene terephthalate, acrylonitrile-styrene-acrylic, ABS (acrylonitrile-butadiene-styrene), polycarbonate, polypropylene, polyethylene, polyurethane, and aramid resins, and blends thereof. Polypropylene and depolymerizable and repolymerizable engineering thermoplastic polyurethanes (disclosed by Edwards et al. in U.S. Pat. No. 5,891,560, starting at column 4, lines 36 through column 6, line 28) are especially preferred resins.
[0032] The use of interchangeable inserts provides a way for a single die unit to produce multiple profiles, thereby reducing the cost of multiple dies. The specific use of the interchangeable split inserts provides a simple way to remove and replace consolidation and cooling inserts without removing glass from the die, thereby saving hours or even days of down time. Furthermore, the use of interchangeable inserts in the glass infeed allows great flexibility is designing the glass architecture.
[0033] Interchangeability of inserts is accomplished by fabricating a standard insert shape which the die is adapted to receive. This concept is not unlike changing the nozzle on a cake icing bag to make different shaped streams of icing.
[0034] The modular pultrusion die of the present invention eliminates the need for a new pultrusion unit any time a change in a shape of a pultruded profile is desired. All that is required is a single unit with removable and replaceable dies. | A modular pultrusion die containing removable and replaceable inserts ( 24, 26, 28 ) is described. The use of small removable and replaceable subunits in a pultrusion die allows for a variety of pultruded profiles to be formed more rapidly and substantially less costly than existing non-modular dies. | 1 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a fingerprint authentication system, especially a secure registration-free fingerprint authentication method and system based on local features.
[0002] With the increasingly popular application of biometrics in real life, more attention has been drawn to security and privacy problems caused thereby. Investigations show that publics' concern about the risk of identity information leakage and thus potential risk of information security have prevented extensive acceptance of the biometrics, especially fingerprint authentication. Theoretically, any biometric system may face a possibility of being attacked. The security of biometric templates is a key factor for preventing such attacks. Therefore, a secure fingerprint authentication system, in which the templates are securely protected from being obtained easily by attackers, is attracting increasing attention.
[0003] Fuzzy commitment scheme is a kind of biometric encryption technology capable of protecting both biometric information and user keys. This scheme can protect the biometric templates from being stolen as well as provide a convenient way for key storage. This scheme was proposed by Juels et al. in 1999 (Ari Juels and Martin Wattenberg. A fuzzy commitment scheme. In Proc. 6 th ACM Conf. Comput. Commun. Secur., pages 28-36. ACM Press, 1999). It can be applied to all fuzzy information or biometric traits that are in compliance with its requirement regarding Hamming metrics. As hamming metrics is employed, this scheme was initially applied mostly to iris instead of fingerprints represented by minutiae sets. Secure Sketch, a kind of key-generation technology, was proposed by Dodis et al. in 2004 (Yevgeniy Dodis, Leonid Reyzin, and Adam Smith. Fuzzy extractors: How to generate strong keys from biometrics and other noisy data. In Advances in Crypology-Eurocrypt, volume 3027, pages 523-540. Springer-Verlag, 2004). A Fuzzy Extractor was also proposed in this paper, trying to convert random biometric data to stable keys that can be applied in any encryption environment, so as to enable reliable and secure user identity authentication. According to the secure sketch technique, some public information is extracted from the biometrics. This operation can tolerate a certain degree of errors. Once a data similar to the template data is input, the public information can be used to perfectly reconstruct the template data. However, the public information alone is not enough for reconstruction. The Fuzzy Extractor extracts an approximately uniformly-distributed random data R from input biometric data. Then R can be applied as a key to any encryption environment. PinSketch is a typical secure sketch technology which operates in set metric spaces. Wrap-around secure sketch is another kind of secure sketch technology operating in Euclidean space. It was proposed by Golic et al. at 2008 (Golic, J. D.; Baltatu, M.; “Entropy Analysis and New Constructions of Biometric Key Generation Systems,” Information Theory, IEEE Transactions on, vol. 54, no. 5, pp. 2026-2040, May 2008. doi: 10.1109/TIT.2008.920211).
[0004] A major factor determining the performance and security of a fingerprint encryption system is the selection of feature. Currently, the minutia, which is the most stable and robust feature of the fingerprint, is adopted in most systems. However, the minutia is a global feature, which needs registration during application. However, the registration in the fingerprint encryption system is still a difficult problem in that: 1) the fingerprint encryption system is aimed to protect the minutiae from leakage, so minutiae information can no longer be used for registration, and other effective features need to be found; 2) it is difficult to detect a stable feature suitable for registration in a fingerprint image, (e.g., the singular point is unstable and can only be used in registration of rigid transformation.)
SUMMARY OF THE INVENTION
[0005] In light of the foregoing, the present invention provides a secure registration-free fingerprint authentication method and system based on local features.
[0006] The secure registration-free fingerprint authentication method based on local features comprises:
[0007] extracting descriptor features and local structure features of fingerprint minutiae from an input fingerprint image;
[0008] performing quantization and feature selection with respect to the features of the fingerprint minutiae; and
[0009] encrypting the selected features and then decrypting the encrypted features to obtain the fingerprint image.
[0010] The present invention adopts the local features to construct the secure fingerprint authentication system, thus avoiding complex registration in encryption domain. The present invention improves the performance and security of the system, and meanwhile lowers the risk of the system being attacked.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 illustrates an overview diagram of a registration-free fingerprint encryption system based on local features.
[0012] FIG. 2 illustrates a schematic diagram of a descriptor feature of a minutia.
[0013] FIG. 3 illustrates a schematic diagram of a structure feature of a minutia.
[0014] FIG. 4 illustrates a schematic diagram for quantization and selection of the descriptor features of the minutiae.
[0015] FIG. 5 illustrates an operation flow of an inner-layer encryption unit.
[0016] FIG. 6 illustrates an operation flow of an inner-layer decryption unit.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0017] The present invention will be described with reference to the accompanied drawings. As shown in FIG. 1 , descriptor features and minutiae local structure features of minutiae are extracted from a fingerprint image. During encryption, quantized descriptor features of the minutiae are encrypted with the fuzzy commitment scheme, and the local structure features of the minutiae are encrypted with the wrap-around secure sketch. Auxiliary data obtained by the two encryptions is then stored for decryption. The foregoing process is called inner-layer encryption. The code obtained by the encryption with the wrap-around secure sketch is then subject to outer-layer encryption with the PinSketch. Auxiliary data thus obtained is stored for decryption. During decryption, part of the auxiliary data is decrypted with the fuzzy commitment scheme, and another part of the auxiliary data is decrypted with the wrap-around secure sketch. Data obtained by the two inner-layer decryptions, together with outer-layer auxiliary data, can be used as input of PinSketch outer-layer decryption. If the outer-layer decryption successes, the code generated by the inner wrap-around encryption can be recovered.
[0018] The present invention may comprise the following operations:
(1) A fingerprint image is input and pre-processed to calculate an orientation field and detect minutiae. Descriptor features and local structure features of the minutiae are then extracted. (2) Each missing descriptor feature value of a certain minutia is predicted by averaging the descriptor feature values of corresponding locations of 5 minutiae neighbouring minutia, so as to obtain all descriptor feature values. (3) Quantization and feature selection are performed with respect to the minutiae. The descriptor features of the minutiae are quantized using Gray code to generate quantized descriptor feature vectors. Then relatively reliable values are selected from respective quantized descriptor feature vectors through Sequential Forward Float Selection (SFFS). (4) Inner-layer encryption: Let m Ti denote an i th minutia of a template fingerprint and m Ti q denote a vector obtained after the quantization and feature selection of the descriptor feature of the minutia corresponding to m Ti . Then the fuzzy commitment scheme is carried on. An error-correction code is selected to have a same length as that of a final descriptor vector. A code word c i is selected from the code book randomly. Then XOR is conducted on the error-correction code and the code word to get e i =m Ti q ⊕c i . Meanwhile, a hash value h(c i ) is calculated for c i , where h(•) denotes a certain hash function. Let l Ti denote the local structure feature of the minutia corresponding to m Ti , and secure sketch operation is performed on it using wrap-around construction, which is shown as equation (1):
[0000] ( y i ,z i )= SS wa ( l Ti ) (1)
Here, SS wa (•) denotes the secure sketch operation based on the wrap-around construction; y i denotes public auxiliary data (also called sketch data) obtained through the secure sketch operation; and z i denotes a code word generated during the secure sketch operation and to be applied for subsequent steps.
Auxiliary data {e i , h(c i ), y i } generated by the above inner-layer encryption is saved as template, and the codeword z i is input to a next-layer encryption as intermediate data.
(5) Outer-layer encryption: Let {z i } i=1 n denote all the code words generated by the above inner-layer encryption for all the minutiae. The code words are then subject to the PinSketch operation, as shown in equation (2).
[0000] P=SS ps ({ z i } i=1 n ) (2)
Here, SS ps (•) denotes the secure sketch operation based on the PinSketch, and P denotes auxiliary data generated by the PinSketch operation. (6) Store as the template all the auxiliary data, including {e i , h(c i ), y i } i=1 n and P, obtained through the inner-layer encryption and the outer-layer encryption. (7) Inner-layer decryption: Let s denote a total number of minutiae in a query fingerprint image, m Qj denote the ith minutia, {m Qj } j=1 s denote a final vector obtained after the quantization and feature selection of the respective descriptor features of all the minutiae {m Qj q } j=1 s , and {l Qj } j=1 s denote the respective local structure vectors of all the minutiae. First, exhaustive search is conducted for the auxiliary data {e i , h(c i )} i=1 n , which is then decoded using the fuzzy commitment scheme as follows: 1) XOR is conducted on a descriptor vector m Qj q corresponding to a jth minutia of a query fingerprint image and the auxiliary data {e i , h(c i )} corresponding to the i th minutia of the fingerprint template, i.e., c i ′=e i ⊕m Qj q .
[0028] 2) Then error correction is conducted on c i ′ using error-correction code algorithm, i.e., c i ″=Dec(c i ′). Here Dec(•) denotes the error-correction algorithm selected during the encryption.
3) Hash-check is conducted, wherein if hash(c i ″)=hash(c i ), the fuzzy commitment decoding successes; whereas if the hash-check fails, another decoding for the exhaustive search is conducted. 4) If the hash-check successes, the auxiliary data y i is decrypted using a corresponding local structure vector l Qj of the minutia of the query fingerprint by means of the wrap-around construction, i.e., z i ′=Rec wa (l Qj , y i ), where Rec wa (•, •) denotes the decoding algorithm of the wrap-around construction. z i ′ denotes a codeword generated by the decoding algorithm. Let p denotes a number of the code words obtained through this process, i.e., {z i ′} i=1 p . (8) Outer-layer decryption: {z i ′} i=1 p is decoded using the auxiliary data P through a PinSketch decoding algorithm, which is shown as equation (3):
[0000] { {circumflex over (z)} i } i=1 p =Rec ps ({ z i ′} i=1 p ,P ) (3)
Here Rec ps (•, •) denotes the PinSketch decoding algorithm, {{circumflex over (z)} i } i=1 p denotes the code words recovered thereby. If the decoding successes, the authentication is successful, and the code words that have been recovered can be used as keys.
[0032] The invention will be described in detail with reference to the accompanied drawings and embodiments.
[0033] FIG. 1 illustrates an overview diagram of a secure registration-free fingerprint encryption system based on local features, in which:
[0034] Image collection unit 1 is configured to collect a template fingerprint and a query fingerprint to generate a template fingerprint image and a query fingerprint image, respectively.
[0035] Feature extraction unit 2 is configured to be connected to the image collection unit 1 and extract fingerprint features of minutiae from the template fingerprint image and the query fingerprint image. The fingerprint feature of a certain minutia comprises a descriptor feature and a local structure feature of this minutia. The descriptor feature of the certain minutia refers to a vector consisting of respective differences between orientations of 76 sampling points distributed on four concentric circles centered at this minutiae and the orientation of this certain minutiae as shown in FIG. 2 . This vector is denoted by m Ti ={θ ij } j=1 76 . The local structure feature of the certain minutia comprises respective relative distances and relative angles between the certain minutia and its two closest neighbouring minutiae as shown in FIG. 3 . This feature is denoted by l Ti =(d i1 , d i2 , θ i1 , θ i2 , φ i1 , φ i2 ).
[0036] A minutiae descriptor quantization and feature selection unit 3 is configured to be connected to the feature extraction unit 2 and calculate missing values of the descriptor feature of the fingerprint minutiae obtained by the feature extraction unit 2 . Then the minutiae descriptor quantization and feature selection unit 3 quantizes the descriptor vectors using Gray code, and then selects relatively reliable elements from the quantized vectors by means of the sequential forward float selection (SFFS) method to obtain final vectors.
[0037] An inner-layer encryption unit 4 is configured to be connected to the minutiae descriptor quantization and feature selection unit 3 and encrypt the quantized descriptor features and local structures of the minutiae with fuzzy commitment construction and wrap-around construction, respectively, to obtain auxiliary data. The auxiliary data is stored into the auxiliary data storage unit 6 . Besides, the code words obtained during the inner-layer encryption of the local structure features of the minutiae are input as intermediate values to an outer-layer encryption unit.
[0038] The outer-layer encryption unit 5 is configured to be connected to the inner-layer encryption unit 4 and encrypt the code words input from the inner-layer encryption unit 4 by means of the PinSketch method to generate auxiliary data, which is input to an auxiliary data storage unit 6 .
[0039] The auxiliary data storage unit 6 is configured to be connected to the inner-layer encryption unit 4 and the outer-layer encryption unit 5 and store the auxiliary data produced by the inner-layer encryption unit 4 and the outer-layer encryption unit 5 .
[0040] An inner-layer decryption unit 7 is configured to be connected to the minutiae descriptor quantization and feature selection unit 3 and the auxiliary data storage unit 6 . The inner layer decryption unit 7 is configured to acquire from the minutiae descriptor quantization and feature selection unit 3 the quantized descriptor vectors and the local structure vectors of the minutiae of the query fingerprint, and acquire the auxiliary data from the auxiliary data storage unit 6 . Afterwards, exhaustive search is carried on, and decryption is conducted using fuzzy commitment and the wrap-around sketch, respectively. The code words obtained by the decryption are used for outer-layer decryption if the decryption successes.
[0041] An outer-layer decryption unit 8 is configured to be connected to the auxiliary data storage unit 6 and the inner-layer decryption unit 7 . The outer-layer decryption unit 8 is configured to acquire code words generated by the inner-layer decryption unit 7 , and acquire the auxiliary data from the auxiliary data storage unit 6 . Then decryption is conducted so using the PinSketch and an authentication result is output.
[0042] FIG. 4 illustrates a schematic diagram of the minutiae descriptor quantization and feature selection unit 3 . A missing feature value estimation unit 31 is configured to be connected to the feature extraction unit 2 . For a certain minutia located at the edge of the fingerprint image, its missing feature values is estimated by averaging the feature values of corresponding locations of 5 minutiae neighbouring certain minutia, so as to obtain all feature values. The feature value quantization unit 32 is configured to be connected to the missing feature value estimation unit 31 and quantize each descriptor feature value to a 5-bit binary string using the Gray code. A feature selection unit 33 is configured to be connected to the feature value quantization unit 32 and select relatively reliable values from the quantized descriptor feature vectors using the sequential forward float selection (SFFS) method.
[0043] FIG. 5 illustrates a schematic diagram of the inner-layer encryption unit 4 . Let m Ti denote an i th minutia of a template fingerprint and m T q denote a final vector obtained after the quantization and feature selection of the descriptor feature of the minutia corresponding to m Ti .
[0044] Let l Ti denote the local structure feature of the minutia corresponding to m Ti . A minutiae descriptor inner-layer encryption unit 41 adopting the Fuzzy Commitment construction is configured to be connected to the minutiae descriptor quantization and feature selection unit 3 . An error-correction code is selected to have a same length as that of the final descriptor vector. A code word q is selected from the code book randomly. Then XOR is conducted on the error-correction code and the code word to get e i =m Ti q ⊕c i . Meanwhile, a hash value h(c i ) is calculated for c i , where h(•) denotes a certain hash function. A minutiae local structure inner-layer encryption unit 42 is configured to be connected to the feature extraction unit 2 and perform PinSketch operation using the wrap-around construction, which is shown as equation. Here, SS wa (•) denotes the secure sketch operation based on the wrap-around construction; y i denotes public auxiliary data (also called sketch data) obtained through the secure sketch operation; and z i denotes a code word generated during the secure sketch operation and to be applied for subsequent steps.
[0045] Auxiliary data {e i , h(c i ), y i } generated by the above inner-layer encryption is saved as template, and the codeword z i is input to a next-layer encryption as intermediate data.
[0046] FIG. 6 illustrates a schematic diagram of an inner-layer decryption unit 7 . Let s denote a total number of minutiae in a query fingerprint image, m Qj denote the ith minutia, {m Qj } j=1 s denote a final vector obtained after the quantization and feature selection of the respective descriptor features of all the minutiae {m Qj } j=1 s , and {l Qj } j=1 s and denote the respective local structure vectors of all the minutiae. A minutiae descriptor inner-layer decryption unit 71 is configured to be connected to the minutiae descriptor quantization and feature selection unit 3 and the auxiliary data storage unit 6 . First, the minutiae descriptor inner-layer decryption unit 71 conducts exhaustive search on the auxiliary data {e i , h(c i )} i=1 1 , and decode the same using the fuzzy commitment scheme as follows:
1) XOR is conducted on a descriptor vector m Qj q corresponding to a jth minutia of the query fingerprint image and the auxiliary data {e i , h(c i )} corresponding to the ith minutia of the fingerprint template, i.e., c i ′=e i ⊕m Qj q . 2) Then error correction is conducted on c i ′ using error-correction code algorithm, i.e., c i ″=Dec(c i ′). Here Dec(•) denotes the error-correction algorithm selected during the encryption. 3) Hash-check is conducted, wherein if hash(c i ″=hash(c i ), the fuzzy commitment decoding successes; whereas if the hash-check fails, another decoding for the exhaustive search is conducted.
[0050] A minutiae local structure inner-layer decryption unit 72 is configured to be connected to the minutiae descriptor quantization and feature selection unit 3 and the auxiliary data storage unit 6 . If the hash-check by the minutiae descriptor inner-layer decryption unit 71 successes, the minutiae local structure inner-layer decryption unit 72 decrypts the auxiliary data y i using a corresponding local structure vector l Qj of the minutia of the query fingerprint by means of the wrap-around construction, i.e., z i ′=Rec wa (l Qj , y i ), where Rec wa (•, •) denotes the decoding algorithm of the wrap-around construction. z i ′ denotes a code word generated by the decoding algorithm. Let p denotes a number of the code words obtained through this process, i.e., {z i ′} i=1 p .
[0051] According to an embodiment, the foregoing solution can be applied to a secure fingerprint authentication system. The system conforms to the specifications of object-oriented programming methods and software engineering and is realized by C++ language on Windows XP SP2+Visual Studio 2005 platform. All the experiments are conducted on a personal computer with an Intel Core2 1.86G CPU.
[0052] The FVC2002 DB2 database, which is used in the second international fingerprint recognition competition, is selected for the experiment. This database includes 100×8=800 fingerprints. The first two fingerprint images of each finer are selected for test. In genuine test, the first image of each finger is taken as a template fingerprint, and the second image of the same finger is used as a query fingerprint. As a result, totally 100 “genuine” results are produced. Imposter test takes the first image of each finger as the template fingerprint, and the first fingerprint image of the other fingers are taken as the query fingerprint, totally 4950 “imposter” results are produced. The FAR (False Accept Rate) and the GAR (Genuine Accept Rate) are calculated to evaluate the performance of the system. The best result achieved in this embodiment is GAR of 92% at zero FAR.
[0053] In light of the foregoing, the secure fingerprint authentication system and method proposed in the present invention provide a solution to the security problems existing in conventional fingerprint authentication systems, and the user's fingerprint template information can be well protected. In addition, the authentication performance satisfies the requirement of practical applications.
[0054] The description above only intends to provide an explanation of the embodiments of the present invention rather than limit the scope thereof. Those skilled in the art can make various changes or substitutions within disclosure of the present invention. These changes and substitutions all fall within the scope of the invention. Therefore, the scope of the present invention shall be defined by the attached claims. | A secure registration-free fingerprint authentication method based on local structures comprising: extracting descriptor features and local structure features of fingerprint minutiae from an input fingerprint image; conducting quantization and feature selection with respect to the features of the fingerprint minutiae; and encrypting the selected features and then decrypting the encrypted features to obtain the fingerprint image. The method adopts local features for fingerprint authentication, thus avoiding the complex registration in encryption domain. The method lowers the risk of the fingerprint authentication being attacked and improves security. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to imidazo[1,2-a]pyridine derivatives, processes for their preparation, pharmaceutical compositions containing them and their use in the treatment of diseases mediated by phosphatidylinositol-3-kinase (PI3K), mammalian target of rapamycin (mTOR), Signal transducer and activator of transcription 3 (STAT 3), tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6) or a combination thereof. In particular these compounds can be used in the treatment of cancer and inflammation.
BACKGROUND OF THE INVENTION
[0002] Cancer can be defined as an abnormal growth of tissues characterized by a loss of cellular differentiation.
[0003] The phosphatidylinositol-3-kinase (PI3K) pathway plays an important role in cellular signaling. Phosphatidylinositol-3-kinases or phosphoinositol-3-kinases (PI3-kinases or PI3 Ks) are a family of related enzymes that are capable of phosphorylating the 3 position hydroxyl group of the inositol ring of phosphatidylinositol. The PI3K family is composed of Class I, II and Class III. The classification is based on primary structure, regulation and in vitro lipid substrate specificity. Class III PI3K enzymes phosphorylate PI alone while, Class II PI3K enzymes phosphorylate both PI and PI 4-phosphate [PI(4)P].
[0004] Class I PI3K enzymes phosphorylate PI, PI(4)P and PI 4,5-biphosphate[PI(4,5)P 2 ]. Class I PI3Ks are further divided into two groups, class Ia and class Ib, in terms of their activation mechanism. Class Ia PI3Ks include PI3K p110α, p110β and p110δ subtypes and are generally activated in response to growth factor-stimulation of receptor tyrosine kinases. The first two p110 isoforms (α and β) are expressed in all cells, but p110δ is primarily expressed in leukocytes. Class Ib enzymes consist of p110γ catalytic subunit that interacts with a p110 regulatory subunit. It is activated in response to G-protein coupled receptor systems and its expression appears to be limited to leukocytes and cardiomyocytes. Class Ia subtypes are considered to be associated with cell proliferation and carcinogenesis.
[0005] mTOR is a class IV PI-3 kinase family member with protein kinase activity, but lacks any lipid kinase activity. It regulates cell growth and metabolism in response to environmental cue hence inhibitors of mTOR may be useful in the treatment of cancer and metabolic disorders (Cell, 2006, 124, 471-484).
[0006] PI3K mediated signaling pathway plays a very important role in cancer cell survival, cell proliferation, angiogenesis and metastasis. The PI3K pathway is activated by stimuli such as growth factors, hormones, cytokines, chemokines and hypoxic stress. Activation of PI3K results in the recruitment and activation of protein kinase B (AKT) to the membrane, which gets phosphorylated at Serine 473 (Ser-473). Thus, phosphorylation of Ser-473 of AKT is a read-out/detector for the activation of the PI3K-mediated pathway. A cell-based ELISA technique can be used to study such activation.
[0007] AKT is known to positively regulate cell growth (accumulation of cell mass) by activating the mTOR serine threonine kinase. mTOR serves as a molecular sensor that regulates protein synthesis on the basis of nutrients. mTOR regulates biogenesis by phosphorylating and activating p70S6 kinase (S6K1), which in turn enhances translation of mRNAs that have polypyrimidine tracts. The phosphorylation status of S6K1 is a bonafide read-out of mTOR function.
[0008] Most tumors have an aberrant PI3K pathway (Nat. Rev. Drug Discov., 2005, 4, 988-1004). Since mTOR lies immediately downstream of PI3K, these tumors also have hyperactive mTOR function. Thus, most of the cancer types can be treated using the molecules that target PI3K and mTOR pathways.
[0009] The compounds that are PI3K and/or mTOR and/or STAT3 inhibitors, find use in the treatment of cancers. Compounds are used to reduce, inhibit, or diminish the proliferation of tumor cells, and thereby assist in reducing the size of a tumor.
[0010] Signal transducer and activator of transcription 3 also known as STAT3 is a transcription factor which in humans is encoded by the STAT3 gene. The protein encoded by this gene is a member of the STAT protein family. In response to cytokines and growth factors, STAT family members are phosphorylated by the receptor associated kinases, and then form homo- or heterodimers that translocate to the cell nucleus where they act as transcription activators. STAT3 mediates the expression of a variety of genes in response to cell stimuli, and thus plays a key role in many cellular processes such as cell growth and apoptosis. Constitutive STAT3 activation is associated with various human cancers and commonly suggests poor prognosis. It has anti-apoptotic as well as proliferative effects.
[0011] The compounds that are STAT3 inhibitors, find use in the treatment of cancers. These compounds are used to reduce, inhibit, or diminish the proliferation of tumor cells.
[0012] SF 1126 (Semaphore, Inc.) is a pan-PI3K inhibitor in phase I clinical trials. SF1126 is a covalent conjugate of LY294002 containing a peptide-based targeting group.
[0013] GDC-0941 (Piramed Ltd. and Genentech, Inc.) is a PI3K inhibitor and is in phase I clinical trials.
[0014] BEZ-235 (Novartis AG), which is currently in phase I/II clinical trials, inhibits all isoforms of PI3K and also inhibits the kinase activity of mTOR.
[0015] XL-765 (Exelixis Inc.) is also a dual inhibitor of mTOR and PI3K. The compound is in phase I clinical trials as an oral treatment for solid tumors.
[0016] PIK-75 (Astellas Pharma Inc.) is in preclinical studies. It is a PI3Kalpha inhibitor and inhibits p110α>200 fold more than plifo.
[0017] Inflammation is the response of a tissue to injury that may be caused by a biological assault such as invading organisms and parasites, ischemia, antigen-antibody reactions or other forms of physical or chemical injury. It is characterized by increased blood flow to the tissue, causing pyrexia, erythema, induration and pain.
[0018] Several proinflammatory cytokines, especially TNF-α and interleukins (IL-1β, IL-6, IL-8) play an important role in the inflammatory process. Both IL-1 and TNF-α are derived from mononuclear cells and macrophages and in turn induce the expression of a variety of genes that contribute to the inflammatory process. An increase in TNF-α synthesis/release is a common phenomenon during the inflammatory process. Inflammation is an inherent part of various disease states like rheumatoid arthritis, Crohn's disease, ulcerative colitis, septic shock syndrome, psoriasis, atherosclerosis, among other clinical conditions.
[0019] The first line of treatment for inflammatory disorders involves the use of non-steroidal anti-inflammatory drugs (NSAIDs) e.g. ibuprofen, naproxen to alleviate symptoms such as pain. However, despite the widespread use of NSAIDs, many individuals cannot tolerate the doses necessary to treat the disorder over a prolonged period of time as NSAIDs are known to cause gastric erosions. Moreover, NSAIDs merely treat the symptoms of disorder and not the cause. When patients fail to respond to NSAIDs, other drugs such as methotrexate, gold salts, D-penicillamine and corticosteroids are used. These drugs also have significant toxic effects.
[0020] Monoclonal antibody drugs such as Infliximab, Etanercept and Adalimumab are useful as anti-inflammatory agents, but have drawbacks such as route of administration (only parenteral), high cost, allergy induction, activation of latent tuberculosis, increased risk of cancer and congestive heart disease.
[0021] PI3K inhibitors are known in the art. For example, U.S. Pat. No. 6,403,588 describes phosphatidylinositol 3 kinase inhibitors useful as antitumor agents. Additionally, WO 2004/017950 describes phosphatidylinositol 3,5-biphosphate inhibitors as anti-viral agents.
SUMMARY OF THE INVENTION
[0022] The present invention provides imidazo[1,2-a]pyridine derivatives of formula (I):
[0000]
[0000] in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates,
wherein,
R a , R b and R d are independently selected from hydrogen, hydroxy, halogen, cyano, nitro, —COR 1 , —COOR 1 , —CONH 2 , —NR 1 R 2 , —C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl and —C 1 -C 8 alkoxy;
R c is halogen or heteroaryl;
R e is hydrogen, —C 1 -C 8 alkyl, —C 6 -C 14 aryl or heteroaryl;
Q is —SO 2 —, —C(O)NR 1 — or —C(S)NR 1 —;
[0023] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p -heterocyclyl, —(CR 1 R 2 ) p -heteroaryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 —, then R c is not halogen;
wherein each of the above alkyl, haloalkyl, alkoxy, cycloalkyl, aryl, heteroaryl and heterocyclyl are unsubstituted or substituted with one or more of the same or different groups selected from halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, haloalkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p -aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl.
[0024] The present invention also provides processes for producing compounds of formula (I).
[0025] The present invention further provides a pharmaceutical composition comprising a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof, or a pharmaceutically acceptable solvate thereof, in combination with a pharmaceutically acceptable excipient, carrier or diluent.
[0026] The present invention also provides a method of treating diseases mediated by PI3K and/or mTOR and/or STAT3 in a mammal comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0027] The present invention also provides a method of treating diseases mediated by TNF-α and/or IL-6 in a mammal comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0028] The present invention also provides a method of inhibiting the tumor cell growth, tumor cell proliferation or tumorigenesis in a mammal comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0029] The present invention also provides a method of treating cancer mediated by PI3K and/or mTOR and/or STAT3 comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0030] The present invention further provides a method of treating cancer comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0031] The present invention also provides a method of treating inflammatory conditions mediated by TNF-α and/or interleukin-6 (IL-6) comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0032] The present invention further provides a method of treating inflammatory conditions comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0033] The present invention further provides the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of diseases mediated by PI3K and/or mTOR and/or STAT3.
[0034] The present invention further provides the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of cancer.
[0035] The present invention further provides the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of diseases mediated by TNF-α and/or IL-6.
[0036] The present invention further provides the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of inflammatory conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 is a graph depicting effect of compound of Example 25 on DSS induced weight loss (%) in C57BL/6J mice. 5-ASA was used as positive control
[0038] FIG. 2 is a graph depicting effect of compound of Example 25 on DSS induced shortening of colon in C57BL/6J mice. 5-ASA was used as positive control
[0039] FIG. 3 is a graph depicting effect of compound of Example 25 on DSS induced decrease in haematocrit in C57BL/6J mice. 5-ASA was used as positive control
[0040] FIG. 4 is a graph depicting effect of compound of Example 25 on DSS induced rectal bleeding in C57BL/6J mice. 5-ASA was used as positive control
[0041] FIG. 5 is a graph depicting effect of compound of Example 25 on DSS induced colon bleeding in C57BL/6J mice. 5-ASA was used as positive control
[0042] FIG. 6 is a graph depicting effect of compound of Example 25 on DSS induced disease activity index in C57BL/6J mice. 5-ASA was used as positive control
DETAILED DESCRIPTION OF THE INVENTION
[0043] Listed below are definitions, which apply to the terms as they are used throughout the specification and the appended claims (unless they are otherwise limited in specific instances), either individually or as part of a larger group. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, as well as represents a stable compound, which does not readily undergo transformation such as by rearrangement, cyclization, elimination, etc.
[0044] As used herein, the term “alkyl” whether used alone or as part of a substituent group, refers to a saturated straight or branched chain hydrocarbon radical containing the indicated number of carbon atoms. For example, C 1 -C 8 alkyl refers to alkyl group having 1 to 8 (both inclusive) carbon atoms. In case of absence of any numerical designation, “alkyl” is a straight or branched-chain containing from 1 to 6 (both inclusive) carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylbutyl and 3-methylbutyl.
[0045] As used herein, the term “lower alkyl” whether used alone or as part of a substituent group, refers to the radical of saturated aliphatic groups, including straight or branched chain containing from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
[0046] Unless stated otherwise, the alkyl and lower alkyl groups as stated above can be unsubstituted or substituted with one or more of the same or different groups selected from halogen, oxo, carbonyl, carboxy, cyano, thioester, sulfonyl, nitro, acyl, acyloxy, cycloalkyl, aryl, heterocyclyl, heteroaryl, —OR x , —SR x , —NR y R z , —CONR y R z , —NR y COR z , —NR y CONR y R z , —NR y SOR z , —NR y SO 2 R z , —S(O) m R y and —S(O) n NR y R z , wherein R x is hydrogen, alkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl; wherein R y and R z are independently selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl and heterocyclyl; m is an integer from 0 to 2 and n is an integer from 0 to 1. Any kind of substituent present in substituted alkyl residues can be present in any desired position provided that the substitution does not lead to an unstable molecule.
[0047] As used herein, the term “alkenyl” whether used alone or as part of a substituent group, refers to a straight or branched chain hydrocarbon radical containing the indicated number of carbon atoms and at least one carbon-carbon double bond (two adjacent sp 2 carbon atoms). For example, C 2 -C 8 alkenyl refers to an alkenyl group having 1 to 8 (both inclusive) carbon atoms. Depending on the placement of double bond and substituents if any, the geometry of the double bond may be entgegen (E), or zusammen (Z), cis or trans. Examples of alkenyl include, but are not limited to, vinyl and allyl. Unless stated otherwise, the alkenyl groups can be unsubstituted or substituted with one or more of the same or different groups selected from halogen, hydroxy, carboxy, acetoxy, amino, cyano, nitro, alkyl, alkoxy, cycloalkyl, aryloxy, aryl, aralkyl and heterocyclyl.
[0048] As used herein, the term “alkynyl” whether used alone or as part of a substituent group, refers to a straight or branched chain hydrocarbon radical containing the indicated number of carbon atoms and at least one carbon-carbon triple bond (two adjacent sp carbon atoms). For example, C 2 -C 8 alkynyl refers to an alkynyl group having 1 to 8 (both inclusive) carbon atoms. Examples of alkynyl include, but are not limited to, ethynyl, 1-propynyl, 3-propynyl and 3-butynyl. Unless stated otherwise, the “alkynyl” may be unsubstituted or substituted with one or more of the same or different groups, selected from alkyl, halogen, hydroxy, carboxy, acetoxy, amino, cyano, nitro, cycloalkyl, alkoxy, aryloxy, aryl, aralkyl and heterocyclyl.
[0049] As used herein, the term “cycloalkyl” whether used alone or as part of a substituent group, refers to a saturated or partially unsaturated cyclic hydrocarbon radical including 1, 2 or 3 rings and including a total of 3 to 14 carbon atoms forming the rings. The term cycloalkyl includes bridged, fused and spiro ring systems. For example, C 3 -C 8 cycloalkyl refers to a cycloalkyl group having 3 to 8 (both inclusive) carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentene, adamantyl, norbornyl, bicyclo[2.1.0]pentane, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]hept-2-ene, spiro[3.3]heptane and 1,2,3,3a-tetrahydropentalene. Unless stated otherwise, the “cycloalkyl” may be unsubstituted or substituted with one or more of the same or different groups selected from halogen, hydroxy, alkoxy, oxo, alkyl, cycloalkyl, carboxy, acyl, acyloxy, amino, cyano, nitro, carbonyl, ester, ether, amide, imino, alkylthio, aryl and heterocyclyl.
[0050] As used herein, the term “alkoxy” whether used alone or as part of a substituent group, refers to an alkyl group as defined above attached via oxygen linkage to the rest of the molecule. Examples of alkoxy include, but are not limited to methoxy and ethoxy.
[0051] As used herein, the term “haloalkyl” refers to an alkyl group in which one or more hydrogen atoms are replaced by one or more halogen atoms. “Halo-C 1 -C 8 alkyl” groups have 1 to 8 carbon atoms, “halo-C 1 -C 6 alkyl” groups have 1 to 6 carbon atoms. Examples of haloalkyl include, but not limited to, mono-, di- or tri-fluoromethyl; mono-, di- or tri-chloromethyl; mono-, di-, tri-, tetra- or pentafluoroethyl; heptafluoropropyl; difluorochloromethyl and dichlorofluoromethyl.
[0052] As used herein, the term “acyl” refers to the group —C(O)R a , wherein R a is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, heterocyclyl and heterocyclylalkyl. Unless otherwise stated, the groups alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, heterocyclyl and heterocyclylalkyl can be unsubstituted or substituted with halogen, carboxy, cycloalkyl, cyano, amide, alkylthio, thioester, sulfonyl, nitro, haloalkyl, —OR x , —SR x , —NR y R z , —NR y COR z , —CONR y R z , —S(O) m R y , —S(O) n NR y R z , —NR y SOR z , —NR y SO 2 R z , wherein R x is hydrogen, alkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl; wherein R y and R z are independently selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and heterocyclyl; m is an integer from 0 to 2 and n is an integer from 0 to 1.
[0053] As used herein, the term “aryl” whether used alone or as part of a substituent group, refers to a monocyclic or polycyclic hydrocarbon group having 6 to 14 ring carbon atoms, in which the carbocyclic ring present has a conjugated n electron system. Examples of aryl include, but are not limited to, phenyl, naphthyl, biphenyl, fluorenyl and anthracenyl. Unless stated otherwise, the “aryl” may be unsubstituted or substituted with one or more of the same or different groups, such as halogen, alkyl, alkenyl, alkynyl, haloalkyl, hydroxy, alkoxy, haloalkoxy, cyano, nitro, acyl, carboxy, thiol, carbonyl, aryl, cycloalkyl, heteroaryl, heterocyclyl, —OR, —SR x , —NR y R z , —CONR y R z , —NR y COR z , —NR y CONR y R z , —NR y SOR z , —NR y SO 2 R z , —S(O) m R y , —S(O) n NR y R z , wherein R x is hydrogen, alkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl; R y and R z are independently selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl and heterocyclyl; m is an integer from 0 to 2 and n is an integer from 0 to 1.
[0054] The term “aryloxy” refers to the —O-aryl wherein the term aryl is as defined above. Exemplary aryloxy groups include, but are not limited to, phenoxy and naphthoxy.
[0055] As used herein, the terms “heterocyclyl” or “heterocyclic” whether used alone or as part of a substituent group, refers to a saturated, partially unsaturated, monocyclic or polycyclic ring system containing 1 to 10 carbon atoms and 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen and sulfur. Examples of heterocyclyl include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, azocinyl, dihydrofuranyl, dihydroisoxazolyl, tetrahydrofuranyl, piperazinyl, morpholinyl, oxazinyl, dihydro-pyridooxazinyl, tetrahydrothiopyranyl, dihydrobenzofuryl, tetrahydroquinoline, tetrahydroisoquinoline, benzoxazinyl, phenoxazinyl, phenothiazinyl and N-oxides thereof. Unless stated otherwise, the “heterocyclyl” or “heterocyclic” may be unsubstituted or substituted with one or more of the same or different groups, such as halogen, hydroxy, cyano, nitro, acyl, oxo, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, —OR x , —SR x , —C(O)R y —NR y R z , —CONR y R z , —NR y COR z , —NR y CONR y R z , —NR y SOR z , —NR y SO 2 R z , —S(O) m R y , —S(O) n NR y R z , aryl, cycloalkyl, heteroaryl wherein R x is hydrogen, alkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl; wherein R y and R z are independently selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl and heterocyclyl; m is an integer from 0 to 2 and n is an integer from 0 to 1.
[0056] As used herein, the term “heteroaryl” whether used alone or as part of a substituent group, refers to aromatic ring structure containing monocyclic or polycyclic ring system containing 1 to 10 carbon atoms and 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen and sulfur. Examples of heteroaryl include, but are not limited to, pyrrolyl, thienyl, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl, isoindolyl, benzoxazolyl, benzothiazolyl, indazolyl, quinolinyl, isoquinolyl, benzofurazanyl and purinyl. The oxidized form of the ring nitrogen and sulfur atom of the heteroaryl to provide N-oxide, sulfinyl or sulfonyl is also encompassed. Unless stated otherwise, the “heteroaryl” may be unsubstituted or substituted with one or more of the same or different groups, such as halogen, hydroxy, cyano, nitro, acyl, oxo, ester, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, —OR x , —SR x , —C(O)R y —NR y R z , —CONR y R z , —NR y COR z , —NR y CONR y R z , —NR y SOR z , —NR y SO 2 R z , —S(O) m R y , —S(O) n NR y R z , aryl, cycloalkyl, heteroaryl, heterocyclyl, wherein R x is hydrogen, alkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl; wherein R y and R z are independently selected from hydrogen, hydroxy, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and heterocyclyl; m is an integer from 0 to 2 and n is an integer from 0 to 1.
[0057] As used herein, the term “aralkyl” refers to an alkyl group substituted with an aryl or heteroaryl group, wherein the terms alkyl, aryl and heteroaryl are as defined above. Exemplary aralkyl groups include —(CH 2 ) p -phenyl, —(CH 2 ) p -pyridyl, wherein p is an integer from 1 to 6. The alkyl, aryl and heteroaryl in the said aralkyl group are as defined earlier.
[0058] As used herein, the term “heteroatom” refers to nitrogen, oxygen and sulfur. It should be noted that, unless stated otherwise, any heteroatom with unsatisfied valences is assumed to have a hydrogen atom to satisfy the valences. The ring heteroatoms can be present in any desired number and in any position with respect to each other provided that the resulting heterocyclic system is stable and suitable as a subgroup in a drug substance.
[0059] As used herein, the term “halo” or “halogen” unless otherwise stated refers to fluorine, chlorine, bromine, or iodine atom.
[0060] As used herein, the term “amino” refers to a group of formula —NH 2 , which may be optionally substituted with alkyl, alkenyl, alkynyl, aryl, heterocyclyl, or cycloalkyl wherein the terms alkyl, alkenyl, alkynyl, aryl, heterocyclyl and cycloalkyl are as defined herein above.
[0061] As used herein, the term “amide” means —C(O)NH—R′, wherein R′ is hydrogen, alkyl, aryl or aralkyl.
[0062] As used herein, the term “imino” refers to a group of formula ═N—R a , wherein R a is selected from hydrogen, hydroxy, alkyl and alkoxy. Examples of such imino radicals include, but are not limited to, ═NH, ═NCH 3 , ═NOH, and ═NOCH 3 .
[0063] As used herein, the term “oxo” refers to a ═O moiety.
[0064] As used herein, the term “sulfonyl” refers to a —SO 2 — group.
[0065] As used herein, the term “carboxy” or “carboxyl” refers to a group of formula —COOH; also referred to as a carboxylic acid group.
[0066] As used herein, the term “carbonyl” whether used alone or as part of a substituent group, refers to a group of formula —(C═O)—.
[0067] As used herein, the term “ester” refers to a group of formula —COOR a , wherein R a is an alkyl, cycloalkyl, aryl, aralkyl, heteroaryl or heterocyclyl as defined above.
[0068] As used herein, the term “ether” refers to a group of formula —R a OR a , wherein R a is independently selected from alkyl, cycloalkyl, aryl, aralkyl, heteroaryl or heterocyclyl as defined above.
[0069] As used herein, the term “thioester” refers to a group of formula —R a SCOR a , wherein R a is an alkyl, cycloalkyl, aryl, aralkyl, heteroaryl or heterocyclyl as defined above.
[0070] As used herein, the term “acyloxy” refers to a group of formula —O-acyl, wherein acyl is as defined above.
[0071] As used herein, the term “alkylthio” refers to an alkyl group, as defined herein, appended to the parent molecular moiety through a sulfur atom. Examples of alkylthio include, but are not limited, methylthio, ethylthio, tert-butylthio and hexylthio. As used herein, the term “pharmaceutically acceptable salts” refers to non-toxic salts of the compounds of present invention. Salts derived from inorganic bases include, but are not limited to, ammonium, calcium, lithium, magnesium, potassium, sodium. Salts derived from pharmaceutically acceptable organic bases include, but are not limited to salts of primary, secondary, and tertiary amines, substituted amines including [(tris(hydroxymethyl)aminomethane], trimethylamine salts, diethylamine salts; salts with amino acids such as lysine, arginine, guanidine and the like. Salts derived from pharmaceutically acceptable organic and inorganic acids include, but are not limited to acetate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, cinnamate, citrate, fumarate, glutamate, lactate, maleate, malonate, methanesulfonate, nitrate, oxalate, propionate, phosphate, p-toluenesulfonate, salicylate, succinate, sulfamate, sulfate, tartrate, hydrochloride, hydrobromide, hydrofluoride, hydroiodide, trifluoromethanesulfonate and valproate.
[0072] The term “N-oxide” as used herein refers to the oxide of the nitrogen atom of a nitrogen-containing heteroaryl or heterocycle. N-oxide can be formed in presence of an oxidizing agent for example peroxide such as m-chloro-perbenzoic acid or hydrogen peroxide.
[0073] As used herein, the term “solvate” describes a complex wherein the compound is coordinated with a proportional amount of a solvent molecule. Specific solvates, wherein the solvent is water, are referred to as hydrates.
[0074] As used herein, the term “pharmaceutically acceptable carrier” refers to a material that is non-toxic, inert, solid, semi-solid or liquid filler, diluent, encapsulating material or formulation auxiliary of any type which is compatible with a subject, preferably a mammal, more preferably a human, and is suitable for delivering an active agent to the target site without terminating the activity of the agent.
[0075] As used herein, the term “prodrug” refers to a compound, which upon administration to a subject undergoes chemical conversion by metabolic or chemical processes to yield a compound of the formula (I) or a salt and/or solvate thereof. The preferable prodrugs are Type I, those that are converted intracellularly, more preferably Type la where the cellular converting location is the site of therapeutic action. Various forms of prodrugs are well known in the art and are described in: (a) “Pro-drugs as Novel Delivery Systems,” by T. Higuchi and W. Stella, Vol. 14 of the A.C.S. Symposium Series, (b) Bioreversible Carriers in Drug Design, ed. Edward B. Roche, American Pharmaceutical Association and Pergamon Press, 1987 and (c) Design of Prodrugs, edited by H. Bundgaard, (Elsevier, 1985).
[0076] As used herein, the term “stereoisomer” is a general term used for all isomers of individual compounds that differ only in the orientation of their atoms in space. The term stereoisomer includes mirror image isomers (enantiomers), mixtures of mirror image isomers (racemates, racemic mixtures), geometric (cis/trans or E/Z) isomers, and isomers of compounds with more than one chiral center that are not mirror images of one another (diastereoisomers). The compounds of the present invention may have asymmetric centers and occur as racemates, racemic mixtures, individual diastereoisomers, or enantiomers, or may exist as geometric isomers, with all isomeric forms of said compounds being included in the present invention.
[0077] As used herein, the term “tautomer” refers to the coexistence of two (or more) compounds that differ from each other only in the position of one (or more) mobile atoms and in electron distribution, for example, keto-enol tautomers.
[0078] As used herein, the terms “treat” and “therapy” and the like refer to alleviate, slow the progression, prophylaxis, modulation, attenuation or cure of existing disease (e.g., cancer or inflammation).
[0079] The present invention also includes within its scope all isotopically labeled forms of compounds of formula (I), wherein one or more atoms of compounds of formula (I) are replaced by their respective isotopes. Examples of isotopes that may be incorporated into the compounds disclosed herein include, but are not limited to, isotopes of hydrogen such as 2 H and 3 H, carbon such as 11 C, 13 C and 14 C, nitrogen such as 13 N and 15 N, oxygen such as 15 O, 17 O and 18 O, chlorine such as 36 Cl, fluorine such as 18 F and sulphur such as 35 S.
[0080] Substitution with heavier isotopes, for example, replacing one or more key carbon-hydrogen bonds with carbon-deuterium bond may show certain therapeutic advantages, for example, longer metabolism cycles, improved safety or greater effectiveness.
[0081] Isotopically labeled forms of compounds of formula (I), can be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described above and in the subsequent Experimental section by using an appropriate isotopically labeled reagent instead of non-labeled reagent.
EMBODIMENTS
[0082] In one embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen, hydroxy, halogen, cyano, nitro, —COR 1 , —COOR 1 , —CONH 2 , —NR 1 R 2 , —C 1 -C 8 alkyl, halo-C 1 -C 8 alkyl and —C 1 -C 8 alkoxy;
R c is halogen or heteroaryl;
R e is hydrogen or —C 1 -C 8 alkyl;
Q is —SO 2 , —C(O)NR 1 or —C(S)NR 1 ;
[0083] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p heterocyclyl, —(CR 1 R 2 ) p heteroaryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 , then R c is not halogen;
wherein each of the above alkyl, haloalkyl, alkoxy, cycloalkyl, aryl, heterocyclyl and heteroaryl are unsubstituted or substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl group;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0084] In another embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 8 alkyl;
R c is halogen or heteroaryl;
R e is hydrogen or —C 1 -C 8 alkyl;
Q is —SO 2 , —C(O)NR 1 or —C(S)NR 1 ;
[0085] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p -heterocyclyl, —(CR 1 R 2 ) p -heteroaryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 , then R c is not halogen;
wherein each of the above alkyl, cycloalkyl, aryl, heterocyclyl and heteroaryl are unsubstituted or substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0086] In another embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is halogen or heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NH or —C(S)NH;
[0087] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p heterocyclyl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heterocyclyl, or heteroaryl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 , then R c is not halogen;
wherein each of the above alkyl, cycloalkyl, aryl, heteroaryl and heterocyclyl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, N-oxides, pharmaceutically acceptable solvates and prodrugs.
[0088] In another embodiment, the present invention provides compound of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is halogen or heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —C(O)NH or —C(S)NH;
[0089] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p — heterocyclyl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl or heteroaryl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
wherein each of the above alkyl, cycloalkyl, aryl and heteroaryl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, cyano, amino, nitro, alkoxy, —C 1 -C 6 alkyl and halo-C 1 -C 6 alkyl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0090] In another embodiment, the present invention provides compound of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is halogen or heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —C(O)NH or —C(S)NH;
[0091] R f is —(CR 1 R 2 ) p -heterocyclyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl or —C 6 -C 14 aryl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
wherein each of the above alkyl, aryl and heteroaryl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, cyano, amino, nitro, alkoxy, —C 1 -C 6 alkyl and halo-C 1 -C 6 alkyl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0092] In another embodiment, the present invention provides compound of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is halogen;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —C(O)NH or —C(S)NH;
[0093] R f is —(CR 1 R 2 ) p -heterocyclyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl or —C 6 -C 14 aryl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
wherein each of the above alkyl, aryl and heteroaryl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, cyano, amino, nitro, alkoxy, —C 1 -C 6 alkyl and halo-C 1 -C 6 alkyl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, N-oxides, pharmaceutically acceptable solvates and prodrugs.
[0094] In another embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NR 1 or —C(S)NR 1 ;
[0095] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —(CR 1 R 2 ) p -heterocyclyl, —(CR 1 R 2 ) p -heteroaryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
wherein each of the above alkyl, cycloalkyl, aryl, heterocyclyl and heteroaryl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0096] In another embodiment, the present invention provides compound of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NH or —C(S)NH;
[0097] R f is —C 1 -C 8 alkyl, —(CH 2 ) p —C 6 -C 14 aryl, —(CH 2 ) p — heterocyclyl, —(CH 2 ) p -heteroaryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
wherein each of the above alkyl, aryl, heterocyclyl and heteroaryl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, N-oxides, and their pharmaceutically acceptable salts and pharmaceutically acceptable solvates.
[0098] In another embodiment, the present invention provides compounds of formula (I), R a , R b and R d are independently selected from hydrogen and methyl;
[0000] R c is halogen or heteroaryl selected from pyridyl, quinolinyl, indolyl, pyrimidinyl and pyrrolyl wherein each of pyridyl, quinolinyl, indolyl, pyrimidinyl and pyrrolyl is optionally substituted with one or more halogen, —C 1 -C 6 -alkyl, —C 1 -C 6 -alkoxy, and halo-C 1 -C 6 -alkyl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NH or —C(S)NH;
[0099] R f is —C 1 -C 8 alkyl, —(CH 2 ) p —C 6 -C 14 aryl, —(CH 2 ) p -heterocyclyl, —C 3 -C 8 -cycloalkyl, —C 6 -C 14 aryl, heterocyclyl or heteroaryl;
p is independently an integer from 1 to 3;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
with the proviso that when Q is —SO 2 , then R c is not halogen;
wherein each of the above alkyl, cycloalkyl, aryl, heteroaryl and heterocyclyl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl group;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, N-oxides, pharmaceutically acceptable solvates and prodrugs.
[0100] In another embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and —C 1 -C 4 alkyl;
R c is heteroaryl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 ;
[0101] R f is —C 1 -C 8 alkyl, —(CR 1 R 2 ) p —C 6 -C 14 aryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
p is independently an integer from 1 to 3;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
wherein each of the above alkyl, cycloalkyl, aryl, heterocyclyl and heteroaryl are unsubstituted or substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl group;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, pharmaceutically acceptable solvates, prodrugs and N-oxides.
[0102] In another embodiment, the present invention provides compounds of formula (I), wherein,
[0000] R a , R b and R d are independently selected from hydrogen and methyl;
R c is heteroaryl selected from indolyl, pyrrolyl, pyridyl, pyrimidinyl and quinolinyl, wherein each of indolyl, pyrrolyl, pyridyl, pyrimidinyl and quinolinyl is optionally substituted with one or more groups selected from halogen, —C 1 -C 6 -alkyl, —C 1 -C 6 -alkoxy, and halo-C 1 -C 6 -alkyl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 ;
[0103] R f is —C 1 -C 8 alkyl, —(CH 2 ) p —C 6 -C 14 aryl, —C 3 -C 8 cycloalkyl, —C 6 -C 14 aryl, heteroaryl or heterocyclyl;
p is independently an integer from 1 to 3;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
wherein each of the above alkyl, cycloalkyl, aryl, heterocyclyl and heteroaryl are unsubstituted or substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl group;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, pharmaceutically acceptable solvates, prodrugs and N-oxides.
[0104] In another embodiment, the present invention provides compounds of formula (I),
[0000] R a , R b and R d are independently selected from hydrogen and methyl;
R c is halogen or heteroaryl selected from pyridyl, quinolinyl, indolyl, pyrimidinyl and pyrrolyl wherein each of pyridyl, quinolinyl, indolyl, pyrimidinyl and pyrrolyl is optionally substituted with one or more halogen, —C 1 -C 6 -alkyl, —C 1 -C 6 -alkoxy, and halo-C 1 -C 6 -alkyl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NH or —C(S)NH;
[0105] R f is hexyl, —(CH 2 )-phenyl, —(CH 2 )-2-morpholinyl, cyclohexyl, phenyl, thiophenyl, imidazolyl, pyrrolyl, furanyl, dihydro-pyridooxazinyl or quinolinyl; wherein each of hexyl, —(CH 2 )— phenyl, —(CH 2 )-2-morpholinyl, cyclohexyl, phenyl, thiophenyl, imidazolyl, pyrrolyl, furanyl, dihydro-pyridooxazinyl and quinolinyl are optionally and independently substituted with one or more of the same or different groups such as halogen, hydroxy, carbonyl, carboxy, ester, ether, acyl, acyloxy, cyano, amino, amide, imino, alkylthio, thioester, sulfonyl, nitro, —C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, halo-C 1 -C 6 alkoxy, —C 1 -C 6 alkoxy, —C 3 -C 8 cycloalkyl, —(CR 1 R 2 ) p —C 6 -C 10 aryl, —C 6 -C 10 aryl, —NHCOMe, —S(O) 2 Me, aryloxy, heterocyclyl and heteroaryl group;
R 1 and R 2 are independently selected from hydrogen and lower alkyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 , then R c is not halogen; in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, N-oxides, pharmaceutically acceptable solvates and prodrugs.
[0106] In another embodiment, the present invention provides compounds of formula (I),
[0000] R a , R b and R d are independently selected from hydrogen and methyl;
R c is halogen, pyridin-3-yl, pyridin-4-yl, 2-fluoropyridin-3yl, 5-fluoropyridin-3yl, 5-trifluoromethylpyridin-3yl, 6-chloropyridin-3yl, 6-fluoropyridin-3yl, 6-fluoro-5-methylpyridin-3yl, 6-methylpyridin-3yl, 6-methoxypyridin-3y1, quinolinyl, 2-indolyl, 1-methyl-1H-indol-3-yl, pyrimidin-5-yl, 2,4-dimethoxypyrimidin-5-yl, 2-methoxypyrimidin-5-yl, and 1H-pyrrol-2-yl;
R e is hydrogen or —C 1 -C 4 alkyl;
Q is —SO 2 , —C(O)NH or —C(S)NH;
[0107] R f is hexyl, —(CH 2 )-phenyl, —(CH 2 ) 2 -morpholinyl, cyclohexyl, phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,5-dibromophenyl, 2-bromo-4-fluorophenyl, 2-bromo-5-trifluoromethylphenyl, 2-bromo-4,6-difluorophenyl, 4-bromo-2,5-difluorophenyl, 4-bromo-2,6-difluorophenyl, 4-bromo-2,6-dichlorophenyl, 4-bromo-3-methylphenyl, 4-bromo-2-chlorophenyl, 4-bromo-2-trifluoromethoxyphenyl, 5-bromo-2-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 2-chloro-4-trifluoromethylphenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-4-fluorophenyl, 3-chloro-2-fluorophenyl, 3-chloro-4-fluoro-phenyl, 3-chloro-2-methylphenyl, 4-chloro-3-nitrophenyl, 4-chloro-2,5-dimethylphenyl, 5-chloro-2-methoyphenyl, 5-chloro-2-fluorophenyl, 2-cyanophenyl, 3-cyanophenyl, 3-cyano-4-fluorophenyl, 4-cyanophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2-fluoro-5-methylphenyl, 3-fluoro-4-methylphenyl, 4-fluoro-2-methylphenyl, 5-fluoro-2-methylphenyl, 5-fluoro-2-methoxyphenyl, 2,3,4-trifluorophenyl, 4-iodophenyl, 2-methylphenyl, 2-methylsulfonylphenyl, 2-methyl-5-nitrophenyl, 3-methylphenyl, 4-methylphenyl, 2,5-dimethylphenyl, 2-methyl-5-carboxyphenyl, 2,4,6-trimethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,5-dimethoxyphenyl, 2-methoxy-5-amidophenyl, 2-methoxy-4-methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-6-methylphenyl, 3-trifluoromethylphenyl, 2-trifluoromethoxyphenyl, 3,5-bis(trifluoromethyl)phenyl, 2-nitrophenyl, 3-nitrophenyl, 2-phenoxyphenyl, 4-phenoxyphenyl, 4-acetamidophenyl, 2-morpholino-5-trifluoromethylphenyl, 2-methyl-5-methylsulfonylphenyl, benzyl, biphenyl-4-yl, 2′-fluoro-5′-(trifluoromethyl)biphenyl, thiophen-2-yl, quinolin-8-yl, 1,2-dimethyl-imidazol-4-yl, cyclohexyl, pyridin-3-yl, 6-morpholino-pyridin-3-yl, methyl(1-methyl-pyrrol-2-yl)-2-carboxylate, 3,4-dihydro-4-methyl-pyrido[3,2-b][1,4]oxazine-7-yl, methyl(thiophen-3-yl)-2-carboxylate, methyl(furan-5-yl)-2-carboxylate or 2-morpholinoethyl;
p is independently an integer from 1 to 3;
with the proviso that when Q is —SO 2 , then R c is not halogen;
in all their stereoisomeric and tautomeric forms and mixtures thereof in all ratios, their pharmaceutically acceptable salts, N-oxides, pharmaceutically acceptable solvates and prodrugs.
[0108] Representative compounds of the present invention include any of the following compounds or their pharmaceutically acceptable salts and solvates as well as stereoisomers and tautomers thereof. However, the present invention is not limited to these compounds alone:
N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; N, 3-dimethyl-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 2-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 3-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 4-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 3-Bromo-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 4-Bromo-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 2-Cyano-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; (E)-3-cyano-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; 4-Cyano-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 4-Methoxy-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 2,4-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 2,6-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 3,4-difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 3,5-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 3-Chloro-2-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 3-Chloro-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 2-Fluoro-N, 5-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 3-Fluoro-N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 5-Fluoro-N, 2-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 3-(3-((2-(5-fluoro-2-methylphenylsulfonyl)-2-methylhydrazono)methyl)imidazo[1,2-a]pyridin-6-yl)pyridine 1-oxide; 4-Bromo-N, 3-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-3,5-bis (trifluoromethyl)benzenesulfonohydrazide; 3-Cyano-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; N, 2-dimethyl-5 nitro-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; 2-Bromo-4,6-difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide; N, 2,4,6-tetramethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; N-methyl-1-phenyl-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)thiophene-2-sulfonohydrazide; N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) quinoline-8-sulfonohydrazide; N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) cyclohexanesulfonohydrazide; 3-Fluoro-N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 3-Cyano-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; (E)-2,3,4-Trifluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-bromo-2,5-difluoro —N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-2-bromo-4-fluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide; (E)-4-bromo-2,6-dichloro-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-3-chloro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-2-chloro-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-4-(trifluoromethyl)benzenesulfonohydrazide; (E)-2-chloro-4-fluoro-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N, 1,2-trimethyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-1H-imidazole-4-sulfonohydrazide; (E)-4-chloro-N, 2,5-trimethyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2,5-difluoro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-5-fluoro-2-methoxy-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-Iodo-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-2′-Fluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5′-(trifluoromethyl)biphenyl-4-sulfonohydrazide; 4-Methyl-3-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)benzoic acid; 4-Methoxy-3-(1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinylsulfonyl)benzamide; (E)-N, 2,5-trimethyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2,5-dibromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2,5-dimethoxy-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-N, 2-dimethyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide; (E)-5-chloro-2-methoxy-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-4-bromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide; (E)-2-bromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide; (E)-N-methyl-2-nitro-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-2-(methylsulfonyl)-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-N-methyl-2-phenoxy-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hexane-1-sulfonohydrazide; (E)-N-methyl-2-morpholino-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide; (E)-N,2-dimethyl-5-(methylsulfonyl)-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2-bromo-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2-chloro-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide; (E)-N-methyl-6-morpholino-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) pyridine-3-sulfonohydrazide; (E)-Methyl 1-methyl-5-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)-1H-pyrrole-2-carboxylate; (E)-N,4-dimethyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-7-sulfonohydrazide; (E)-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) pyridine-3-sulfonohydrazide; (E)-N-methyl-4-phenoxy-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-Methyl 3-(1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)thiophene-2-carboxylate; (E)-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) biphenyl-4-sulfonohydrazide; (E)-Methyl 5-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl) furan-2-carboxylate; (E)-4-chloro-N-methyl-3-nitro-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-5-bromo-2-methoxy-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-3-chloro-N, 2-dimethyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-5-chloro-2-fluoro-N-methyl-N-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-4-Fluoro-N, 2-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2-methoxy-N, 6-dimethyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-Bromo-2-chloro-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-2-chloro-N-methyl-N′((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-N-(4-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)phenyl)acetamide; N′-((6-(6-fluoropyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-n, 2-dimethyl-5-nitrobenzenesulfonohydrazide; (E)-N-ethyl-2-methyl-5-nitro-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; N, 2-dimethyl-5-nitro-N′-((6-(pyridine-4-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; 5-Fluoro-N, 2-dimethyl-N′-((6-(pyridine-4-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; (E)-5-Fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide; (E)-5-Fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide; (E)-3-fluoro-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide; (E)-5-chloro-2-fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide; (E)-5-bromo-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide; (E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2,5-dimethoxy-N-methylbenzenesulfonohydrazide; (E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N, 2-dimethyl-5-(methylsulfonyl)benzenesulfonohydrazide; (E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylhexane-1-sulfonohydrazide; (E)-N-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N, 4-dimethylbenzenesulfonohydrazide; (E)-2-bromo-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide; (E)-2-cyano-N-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide; (E)-N-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N,5-dimethylbenzenesulfonohydrazide; N, 2-Dimethyl-5-nitro-N′((6-(quinolin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide; (E)-5-Fluoro-N,2-dimethyl-N-((8-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-3,5-Difluoro-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-Bromo-2,6-difluoro-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N,3-dimethyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-2-cyano-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-3-cyano-4-fluoro-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-3-cyano-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-Bromo-N,3-dimethyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-3-Methoxy-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-nitrobenzenesulfonohydrazide; (E)-3-Chloro-N-methyl-N-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide; (E)-2-Bromo-4,6-difluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-4-Chloro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-nitrobenzenesulfonohydrazide; (E)-2-Bromo-4-fluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N′-((6-(1H-indol-2-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide; (E)-5-fluoro-N,2-dimethyl-N′-((6-(1-methyl-1H-indol-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; 2-Cyano-N-methyl-N′((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; 5-Fluoro-N, 2-dimethyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; N, 3-dimethyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; 3-Fluoro-N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; 3-Chloro-N-methyl-N′-((7-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide; 3-Bromo-N-methyl-N′((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; 5-Fluoro-N, 2-dimethyl-N′-((7-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; N′-((6-(2,4-dimethoxypyrimidin-5-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N, 2-dimethylbenzenesulfonohydrazide; (E)-5-Fluoro-N,2-dimethyl-N′-((5-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N,3-dimethyl-N′-((5-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-5-fluoro-N,2-dimethyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-methyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide; (E)-5-Fluoro-2-methoxy-N-methyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N,2-dimethyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-5-fluoro-N′-((6-(5-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N, 2-dimethylbenzenesulfonohydrazide; (E)-5-Fluoro-N′-((6-(5-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide; (E)-5-Fluoro-N′-((6-(6-fluoro-5-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide; (E)-N′-((6-(6-Chloropyridins-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide; (E)-N′-((6-(1H-Pyrrol-2-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide; (E)-5-fluoro-N′-((6-(6-methoxypyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide; (E)-5-Fluoro-N′-((6-(2-methoxypyrimidin-5-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-N, 2-dimethylbenzenesulfonohydrazide; (E)-5-fluoro-N, 2-dimethyl-N′-((6-(5-(trifluoromethyl)pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide; (E)-5-Fluoro-N, 2-dimethyl-N′-((6-(pyrimidin-5-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide; (E)-N-benzyl-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide; (E)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N-p-tolylhydrazinecarboxamide; (E)-N-(2-fluoro-5-methylphenyl)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide; (E)-N-(5-fluoro-2-methylphenyl)-1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide; N-benzyl-2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methylhydrazinecarboxamide; (6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-N-(2-fluoro-5-methylphenyl)-1-methylhydrazinecarboxamide; (6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-N-(5-fluoro-2-methylphenyl)-1-methylhydrazinecarboxamide; (E)-1-methyl-N-(2-morpholinoethyl)-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide; (E)-N-(4-cyanophenyl)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide; (E)-N-(4-methoxyphenyl)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide; 2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methyl-N-(2-morpholinoethyl) hydrazinecarbothioamide; 2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methyl-N-(4-(trifluoromethyl)phenyl) hydrazinecarbothioamide; or their pharmaceutically acceptable salts and solvates.
[0262] According to a further aspect of the present invention, there is provided a process for the preparation of a compound of formula (I)
[0000]
[0000] wherein, Q is SO 2 ; R a , R b and R d are hydrogen or methyl; R c , R e and R f are as defined for formula (I), which comprises, refluxing a compound of formula (3)
[0000]
[0000] with a compound of formula H 2 N—NH—R e in presence of alcoholic solvent followed by reacting with a compound of formula R f SO 2 X, wherein Q is SO 2 ; X is halogen, R a , R b and R d are hydrogen or methyl, R c , R e and R f are as defined above for formula (I) in presence of a base, such as pyridine; and optionally converting the resulting compound into a pharmaceutically acceptable salt.
[0263] According to a further aspect of the present invention, there is provided a process for the preparation of a compound of formula (I)
[0000]
[0000] wherein, Q is —C(O)NH or —C(S)NH; R a , R b and R d are hydrogen or methyl, R c , R e and R f are as defined for formula (I), which comprises, refluxing a compound of formula (3)
[0000]
[0000] with a compound of formula H 2 N—NH—R e in presence of an alcoholic solvent followed by reacting with a compound of formula O═C═N═R f or S═C═N═R f , wherein R a , R b and R d are hydrogen or methyl, R c , R e and R f are as defined above for formula (I); and optionally converting the resulting compound into a pharmaceutically acceptable salt.
[0264] A convenient method for the synthesis of a compound of the present invention typically involves the series of steps described herein below:
[0265] The compounds of formula (I) are prepared using techniques known to one skilled in the art through the reaction sequences shown in the Schemes 1-2. Those with skill in the art will appreciate that the specific starting compounds and reagents, such as acids, bases, solvents, etc., identified in the schemes can be altered to prepare compounds encompassed by the present invention.
Schemes
[0266] The compounds of the present invention also include all stereoisomeric forms and mixtures thereof in all ratios and their pharmaceutically acceptable salts, solvates and polymorphs. Furthermore, all the compounds of the present invention are a subject of the present invention in the form of their prodrugs and other derivatives.
[0267] According to another aspect of present invention, the imidazo[1,2-a]pyridine derivatives of formula (I) can be prepared in a number of ways using methods well known to the person skilled in the art. Examples of methods to prepare the present compounds are described below and illustrated in Schemes 1 and 2 but are not limited thereto. It will be appreciated by persons skilled in the art that within certain of the processes described herein, the order of the synthetic steps employed may be varied and will depend inter alia on factors such as the nature of functional groups present in a particular substrate and the protecting group strategy (if any) to be adopted clearly, such factors will also influence the choice of reagent to be used in the synthetic steps. Although specific starting materials, reagents and reaction conditions are revealed in the schemes and the description below, other starting materials, reagents and reaction conditions can be used to obtain the compounds of formula (I).
[0268] The reagents, reactants and intermediates used in the following processes are either commercially available or can be prepared according to standard literature procedures known in the art. The starting compounds and the intermediates used for the synthesis of compounds of the present invention, are referred to with general symbols namely (1), (2), (3) and (4). The process used in schemes 1 and 2 of the present invention, is referred to with general symbols namely 1a, 1b, 1c, 1d, 1e, if and 1 g.
[0269] Processes for the preparation of compounds of the present invention are set forth in the following schemes:
[0000]
[0000] wherein X is halogen, R a , R b and R d are hydrogen; R c , R e and R f are as defined for formula (I). Reaction Conditions
1a: HC(O)—CH(X)—CH(O), reflux, 1 to 2 hours;
1b: R e —B(OH) 2 , 100-120° C., 3 to 4 hours;
1c: a) H 2 N—NH—R e , reflux, 85° C., 2 to 3 hours;
[0270] b) R f SO 2 X, room temperature, 1 to 2 hours;
[0000] The compound of formula (2) can be prepared by refluxing compound of formula (I) with a compound of formula HC(O)—CH(X)—CH(O) in an appropriate solvent such as acetonitrile, dimethylformamide, dimethylsulfoxide or a mixture thereof. The compound of formula (2) can be refluxed with a boronic acid derivative of formula R c —B(OH) 2 in presence of a base such as sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate or a mixture thereof and a catalyst such as dichlorobis(triphenylphosphine) palladium (II) in an appropriate solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran or a mixture thereof to form a compound of formula (3). The compound of formula (3) can be refluxed with a compound of formula H 2 N—NH—R e in a polar solvent such as ethanol, methanol, isopropanol or mixture thereof to form the corresponding hydrazide. The hydrazide so formed can be treated with compound of formula R f SO 2 X in presence of a base, such as pyridine, triethylamine, ammonia or mixture thereof to form a compound of formula (I).
[0000]
[0000] wherein, R a , R b and R d are hydrogen or methyl; R c is halogen or heteroaryl; Q is —C(O)NH or —C(S)NH; R e and R f are as defined earlier for formula (I).
Reaction Conditions
[0271] 1d: a) NH 2 NH-Me, 85° C., 1.5 hours,
[0272] b) O═C═N═R f or S═C═N═R f , reflux, 2 hours
[0273] The compound of formula (3) can be reacted with methyl hydrazine in an appropriate solvent such as ethanol to obtain a hydrazine intermediate. The hydrazine so formed can be refluxed for about 2 hours with compound of formula O═C═N═R f or S═C═N═R f to obtain a compound of formula (I), wherein, R a , R b and R d are hydrogen or methyl; R c is halogen or heteroaryl; Q is —C(O)NH or —C(S)NH and R e and R f are as defined earlier.
[0274] It will be appreciated by those skilled in the art that the compounds of the present invention may also be utilized in the form of their pharmaceutically acceptable salts or solvates. The pharmaceutically acceptable salts of the compounds of the present invention are non-toxic and can be used physiologically.
[0275] The pharmaceutically acceptable salts of the present invention can be synthesized from the subject compound, which contains a basic or an acidic moiety, by conventional chemical methods. Generally the salts are prepared by contacting the free base or acid with required amount of the desired salt-forming inorganic or organic acid or base in a suitable solvent or dispersant or from another salt by cation or anion exchange. Suitable solvents are, for example, ethyl acetate, ether, alcohols, acetone, tetrahydrofuran (THF), dioxane or mixtures of these solvents.
[0276] When the compounds of the present invention represented by the formula (I) contain one or more basic groups, i.e. groups which can be protonated, they can form an addition salt with an inorganic or organic acid. Examples of suitable inorganic acid salts include, but are not limited to, hydrochloride, hydrobromide, hydrofluoride, sulfate, sulfamate, phosphate, nitrate and bisulfate. Examples of suitable organic acid salts include, but are not limited to acetate, cinnamate, citrate, benzoate, benzenesulfonate, fumarate, maleate, malonate, methanesulfonate, oxalate, p-toluenesulfonate, succinate, tartrate, trifluoromethanesulfonate and valproate.
[0277] Thus, when the compounds of the present invention represented by the formula (I) contain an acidic group they can form an addition salt with a suitable base. For example, such salts of the compounds of the present invention may include their alkali metal salts such as Li, Na, and K salts, or alkaline earth metal salts like Ca, Mg salts, or aluminium salts, or salts with ammonia or salts of organic bases such as lysine, and arginine.
[0278] The pharmaceutically acceptable salts of the present invention can be synthesized from the subject compound, which contains a basic or an acidic moiety, by conventional chemical methods. Generally the salts are prepared by contacting the free base or acid with desired salt-forming inorganic or organic acid or base in a suitable solvent or dispersant or from another salt by cation or anion exchange. Suitable solvents are, for example, ethyl acetate, ether, alcohols, acetone, tetrahydrofuran (THF), dioxane or mixtures of these solvents.
[0279] The present invention furthermore includes all solvates of the compounds of the formula (I), for example hydrates, and the solvates formed with other solvents of crystallization, such as alcohols, ethers, ethyl acetate, dioxane, dimethylformamide (DMF), or a lower alkyl ketone, such as acetone, or mixtures thereof.
Methods of Treatment
[0280] The compounds of formula (I) are inhibitors of PI3K and/or mTOR and/or STAT3 and/or TNFα and/or IL-6 and find use in the treatment of benign or malignant tumors and/or inflammation.
[0281] The present invention further provides a method of inhibiting the tumor cell growth, tumor cell proliferation or tumorigenesis in a mammal comprising administering to a mammal in need of such treatment an effective amount of a compound of formula (I) or a pharmaceutically acceptable salt thereof.
[0282] Compounds of the present invention can be used to reduce, inhibit, or diminish the proliferation of tumor cells, and thereby assist in reducing the size of a tumor. Benign or malignant tumors that can be treated by compounds of formula (I) include, but are not limited to brain stem glioma, cerebellar astrocytoma, cerebral astrocytoma, brain tumors, glioblastoma, ependymoma, extracranial cancer, medulloblastoma, head & neck cancer, oral cancer, thyroid cancer, esophageal cancer, hypopharyngeal cancer, breast cancer, lung cancer including non-small-cell lung cancer and small-cell lung cancer, pancreatic cancer, lymphoma, melanoma, endometrial cancer, cervical cancer, liver cancer, intrahepatic bile duct, gastric cancer, bladder cancer, uterine cancer, colon cancer, colorectal cancer, ovarian cancer, prostate cancer, testicular cancer, leukemia, Ewing's sarcoma family of tumors, germ cell tumor, Hodgkin's disease, acute lymphoblastic leukemia, acute myeloid leukemia, adult acute myeloid leukemia, chronic myeloid leukemia, acute lymphocytic leukemia, chronic lymphocytic leukemia, hairy cell leukemia, human melanoma, neuroblastoma, non-Hodgkin's lymphoma, osteosarcoma, malignant fibrous histiocytoma of bone, retinoblastoma, rhabdomyosarcoma, soft tissue sarcomas, supratentorial primitive neuroectodermal and pineal tumors, visual pathway and hypothalamic glioma, Wilms' tumor, adult non-Hodgkin's lymphoma, kidney cancer, multiple myeloma, primary central nervous system lymphoma and skin cancer. Compounds of the formula (I) are also of use in the treatment of inflammatory diseases, for example psoriasis, contact dermatitis, atopic dermatitis, alopecia greata, erythema multiforme, dermatitis herpetiformis, scleroderma, vitiligo, hypersensitivity angiitis, urticaria, bullous pemphigoid, lupus erythematosus, pemphigus, epidermolysis bullosa acquisita, and other inflammatory or allergic conditions of the skin.
[0283] Compounds of the present invention may also be used for the treatment of other diseases or conditions, such as inflammatory bowel disease, inflammation, rheumatoid arthritis, juvenile rheumatoid arthritis, psoriatic arthritis, osteoarthritis, refractory rheumatoid arthritis, chronic non-rheumatoid arthritis, osteoporosis/bone resorption, Crohn's disease, septic shock, endotoxic shock, atherosclerosis, ischemia-reperfusion injury, coronary heart disease, vasculitis, amyloidosis, multiple sclerosis, sepsis, chronic recurrent uveitis, hepatitis C virus infection, malaria, ulcerative colitis, cachexia, psoriasis, plasmocytoma, endometriosis, Behcet's disease, Wegenrer's granulomatosis, AIDS, HIV infection, autoimmune disease, immune deficiency, common variable immunodeficiency (CVID), chronic graft-versus-host disease, trauma and transplant rejection, adult respiratory distress syndrome, pulmonary fibrosis, recurrent ovarian cancer, lymphoproliferative disease, refractory multiple myeloma, myeloproliferative disorder, diabetes, juvenile diabetes, meningitis, ankylosing spondylitis, skin delayed type hypersensitivity disorders, Alzheimer's disease, systemic lupus erythematosus and allergic asthma.
[0284] According to another aspect of the present invention, there is provided a method for the treatment of diseases mediated by PI3K and/or mTOR and/or STAT3, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0285] According to another aspect of the present invention, the disease mediated by PI3K and/or mTOR and/or STAT3 is cancer.
[0286] According to another aspect of the present invention, there is provided a method for the treatment of cancer, wherein the cancer is selected from the group comprising of brain stem glioma, cerebellar astrocytoma, cerebral astrocytoma, brain tumors, glioblastoma, ependymoma, extracranial cancer, medulloblastoma, head & neck cancer, oral cancer, thyroid cancer, hypopharyngeal cancer, breast cancer, endometrial cancer, leukemia, lung cancer including non-small-cell lung cancer and small-cell lung cancer, pancreatic cancer, lymphoma, melanoma, cervical cancer, liver cancer, gastric cancer, bladder cancer, uterine cancer colon cancer, colorectal cancer, ovarian cancer, prostate cancer, testicular cancer, Ewing's sarcoma family of tumors, germ cell tumor, Hodgkin's disease, acute lymphoblastic leukemia, acute myeloid leukemia, adult acute myeloid leukemia, chronic myeloid leukemia, acute lymphocytic leukemia, chronic lymphocytic leukemia, hairy cell leukemia, human melanoma, neuroblastoma, non-Hodgkin's lymphoma, osteosarcoma, malignant fibrous histiocytoma of bone, retinoblastoma, rhabdomyosarcoma, soft tissue sarcomas, supratentorial primitive neuroectodermal and pineal tumors, visual pathway and hypothalamic glioma, Wilms' tumor, adult non-Hodgkin's lymphoma, esophageal cancer, kidney cancer, multiple myeloma, primary central nervous system lymphoma and skin cancer comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0287] According to another aspect of the present invention, there is provided a method for the treatment of cancer, wherein the cancer is selected from the group comprising of glioblastoma, hypopharyngeal cancer, lung cancer, including non-small-cell lung cancer and small-cell lung cancer, breast cancer, pancreatic cancer, colon cancer, cervical cancer, prostate cancer, ovarian cancer, multiple myeloma and human melanoma comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0288] According to further aspect of the present invention, there is provided a method for the treatment of diseases mediated by TNF-α and/or IL-6, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0289] According to another aspect of the present invention, there is provided a method for the treatment of diseases mediated by TNF-α and/or IL-6 selected from the group comprising of psoriasis, contact dermatitis, atopic dermatitis, alopecia greata, erythema multiforme, dermatitis herpetiformis, scleroderma, vitiligo, hypersensitivity angiitis, urticaria, bullous pemphigoid, lupus erythematosus, pemphigus, epidermolysis bullosa acquisita, inflammatory bowel disease, inflammation, rheumatoid arthritis, chronic non-rheumatoid arthritis, osteoporosis/bone resorption, Crohn's disease, septic shock, endotoxic shock, atherosclerosis, ischaemia-reperfusion injury, coronary heart disease, vasculitis, amyloidosis, multiple sclerosis, sepsis, chronic recurrent uveitis, hepatitis C virus infection, malaria, ulcerative colitis, cachexia, plasmocytoma, endometriosis, Behcet's disease, Wegenrer's granulomatosis, AIDS, HIV infection, autoimmune disease, immune deficiency, common variable immunodeficiency (CVID), chronic graft-versus-host disease, trauma and transplant rejection, adult respiratory distress syndrome, pulmonary fibrosis, recurrent ovarian cancer, lymphoproliferative disease, refractory multiple myeloma, myeloproliferative disorder, diabetes, juvenile diabetes, meningitis, ankylosing spondylitis, skin delayed type hypersensitivity disorders, Alzheimer's disease, systemic lupus erythematosus and allergic asthma, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0290] According to another aspect of the present invention, there is provided a method for the treatment of diseases mediated by TNF-α and/or IL-6 selected from the group comprising of rheumatoid arthritis, Crohn's disease, ulcerative colitis, septic shock, psoriasis and atherosclerosis, comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0291] According to another aspect of the present invention, there is provided a method for the treatment of inflammatory diseases such as rheumatoid arthritis, Crohn's disease, ulcerative colitis, septic shock syndrome, psoriasis and atherosclerosis comprising administering to a mammal in need thereof a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or a pharmaceutically acceptable solvate thereof.
[0292] According to another aspect of the present invention, there is provided the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof containing either entity for the manufacture of a medicament for the treatment of diseases mediated by PI3K and/or mTOR.
[0293] According to another aspect of the present invention, there is provided the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof containing either entity for the manufacture of a medicament for the treatment of cancers wherein the cancer is selected from the group comprising of brain stem glioma, cerebellar astrocytoma, cerebral astrocytoma, brain tumors, glioblastoma, ependymoma, extracranial cancer, medulloblastoma, head & neck cancer, oral cancer, thyroid cancer, hypopharyngeal cancer, breast cancer, endometrial cancer, leukemia, lung cancer including non-small-cell lung cancer and small-cell lung cancer, pancreatic cancer, lymphoma, melanoma, cervical cancer, liver cancer, gastric cancer, bladder cancer, uterine cancer colon cancer, colorectal cancer, ovarian cancer, prostate cancer, testicular cancer, Ewing's sarcoma family of tumors, germ cell tumor, Hodgkin's disease, acute lymphoblastic leukemia, acute myeloid leukemia, adult acute myeloid leukemia, chronic myeloid leukemia, acute lymphocytic leukemia, chronic lymphocytic leukemia, hairy cell leukemia, human melanoma, neuroblastoma, non-Hodgkin's lymphoma, osteosarcoma, malignant fibrous histiocytoma of bone, retinoblastoma, rhabdomyosarcoma, soft tissue sarcomas, supratentorial primitive neuroectodermal and pineal tumors, visual pathway and hypothalamic glioma, Wilms' tumor, adult non-Hodgkin's lymphoma, esophageal cancer, kidney cancer, multiple myeloma, primary central nervous system lymphoma and skin cancer.
[0294] According to another aspect of the present invention, there is provided the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of cancers such as glioblastoma, hypopharyngeal cancer, lung cancer, including non-small-cell lung cancer and small-cell lung cancer, breast cancer, pancreatic cancer, colon cancer, cervical cancer, prostate cancer, ovarian cancer, multiple myeloma and human melanoma.
[0295] According to another aspect of the present invention there is provided the use of compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of diseases mediated by TNF-α and/or IL-6.
[0296] According to another aspect of the present invention there is provided the use of compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of diseases selected from the group comprising of psoriasis, contact dermatitis, atopic dermatitis, alopecia greata, erythema multiforme, dermatitis herpetiformis, scleroderma, vitiligo, hypersensitivity angiitis, urticaria, bullous pemphigoid, lupus erythematosus, pemphigus, epidermolysis bullosa acquisita, inflammatory bowel disease, inflammation, rheumatoid arthritis, chronic non-rheumatoid arthritis, osteoporosis/bone resorption, Crohn's disease, septic shock, endotoxic shock, atherosclerosis, ischaemia-reperfusion injury, coronary heart disease, vasculitis, amyloidosis, multiple sclerosis, sepsis, chronic recurrent uveitis, hepatitis C virus infection, malaria, ulcerative colitis, cachexia, plasmocytoma, endometriosis, Behcet's disease, Wegenrer's granulomatosis, AIDS, HIV infection, autoimmune disease, immune deficiency, common variable immunodeficiency (CVID), chronic graft-versus-host disease, trauma and transplant rejection, adult respiratory distress syndrome, pulmonary fibrosis, recurrent ovarian cancer, lymphoproliferative disease, refractory multiple myeloma, myeloproliferative disorder, diabetes, juvenile diabetes, meningitis, ankylosing spondylitis, skin delayed type hypersensitivity disorders, Alzheimer's disease, systemic lupus erythematosus and allergic asthma.
[0297] According to another aspect of the present invention, there is provided the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament for the treatment of cancer mediated by STAT3.
[0298] According to another aspect of the present invention, there is provided the use of a compound of formula (I) or a pharmaceutically acceptable salt thereof for the manufacture of a medicament containing either entity for the treatment of inflammatory diseases such as rheumatoid arthritis, Crohn's disease, ulcerative colitis, septic shock syndrome, psoriasis and atherosclerosis.
[0299] According to another aspect of the present invention there are provided methods for the manufacture of medicaments comprising compounds of formula (I), which are useful for the treatment of cancers such as glioblastoma, hypopharyngeal cancer, lung cancer, including non-small-cell lung cancer and small-cell lung cancer, breast cancer, pancreatic cancer, colon cancer, cervical cancer, prostate cancer, ovarian cancer, multiple myeloma and human melanoma
[0300] According to another aspect of the present invention there are provided methods for manufacture of medicaments comprising compounds of formula (I), which are useful for the treatment of inflammation, including diseases such as rheumatoid arthritis, Crohn's disease, ulcerative colitis, septic shock syndrome, psoriasis and atherosclerosis.
Pharmaceutical Compositions and Methods
[0301] According to another aspect of the present invention there are provided pharmaceutical compositions comprising the compound of formula (I) as active ingredients, useful in the treatment of cancer and inflammation.
[0302] The pharmaceutical preparations according to the invention are prepared in a manner known per se and familiar to one skilled in the art. Pharmaceutically acceptable inert inorganic and/or organic carriers and/or additives can be used in addition to the compounds of formula (I), and/or their physiologically tolerable salts. For the production of pills, tablets, coated tablets and hard gelatin capsules it is possible to use, for example, lactose, corn starch or derivatives thereof, gum arabica, magnesia or glucose, etc. Carriers for soft gelatin capsules and suppositories are, for example, fats, waxes, natural or hardened oils, etc. Suitable carriers for the production of solutions, for example injection solutions, or of emulsions or syrups are, for example, water, physiological sodium chloride solution or alcohols, for example, ethanol, propanol or glycerol, sugar solutions, such as glucose solutions or mannitol solutions, or a mixture of the various solvents which have been mentioned.
[0303] The pharmaceutical preparations normally contain about 1 to 99%, for example, about 5 to 70%, or from about 5 to about 30% by weight of the compound of the formula (I) and/or its physiologically tolerable salt. The amount of the active ingredient of the formula (I) and/or its physiologically tolerable salt in the pharmaceutical preparations normally is from about 1 to 1000 mg.
[0304] The dose of the compounds of this invention, which is to be administered, can cover a wide range. The dose to be administered daily is to be selected to suit the desired effect. A suitable dosage is about 0.001 to 100 mg/kg/day of the compound of formula (I) and/or their physiologically tolerable salt, for example, about 0.01 to 50 mg/kg/day of a compound of formula (I) or a pharmaceutically acceptable salt of the compound. If required, higher or lower daily doses can also be administered. Actual dosage levels of the active ingredients in the pharmaceutical compositions of this invention may be varied so as to obtain an amount of the active ingredient, which is effective to achieve the desired therapeutic response for a particular patient, composition, and mode of administration without being toxic or resulting in unacceptable side effects to the patient.
[0305] The pharmaceuticals can be administered orally, for example in the form of pills, tablets, coated tablets, lozenges, capsules, dispersible powders or granules, suspensions, emulsions, syrups or elixirs. Administration, however, can also be carried out rectally, for example in the form of suppositories, or parenterally, for example intravenously, intramuscularly or subcutaneously, in the form of injectable sterile solutions or suspensions, or topically, for example in the form of solutions, ointments, gels, lotions or transdermally, for example, in the form of transdermal patches, or in other ways, for example in the form of aerosols or nasal sprays.
[0306] The selected dosage level will depend upon a variety of factors including the activity of the particular compound of the present invention employed, the route of administration, the time of administration, the rate of excretion of the particular compound being employed, the duration of the treatment, other drugs, compounds and/or materials used in combination with the particular compounds employed, the age, sex, weight, condition, general health and prior medical history of the patient being treated, and like factors well known in the medical arts.
[0307] In addition to the active ingredient of the formula (I) and/or its physiologically acceptable salt and carrier substances, the pharmaceutical preparations can contain additives such as, for example, fillers, antioxidants, dispersants, emulsifiers, defoamers, flavors, preservatives, solubilizers or colorants. They can also contain two or more compounds of the formula (I) and/or their physiologically tolerable salts. Furthermore, in addition to at least one compound of the formula (I) and/or its physiologically tolerable salt, the pharmaceutical preparations can also contain one or more other therapeutically or prophylactically active ingredients.
[0308] By “pharmaceutically acceptable” it is meant the carrier, diluent, excipients, and/or salt must be compatible with the other ingredients of the formulation, and not deleterious to the recipient thereof.
[0309] It is understood that modifications that do not substantially affect the activity of the various embodiments of this invention are included within the invention disclosed herein. Accordingly, the following examples are intended to illustrate but not to limit the present invention.
Experimental
[0310] The invention is further understood by reference to the following examples, which are intended to be purely exemplary of the invention. The present invention is not limited in scope by the exemplified embodiments, which are intended as illustrations of single aspects of the invention only. Any methods that are functionally equivalent are within the scope of the invention. Various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description. Such modifications fall within the scope of the appended claims.
[0000] Unless otherwise stated all temperatures are in degree Celsius. Also, in these examples and elsewhere, abbreviations have the following meanings:
[0000]
List of abbreviations
CO 2
Carbon dioxide
CHCl 3
Chloroform
DCM/CH 2 Cl 2
Dichloromethane
DMEM
Dulbecco's Modified Eagle Medium
DMF
Dimethyl formamide
DMSO
Dimethyl sulfoxide
EtOAc
Ethyl acetate
FCS
Fetal calf serum
FBS
Fetal Bovine Serum
g
Gram
HCl
Hydrochloric acid
Hepes
N-2-Hydroxyethylpiperazine-
N′-2-ethanesulfonic acid
H 2
Hydrogen
H 2 SO 4
Sulphuric acid
MeOH
Methanol
mL
Milliliter
MgCl 2
Magnesium chloride
mmol
Millimoles
MTS
(3-(4,5-Dimethylthiazol-2-yl)-
5-(3-carboxymethoxyphenyl)-
2-(4-sulfonyl)-2H-tetrazolium)
Na 2 CO 3
Sodium carbonate
NaHCO 3
Sodium bicarbonate
NaOH
Sodium hydroxide
NaH
Sodium hydride
Na 2 SO 4
Sodium sulphate
PBS
Phosphate buffer saline
Pet ether
Petroleum ether
POCl 3
Phosphorus oxychloride
RPMI
Roswell Park Memorial Institute
RT
Room Temperature (20-30° C.)
THF
Tetrahydrofuran
Intermediate 1: 6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0311] Step 1: 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde Bromomalonaldehyde (5230 mg, 34.68 mmol) was added to a solution of 5-bromopyridin-2-amine in acetonitrile (5000 mg, 28.90 mmol). The reaction mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was quenched with sodium bicarbonate solution and extracted with EtOAc. The organic layer was washed with brine and dried over sodium sulfate. The organic layer was concentrated in vacuo and the product was purified by column chromatography using EtOAc-petroleum ether gradient to obtain the title compound. Yield: 53%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.94 (s, 1H), 9.50 (s, 1H), 8.54 (s, 1H), 7.86-7.85 (m, 2H); MS (m/z): 226 (M+1) + .
[0312] Step 2: 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde (Compound of step 1, 4000 mg, 17.77 mmol), Pyridine-3-boronic acid (3280 mg, 26.66 mmol), dichlorobis(triphenylphosphine) palladium (II) (800 mg, 20% mmol) and 2M aqueous Na 2 CO 3 (14 mL) were added to DMF (50 mL) and refluxed for 2 hours. The reaction mixture was diluted with EtOAc and washed with H 2 O and brine. The solvent was evaporated to obtain oil, which was purified by column chromatography (silica gel, 1% MeOH in CHCl 3 ) to obtain the title compound. Yield: 62%; 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.96 (s, 1H), 9.59 (s, 1H), 8.92 (s, 1H), 8.63-8.61 (d, 1H), 8.55 (s, 1H), 8.15-8.11 (d, 1H), 8.06-7.96 (m, 2H), 7.56-7.51 (M, 1H); MS: m/z 224 (M+1) + .
[0313] 6-(pyridin-4-yl)imidazo[1,2-a]pyridine-3-carbaldehyde was prepared by following the procedure as described for Intermediate 1, except that Pyridine-4-boronic acid was used in place of Pyridine-3-boronic acid.
Intermediate 2: 6-(6-fluoropyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde
[0314] The title compound was prepared by following the process as described for Intermediate 1. 6-fluoropyridin-3-ylboronic acid (68.88 mg, 0.488 mmol) was used instead of pyridine-3-boronic acid. Yield: 50%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.99 (s, 1H), 9.60 (s, 1H), 8.61-8.62 (d, 1H, J=1.8 Hz), 8.58 (s, 1H), 8.34-8.37 (dd, 1H, J=3 Hz, 6 Hz), 7.99-8.04 (m, 2H), 7.35-7.38 (dd, 1H, J=3 Hz); MS: m/z 242 (M+1) + .
Intermediate 3: 6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde
[0315] The title compound was prepared by following the process as described for Intermediate 1. 2-fluoropyridin-3-ylboronic acid (71 mg, 0.462 mmol) was used instead of pyridine-3-boronic acid. Yield: 45%; 1 H NMR (DMSO-d 6 ; 300 MHz): 9.99 (s, 1H), 9.66 (s, 1H), 8.62 (s, 1H), 8.28-8.33 (m, 2H), 7.99-8.02 (m, 2H), 7.56 (s, 1H); MS: m/z 242 (M+1) + .
Intermediate 4: 6-(Quinolin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde
[0316] The title compound was prepared by following the process as described for Intermediate 1. Quinolin-3-ylboronic acid (84.6 mg, 0.488 mmol) was used instead of pyridine-3-boronic acid. Yield: 66%; 1 H NMR (DMSO-d 6 ; 300 MHz): 10.01 (s, 1H), 9.88 (s, 1H), 9.19-9.20 (d, 1H, J=2.4 Hz), 8.39 (s, 2H), 8.16-8.19 (d, 1H, J=8.4 Hz), 7.94-7.95 (m, 2H), 7.76-7.82 (m, 1H), 7.62-7.67 (t, 1H, J=7.8 Hz, 7.2 Hz), 7.50-7.52 (m, 1H); MS: m/z 274(M+1) + .
Intermediate 5: 8-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0317] Step 1: 6-bromo-8-methylimidazo[1,2-a]pyridine-3-carbaldehyde The title compound was prepared by following the procedure as described for step 1 of Intermediate 1. 5-bromo-3-methylpyridin-2-amine (500 mg, 2.673 mmol) was used instead of 5-bromopyridin-2-amine in acetonitrile to obtain the title compound.
[0318] Yield: 52%; 1 H NMR (CDCl 3 ; 300 MHz): δ 9.961 (s, 1H), 9.557 (s, 1H), 8.298 (s, 1H), 7.484 (s, 1H), 2.711 (s, 3H); MS: m/z 239 (M+1) +
[0319] Step 2: 8-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde The title compound was prepared by following the process as described for step 2 of Intermediate 1. 6-Bromo-8-methylimidazo[1,2-a]pyridine-3-carbaldehyde (150 mg, 0.630 mmol) was used instead of 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde.
[0320] Yield: 60%; 1 H NMR (CDCl 3 ; 300 MHz): δ 10.00 (s, 1H), 9.63 (s, 1H), 8.91 (s, 1H), 8.70 (s, 1H), 8.37 (s, 1H), 7.95 (d, 1H, J=5.7 Hz), 7.62 (s, 1H), 7.46 (s, 1H), 2.79 (s, 3H); MS: m/z 236 (M+1) + .
Intermediate 6: Tert-butyl 2-(3-formylimidazo[1,2-a]pyridin-6-yl)-1H-indole-1-carboxylate
[0321] 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde (step 1 of Intermediate 1, 150 mg, 0.6729 mmol), 1-(tert-butoxycarbonyl)-1H-indol-2-ylboronic acid (228 mg, 0.8742 mmol), dichlorobis(triphenylphosphine) palladium (II) (30 mg, 20% mmol) and 2M aqueous Na 2 CO 3 (1 mL) were added to DMF (5 mL) and refluxed for 2 h. The reaction mixture was diluted with EtOAc and washed with water and brine. The solvent was evaporated to obtain solid residue, which was purified by column chromatography (silica gel, 1% methanol in chloroform) to obtain the title compound. Yield: 51%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 11.91 (s, 1H), 9.99 (s, 1H), 9.81 (s, 1H), 8.55 (s, 1H), 8.17 (dd, 1H, J=9.3, 1.8 Hz), 7.95 (d, 1H, J=9.3 Hz), 7.56 (d, 1H, J=7.8 Hz), 7.43 (d, 1H, J=8.4 Hz), 7.142 (t, 1H, J=7.2 Hz), 7.03 (m, 2H); MS: m/z 260 (M−1) + .
Intermediate 7: 7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0322] Step 1: 6-bromo-7-methylimidazo[1,2-a]pyridine-3-carbaldehyde 1402-67 Bromomalonaldehyde (5000 mg, 26.74 mmol) was added to a solution of 5-bromo-4-methylpyridin-2-amine in acetonitrile (5250 mg, 34.76 mmol). The reaction mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was quenched with sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate. The organic layer was concentrated in vacuum and the product was purified by column chromatography using ethyl acetate-petroleum ether gradient to obtain the title compound. Yield: 79.81%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.90 (s, 1H), 9.52 (s, 1H), 8.51 (s, 1H), 7.94 (s, 1H), 2.50 (s, 3H); MS (m/z): 239 (M+1) + .
[0323] Step 2: 7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde 6-bromo-7-methylimidazo[1,2-a]pyridine-3-carbaldehyde (Compound of step 1, 2000 mg, 7.90 mmol), Pyridine-3-boronic acid (1170 mg, 9.49 mmol), dichlorobis (triphenylphosphine) palladium (II) (200 mg, 10% mmol) and 2M aqueous Na 2 CO 3 (7 mL) were added to DMF (25 mL) and refluxed for 2 hours. The reaction mixture was diluted with ethyl acetate and washed with H 2 O and brine. The solvent was evaporated to obtain crude product, which was purified by column chromatography (silica gel, 1% methanol in chloroform) to obtain the title compound. Yield: 62%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.92 (s, 1H), 9.20 (s, 1H), 8.69-8.70 (m, 2H), 8.54 (s, 1H), 7.95-7.99 (m, 1H), 7.90 (s, 1H), 7.53-7.58 (m, 1H), 2.34 (s, 3H); MS: m/z 238 (M+1)+
Intermediate 8: 6-(2,4-dimethoxypyrimidin-5-yl) imidazo[1,2-a]pyridine-3-carbaldehyde 1402-159
[0324] 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde (Compound of step 1 of Intermediate 1, 200 mg, 0.89 mmol), 2,4-dimethoxypyrimidin-5-ylboronic acid (212.57 mg, 1.15 mmol), dichlorobis(triphenylphosphine) palladium (II) (20 mg, 10% mmol) and 2M aqueous Na 2 CO 3 (1 mL) were added to DMF (8 mL) and refluxed for 3 hours. The reaction mixture was diluted with ethyl acetate and washed with H 2 O and brine. The solvent was evaporated to obtain crude product, which was purified by column chromatography (silica gel, 1% methanol in chloroform) to obtain the title compound. Yield: 47.43%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.97 (s, 1H), 9.59 (s, 1H), 8.56-8.58 (d, 2H, J=4.5 Hz), 7.88-7.98 (m, 2H), 3.96 (s, 3H), 3.98 (s, 3H); MS: m/z 285.1 (M+1)+
Intermediate 9: 5-Methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0325] Step 1: 6-bromo-5-methylimidazo[1,2-a]pyridine-3-carbaldehyde Bromomalonaldehyde (464 mg, 3.07 mmol) was added to a solution of 5-bromo-6-methylpyridin-2-amine (500 mg, 2.67 mmol) in acetonitrile. The reaction mixture was refluxed for 1 hour. After completion of the reaction, the reaction mixture was quenched with sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate. The organic layer was concentrated and the product was purified by column chromatography using up to 0.5% methanol in chloroform gradient to obtain the title compound. Yield: 28%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.06 (s, 1H), 8.51 (s, 1H), 7.86-7.83 (d, 1H, J=9.3 Hz), 7.68 (d, 1H, J=9.3 Hz), 3.03 (s, 3H); MS: m/z 240.1 (M+1) + .
[0326] Step 2: 5-Methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde 6-bromo-5-methylimidazo[1,2-a]pyridine-3-carbaldehyde (125 mg, 0.523 mmol), Pyridine-3-boronic acid (77.5 mg, 0.603 mmol), dichlorobis(triphenylphosphine) palladium (II) (36.7 mg, 0.05 mmol) and 2M aqueous Na 2 CO 3 (2 ml) were dissolved in DMF (3 ml) and refluxed for 2 hours. The reaction mixture was diluted with ethyl acetate and washed with water and brine. The solvent was evaporated to obtain crude product, which was purified by column chromatography (silica gel, 0.5% methanol in chloroform) to obtain the title compound. Yield: 40%; 1 H NMR (DMSO-d 6 ; 300 MHz): 69.90(s, 1H), 8.39 (s, 1H), 7.73 (d, 1H, J=9.6 Hz), 7.56 (d, 1H, J=9.3 Hz), 3.11 (s, 3H); MS: m/z 238 (M+1) + .
Intermediate 10: 6-(6-methylpyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0327] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 6-methylpyridin-3-ylboronic acid. Yield: 40%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.0 (s, 1H), 9.74 (s, 1H), 8.79 (d, 1H, J=1.8 Hz), 8.38 (s, 1H), 7.93-7.78 (m, 4H), 7.33 (d, 1H, J=8.1 Hz), 2.66 (s, 3H); MS: m/z 238(M+1) + .
Intermediate 11: 6-(5-fluoropyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0328] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 5-fluoropyridin-3-ylboronic acid. Yield: 52%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.01 (s, 1H), 9.66 (s, 1H), 8.84 (s, 1H), 8.66-8.67 (d, 1H, J=2.1 Hz), 8.59 (s, 1H), 8.18-8.21 (d, 1H, J=9 Hz), 8.08-8.11 (d, 1H, J=9.6 Hz), 8.03 (s, 1H); MS: m/z 241.6 (M+1) + .
Intermediate 12: 6-(6-fluoro-5-methylpyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0329] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 6-fluoro-5-methylpyridin-3-ylboronic acid. Yield: 44%; 1 H NMR (DMSO-d 6 ; 300 MHz): 610.0 (s, 1H), 9.59 (s, 1H), 8.58-8.00 (m, 5H), 2.24 (s, 3H), MS: m/z 256(M+1) + .
Intermediate 13: 6-(6-chloropyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0330] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 6-chloropyridin-3-ylboronic acid. Yield: 44%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.02 (s, 1H), 9.76 (s, 1H), 8.68 (s, 1H), 8.40 (s, 1H), 7.93 (bs, 2H), 7.79 (d, 1H, J=9 Hz), 7.52 (d, 1H, J=8.1 Hz); MS: m/z 258(M+1) + .
Intermediate 14: 6-(1H-pyrrol-2-yl)imidazo[1,2-a]pyridine-3-carbaldehyde
[0331] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 1H-pyrrol-2-ylboronic acid.
[0332] Yield: 21%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 11.69 (s, 1H), 9.94 (s, 1H), 9.58 (s, 1H), 8.48 (s, 1H), 8.00-7.86 (m, 2H), 6.94 (s, 1H), 6.61 (s, 1H), 6.18 (s, 1H); MS: m/z 212 (M+1).
Intermediate 15: 6-(2-methoxypyrimidin-5-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0333] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 2-methoxypyrimidin-5-ylboronic acid. Yield: 55.55%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.01 (s, 1H), 9.62 (s, 1H), 9.00 (s, 2H), 8.59 (s, 1H), 8.04-8.05 (m, 2H), 3.99 (s, 3H); MS: m/z 254 (M+1) + .
Intermediate 16: 6-(5-(trifluoromethyl)pyridin-3-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0334] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and 5-(trifluoromethyl)pyridin-3-ylboronic acid. Yield: 48%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.04 (s, 1H), 9.71 (s, 1H), 9.27 (s, 1H), 9.07 (s, 1H), 8.62 (s, 2H), 8.16-8.19 (dd, 1H, J=1.8&9.3 Hz), 8.03-8.04 (d, 1H, J=9.3 Hz); MS: m/z 292 (M+1) + .
Intermediate 17: 6-(pyrimidin-5-yl) imidazo[1,2-a]pyridine-3-carbaldehyde
[0335] The title compound was prepared by following the procedure as described for Intermediate 1 using 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde and pyrimidin-5-ylboronic acid.
[0336] Yield: 50%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.01 (s, 1H), 9.77-9.79 (m, 1H), 9.29-9.32 (m, 1H), 9.04 (s, 2H), 8.39-8.40 (m, 1H), 7.94-7.99 (m, 1H), 7.78-7.82 (dd, 1H, J=1.8 &9.3 Hz); MS: m/z 224 (M+1) + .
Intermediate 18: 6-Bromoimidazo[1,2-a]pyrimidine-3-carbaldehyde 1402-113
[0337] Bromomalonaldehyde (500 mg, 2.90 mmol) was added to a solution of 5-bromopyrimidin-2-amine (526 mg, 3.49 mmol) in acetonitrile. The reaction mixture was refluxed for 2 hours. After completion of the reaction, the reaction mixture was quenched with sodium bicarbonate solution and extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate. The organic layer was concentrated and the product was purified by column chromatography using up to 2% methanol in chloroform gradient to obtain the title compound. Yield: 40%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.98(s, 1H), 9.75-9.76 (d, 1H, J=2.4 Hz), 8.97-8.98 (d, 1H, 2.4 Hz), 8.70 (s, 1H); MS (m/z): 226 (M+1) + .
EXAMPLES
Example 1
N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0338] To a solution of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (Intermediate 1, 70 mg, 0.31 mmol) in ethanol (3 mL) was added methyl hydrazine (17 mg, 0.47 mmol) at RT.
[0339] The reaction was heated at 85° C. for 3 h. Ethanol was evaporated. Pyridine (2 mL) was added to this residue, followed by addition of benzene sulfonylchloride (83 mg, 0.47 mmol). The reaction mixture was stirred at RT overnight. Pyridine was evaporated. Water was added to this residue and extracted with dichloromethane. Organic layer was dried over sodium sulfate and evaporated. The crude product was purified by column chromatography (silica gel, 1.5% methanol in chloroform) to obtain the title compound.
[0340] Yield: 68%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.69 (s, 1H), 8.96 (s, 1H), 8.64-8.65 (d, 1H, J=4.5 Hz), 8.27 (s, 1H), 8.12-8.15 (d, 1H, J=8.1 Hz), 7.99 (s, 1H), 7.86 (s, 2H), 7.78-7.75 (d, 2H, J=8.1 Hz), 7.57-7.62 (t, 2H, J=6.3 Hz), 7.42-7.47 (t, 2H, J=7.8 Hz), 3.22 (s, 3H); MS: m/z 392 (M+1) + .
[0341] The compounds of Examples 2-82 were prepared by following the procedure as described for Example 1, using Intermediate 1, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 2
N, 3-dimethyl-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0342] Yield: 47%; 1 H NMR (DMSO-d 6 ; 300 MHz,): δ 9.74 (s, 1H), 9.00-9.01 (d, 1H, J=3 Hz), 8.67-8.69 (dd, 1H, J=1.2, 4.8 Hz,), 8.29 (s, 1H), 8.16-8.20 (m, 1H), 8.02 (s, 1H), 7.86 (s, 2H), 7.57-7.64 (m, 3H), 7.34-7.41 (m, 2H), 3.27 (s, 3H), 2.07 (s, 3H); MS m/z 406 (M+1) + .
Example 3
N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0343] Yield: 55%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.73 (s, 1H), 8.98-8.99 (d, 1H, J=3 Hz), 8.67-8.69 (dd, 1H, J=3, 6 Hz), 8.24 (s, 1H), 8.15-8.18 (dt, 1H, J=3.6Hz), 8.02 (s, 1H), 7.88 (s, 2H); 7.66-7.68 (d, 2H, J=6 Hz), 7.59-7.63 (m, 1H), 7.25-7.28 (d, 2H, J=9 Hz), 3.22 (s, 3H), 2.27 (s, 3H); MS m/z 407 (M+1) + .
Example 4
2-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0344] Yield: 62.5%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.56 (s, 1H), 8.91-8.92 (d, 1H, J=1.8 Hz), 8.68-8.67 (dd, 1H, J=1.5, 4.8 Hz), 8.34 (s, 1H), 8.08-8.12 (m, 1H), 8.03 (s, 1H), 7.81-7.86 (m, 3H), 7.60-7.64 (m, 2H), 7.37-7.44 (t, 1H, J=8.7 Hz), 7.11-7.16 (t, 1H, J=7.2 Hz), 3.39 (s, 3H); MS: m/z 410 (M+1) + .
Example 5
3-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide
[0345] Yield: 51%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.69 (s, 1H), 8.97-8.96 (d, 1H, J=2.1 Hz), 8.66-8.64 (d, 1H, J=4.8 Hz), 8.32 (s, 1H), 8.12-8.15 (d, 1H, J=8.1 Hz), 8.03 (s, 1H), 7.88 (s, 2H), 7.57-7.64 (m, 3H), 7.50-7.54 (m, 2H), 3.28 (s, 3H); MS: m/z 410 (M+1) + .
Example 6
4-Fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0346] Yield: 55%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.72 (s, 1H), 8.97-8.78 (d, 1H, J=2.1 Hz), 8.64-8.66 (dd, 1H, J=4.5, 9Hz), 8.31 (s, 1H), 8.13-8.16 (m, 1H), 8.03 (s, 1H), 7.88 (s, 2H), 7.83-7.86 (m, 2H), 7.56-7.61 (m, 1H), 7.30-7.36 (t, 2H, J=9 Hz), 3.22 (s, 3H); MS: m/z 410 (M+1) + .
Example 7
3-Bromo-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0347] Yield: 16%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.74 (s, 1H), 9.00-9.01 (d, 1H, J=3 Hz), 8.66-8.67 (d, 1H, J=3 Hz), 8.33 (s, 1H), 8.15-8.19 (m, 1H), 8.05 (s, 1H), 7.91-7.92 (m, 2H), 7.88-7.89 (m, 1H), 7.79-7.84 (m, 2H), 7.59-7.63 (dd, 1H, J=3.6Hz), 7.43-7.49 (t, 1H, J=8.1, 7.8 Hz), 3.29 (s, 3H); MS: m/z 470 (M+1) + .
Example 8
4-Bromo-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0348] Yield: 54.4%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.70 (s, 1H), 8.98-8.99 (d, 1H, J=2.1 Hz), 8.66-8.68 (dd, 1H, J=1.2, 4.8 Hz), 8.32 (s, 1H), 8.13-8.17 (m, 1H), 8.04 (s, 1H), 7.89 (s, 2H), 7.72 (s, 4H), 7.58-7.62 (m, 1H), 3.24 (s, 3H); MS: m/z 470 (M+1) + .
Example 9
2-Cyano-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0349] Yield: 61.5%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.44 (s, 1H), 8.87-8.88 (d, 1H, J=2.1 Hz), 8.67-8.68 (d, 1H, J=4.8 Hz), 8.40 (s, 1H), 8.10 (s, 1H), 8.05-8.08 (m, 3H), 7.85 (s, 2H), 7.78-7.81 (d, 1H, J=7.5 Hz), 7.65-7.70 (m, 1H), 7.58-7.62 (m, 1H), 3.42 (S, 3H); MS: m/z 417 (M+1) + .
Example 10
(E)-3-cyano-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0350] Yield: 63%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.67 (s, 1H), 8.96-8.97 (d, 1H, J=3 Hz), 8.46-8.66 (d, 1H, J=6 Hz), 8.33 (s, 1H), 8.23 (s, 1H), 8.13-8.15 (d, 1H J=8.1 Hz), 8.08-8.11 (m, 2H), 8.04-8.05 (m, 1H), 7.85-7.93 (m, 2H), 7.65-7.70 (t, 1H, J=6, 9 Hz), 7.57-7.61 (m, 1H), 3.29 (s, 3H); MS: m/z 417 (M+1) + .
Example 11
4-Cyano-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0351] Yield: 58%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.68 (s, 1H), 8.96-8.97 (d, 1H, J=2.1 Hz), 8.66-8.68 (d, 1H, J=4.8 Hz), 8.35 (s, 1H), 8.14-8.17 (m, 1H), 8.05 (s, 1H), 7.95-8.01 (m, 4H), 7.90 (s, 2H), 7.58-7.62 (m, 1H), 3.27 (s, 3H); MS: m/z 417 (M+1) + .
Example 12
4-Methoxy-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0352] Yield: 53%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.80 (s, 1H), 8.95 (s, 1H), 8.69-8.70 (d, 1H, J=3 Hz), 8.09-8.11 (d, 1H, J=6 Hz), 8.00 (s, 1H), 7.91 (s, 1H), 7.82-7.85 (d, 1H, 9 Hz), 7.67-7.70 (d, 1H, J=9 Hz), 7.44-7.52 (m, 1H), 7.36-7.39 (d, 1H, J=9 Hz), 7.23-7.28 (m, 2H), 7.01-7.04 (d, 1H, J=3 Hz), 3.54 (s, 3H), 3.30 (s, 3H); MS: m/z 422 (M+1) + .
Example 13
2,4-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0353] Yield: 52%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.61 (s, 1H), 8.92-8.93 (d, 1H, J=2.1 Hz), 8.66-8.68 (dd, 1H, J=1.5, 4.8 Hz), 8.35 (s, 1H), 8.09-8.13 (m, 1H), 8.04 (s, 1H), 7.87-7.94 (m, 3H), 7.58-7.63 (m, 1H), 7.49-7.56 (m, 1H), 7.08-7.11 (m, 1H), 3.25 (s, 3H); MS: m/z 428 (M+1) + .
Example 14
2,6-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0354] Yield: 49%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.61 (s, 1H), 8.90 (s, 1H), 8.64-8.66 (d, 1H, J=4.5 Hz), 8.38 (s, 1H), 8.08 (s, 1H), 8.05 (s, 1H), 7.87 (s, 2H), 7.67-7.71 (m, 1H), 7.54-7.58 (m, 1H), 7.19-7.25 (t, 2H, J=9.18 Hz), 3.14 (s, 3H); MS: m/z 428 (M+1) + .
Example 15
3,4-difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0355] Yield: 42.85%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.72 (s, 1H), 9.00-9.00 (d, 1H, J=2.1 Hz), 8.68-8.70 (dd, 1H, J=1.5, 4.8 Hz), 8.37 (s, 1H), 8.16-8.20 (m, 1H), 8.08 (s, 1H), 7.87-7.93 (m, 3H), 7.68-7.71 (m, 1H), 7.59-7.65 (m, 2H), 3.30 (s, 3H); MS: m/z 428 (M+1) + .
Example 16
3,5-Difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0356] Yield: 37%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.66 (s, 1H), 8.97-8.98 (d, 1H, J=2.1 Hz), 8.65-8.67 (d, 1H, J=4.8 Hz), 8.36 (s, 1H), 8.12-8.15 (d, 1H, J=8.1 Hz), 8.06 (s, 1H), 7.90 (s, 2H), 7.57-7.61 (m, 2H), 7.48-7.50 (d, 2H, J=4.5 Hz), 3.25 (s, 3H); MS: m/z 428 (M+1) + .
Example 17
3-Chloro-2-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0357] Yield: 46%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.56 (s, 1H), 8.93-8.94 (d, 1H, J=1.8 Hz), 8.70-8.72 (dd, 1H, J=4.8, 1.5 Hz), 8.40 (s, 1H), 8.10-8.14 (m, 1H), 8.08 (s, 1H), 7.91-7.92 (d, 1H, J=1.5 Hz), 7.89-7.90 (d, 2H, J=1.2 Hz), 7.78-7.82 (m, 1H), 7.62-7.66 (m, 1H), 7.19-7.24 (dt, 1H, J=8.1, 0.6 Hz), 3.44 (s, 3H); MS m/z 444 (M+1) + .
Example 18
3-Chloro-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0358] Yield: 57%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.00 (s, 1H), 8.67-8.69 (d, 1H, J=4.5 Hz), 8.35 (s, 1H), 8.18-8.20 (d, 1H, J=8.1 Hz), 8.09 (s, 1H), 7.85-7.98 (m, 3H), 7.80-7.84 (m, 1H), 7.53-7.65 (m, 1H), 7.35-7.38 (d, 2H, J=9.3 Hz), 3.29 (s, 3H); MS: m/z 444 (M+1) + .
Example 19
2-Fluoro-N, 5-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0359] Yield: 60.06%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.67 (s, 1H), 8.97-8.98 (d, 1H, J=2.1 Hz), 8.67-8.69 (dd, 1H, J=1.2, 4.8 Hz), 8.32 (s, 1H), 8.14-8.17 (m, 1H), 8.02 (s, 1H), 7.87 (s, 2H), 7.60-7.65 (m, 1H), 7.55-7.56 (d, 1H, J=1.5 Hz), 7.39-7.42 (m, 1H), 7.24-7.27 (t, 1H, J=1.8 Hz), 3.39 (s, 3H), 1.90 (s, 3H); MS: m/z 424 (M+1) + .
Example 20
3-Fluoro-N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0360] Yield: 48%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.74 (s, 1H), 9.00-9.01 (d, 1H, J=1.8 Hz), 8.68-8.70 (dd, 1H, J=4.8, 1.2 Hz), 8.34 (s, 1H), 8.16-8.20 (m, 1H), 8.06 (s, 1H), 7.91 (s, 2H), 7.62-7.64 (m, 1H), 7.56-7.60 (m, 2H), 7.45-7.52 (m, 1H), 3.28 (s, 3H), 2.21 (s, 3H); MS m/z 424 (M+1) + .
Example 21
5-Fluoro-N, 2-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0361] Yield: 61%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.53 (s, 1H), 8.89-8.90 (d, 1H, J=2.1 Hz), 8.65-8.67 (dd, 1H, J=1.2, 4.5 Hz), 8.31 (s, 1H), 8.02-8.07 (m, 2H), 7.85 (s, 2H), 7.55-7.60 (m, 2H), 7.34-7.44 (m, 2H), 3.39 (s, 3H), 3.31 (s, 3H); MS: m/z 424 (M+1) + .
Example 21a
3-(3-((2-(5-fluoro-2-methylphenylsulfonyl)-2-methylhydrazono) methyl)imidazo[1,2-a]pyridin-6-yl)pyridine 1-oxide
[0362] To an ice-cooled solution of 5-fluoro-N, 2-dimethyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide (step 1, 18 mg, 0.043 mmol) in CH 2 Cl 2 was added 3-chloroperoxybenzoic acid (14.46 mg, 0.065 mmol). The reaction mixture was stirred for 3 h at RT. The reaction mixture was then poured on to water. Organic layer was separated, washed with saturated solution of NaHCO 3 and dried over Na 2 SO 4 . Crude compound was purified by column chromatography (silica gel, 5% EtOAc in petroleum ether) to obtain the title compound. Yield: 64%; 1 H NMR (DMSO-d 6 ; 300 MHz,): δ 9.45 (s, 1H), 8.57 (s, 1H), 8.32-8.31 (m, 2H), 8.03 (s, 1H), 7.83-7.79 (m, 2H), 7.67-7.64 (dd, 1H, J=8.4 Hz, 2.4 Hz), 7.56 (m, 1H), 7.43-7.36 (m, 3H), 3.40 (s, 3H), 2.54 (s, 3H); MS: m/z 440 (M+1) + .
Example 22
4-Bromo-N, 3-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0363] Yield: 39.7%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.78 (s, 1H), 9.03-9.04 (d, 1H, J=2.1 Hz), 8.71-8.73 (dd, 1H, J=1.2, 4.8 Hz), 8.32 (s, 1H), 8.23-8.26 (m, 1H), 8.15 (s, 1H), 8.02-8.06 (dd, 1H, J=1.5, 9.3 Hz), 7.94-7.97 (d, 1H, J=9.3 Hz), 7.73-7.74 (d, 1H, J=2.1 Hz), 7.68-7.72 (m, 2H), 7.50-7.54 (dd, 1H, J=2.1, 8.4 Hz), 3.29 (s, 3H), 2.17 (s, 3H); MS: m/z 484 (M+1) + .
Example 23
N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-3,5-bis(trifluoromethyl)benzenesulfonohydrazide
[0364] Yield: 47%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.79 (s, 1H), 9.01-9.02 (d, 1H, J=2.1 Hz), 8.64-8.66 (dd, 1H, J=1.2, 4.8 Hz), 8.44 (s, 1H), 8.35 (s, 1H), 8.28 (s, 2H), 8.17-8.21 (m, 1H), 8.05 (S, 1H), 7.89-7.94 (m, 2H), 7.57-7.61 (m, 1H), 3.36 (s, 3H); MS: m/z 528 (M+1) + .
Example 24
3-Cyano-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0365] Yield: 37%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.71 (s, 1H), 8.99-9.00 (d, 1H, J=1.5 Hz), 8.67-8.69 (dd, 1H, J=9, 4.8 Hz), 8.40-8.42 (dd, 1H, J=8.4, 2.4 Hz), 8.38 (s, 1H), 8.16-8.19 (m, 2H), 8.10 (s, 1H), 7.92-7.93 (m, 2H), 7.66-7.69 (d, 1H, J=9 Hz), 7.60-7.63 (m, 1H), 3.31 (s, 3H); MS: m/z 435 (M+1) + .
Example 25
N, 2-dimethyl-5 nitro-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)benzenesulfonohydrazide
[0366] Yield: 35%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.58 (s, 1H), 8.86-8.87 (d, 1H, J=3 Hz), 8.61-8.63 (dd, 1H, J=1.2, 4.8 Hz), 8.53-8.54 (d, 1H, J=3 Hz), 8.35 (s, 1H), 8.28-8.32 (m, 1H), 8.06-8.10 (m, 1H), 8.03 (s, 1H), 7.86 (s, 2H), 7.68-7.71 (d, 1H, J=8.4 Hz), 7.58-7.56 (m, 1H), 3.41 (s, 3H), 2.66 (s, 3H); MS: m/z 451 (M+1).
Example 26
2-Bromo-4,6-difluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0367] Yield: 17.85%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.51 (s, 1H), 8.86 (s, 1H), 8.68 (s, 1H), 8.39 (s, 1H), 8.08 (s, 1H), 8.03-8.05 (d, 1H, J=6.6 Hz), 7.88 (s, 2H), 7.72-7.73 (d, 1H, J=1.2 Hz), 7.59 (S, 1H), 7.47-7.49 (m, 1H), 3.52 (s, 3H); MS: m/z 506 (M+1) + .
Example 27
N, 2,4,6-tetramethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0368] Yield: 37%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.06 (s, 1H), 8.70-7.71 (d, 2H, J=2.7 Hz), 8.25 (s, 1H), 7.98 (s, 1H), 7.93-7.97 (m, 1H), 7.80-7.83 (d, 1H, J=9.3 Hz), 7.65-7.69 (dd, 1H, J=1.8, 9.3 Hz), 7.56-7.60 (m, 1H), 6.87 (s, 2H), 3.36 (s, 3H), 2.43 (s, 6H), 2.16 (s, 3H); MS: m/z 434 (M+1) + .
Example 28
N-methyl-1-phenyl-N′-((6-pyridin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0369] Yield: 50%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.60 (s, 1H), 8.97-8.98 (d, 1H, J=2.1 Hz), 8.61-8.63 (dd, 1H, J=1.2, 4.5 Hz), 8.21 (s, 1H), 8.11-8.14 (m, 1H), 8.01 (s, 1H), 7.81-7.89 (m, 2H), 7.48-7.54 (m, 1H), 7.23-7.26 (m, 2H), 7.07-7.13 (m, 3H), 4.66 (s, 2H), 3.20 (s, 3H); MS: m/z 406 (M+1) + .
Example 29
N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) thiophene-2-sulfonohydrazide
[0370] Yield: 64%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.90 (s, 1H), 9.03 (s, 1H), 8.62-8.63 (d, 1H, J=4.2 Hz), 8.35 (s, 1H), 8.18-8.20 (d, 1H, J=7.8 Hz), 8.05 (s, 1H), 7.87-7.96 (m, 3H), 7.69-7.70 (d, 1H, J=3.3 Hz), 7.54-7.59 (m, 1H), 7.15-7.18 (t, 1H, J=3.9, 8.4 Hz), 3.19 (s, 3H); MS: m/z 398 (M+1) + .
Example 30
N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) quinoline-8-sulfonohydrazide
[0371] Yield: 64%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.34 (s, 1H), 8.98-8.99 (d, 1H, J=3 Hz), 8.85 (s, 1H), 8.75-8.76 (d, 1H, J=4.8 Hz), 8.41-8.43 (d, 1H, J=7.2 Hz), 8.16-8.19 (d, 3H, J=7.8 Hz), 8.03-8.06 (d, 1H, J=8.1 Hz), 7.90 (s, 1H), 7.77 (s, 2H), 7.60-7.73 (m, 2H), 7.27-7.32 (t, 1H, J=7.8 Hz), 3.68 (s, 3H); MS: m/z 443 (M+1) + .
Example 31
N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) cyclohexanesulfonohydrazide
[0372] Yield: 20%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.84 (s, 1H), 8.97-8.98 (d, 1H, J=1.8 Hz), 8.61-8.63 (dd, 1H, J=1.2, 4.5 Hz), 8.26 (s, 1H), 8.14-8.17 (m, 1H), 8.05 (s, 1H), 7.88 (s, 2H), 7.52-7.56 (m, 1H), 3.38 (s, 3H), 1.98-2.02 (d, 2H, J=11.4 Hz), 1.70-1.74 (m, 2H), 1.44-1.53 (m, 3H), 1.20-1.24 (m, 3H); MS: m/z 398 (M+1) + .
Example 32
3-Fluoro-N, 4-dimethyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0373] Yield: 48%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.74 (s, 1H), 9.00-9.01 (d, 1H, J=1.8 Hz), 8.68-8.70 (dd, 1H, J=4.8, 1.2 Hz), 8.34 (s, 1H), 8.16-8.20 (m, 1H), 8.06 (s, 1H), 7.91 (s, 2H), 7.62-7.64 (m, 1H), 7.56-7.60 (m, 2H), 7.45-7.52 (m, 1H), 3.28 (s, 3H), 2.21 (s, 3H); MS: m/z 424 (M+1) + .
Example 33
3-Cyano-4-fluoro-N-methyl-N′-((6-(pyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0374] Yield: 37%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.71 (s, 1H), 8.99-9.00 (d, 1H, J=1.5 Hz), 8.67-8.69 (dd, 1H, J=9, 4.8 Hz), 8.40-8.42 (dd, 1H, J=8.4, 2.4 Hz), 8.38 (s, 1H), 8.16-8.19 (m, 2H), 8.10 (s, 1H), 7.92-7.93 (m, 2H), 7.66-7.69 (d, 1H, J=9 Hz), 7.60-7.63 (m, 1H), 3.31 (s, 3H); MS: m/z 435 (M+1) + .
Example 34
(E)-2,3,4-Trifluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0375] Yield: 50%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.64 (s, 1H), 8.94-8.95 (d, 1H, J=1.8 Hz), 8.68-8.69 (dd, 1H, J=1.2, 4.5 Hz), 8.40 (s, 1H), 8.12-8.15 (m, 1H), 8.08 (s, 1H), 7.90 (s, 2H), 7.63-7.74 (m, 1H), 7.59-7.62 (m, 1H), 7.33-7.41 (m, 1H), 3.39 (s, 3H); MS: m/z 446 (M+1) + .
Example 35
(E)-4-bromo-2,5-difluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0376] Yield: 16%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.69 (s, 1H), 8.98 (s, 1H), 8.67-8.68 (d, 1H, J=4.5 Hz), 8.39 (s, 1H), 8.08-8.15 (m, 1H), 8.05 (s, 1H), 8.00-8.03 (m, 1H), 7.88 (s, 2H), 7.71-7.75 (t, 1H, J=6, 7.2 Hz), 7.60-7.63 (m, 1H), 3.40 (s, 3H); MS: m/z 506 (M+1) + .
Example 36
(E)-2-bromo-4-fluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0377] Yield: 23%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.28 (s, 1H), 8.82-8.83 (d, 1H, J=2.1 Hz), 8.72-8.74 (dd, 1H, J=1.5, 4.8 Hz), 8.35 (s, 1H), 8.08-8.13 (m, 1H), 8.05 (s, 1H), 8.02-8.03 (m, 1H), 7.78-7.88 (m, 3H), 7.63-7.67 (m, 1H), 6.95-6.98 (t, 1H, J=2.7, 6.3 Hz), 3.55 (s, 3H); MS: m/z 488 (M+1) + .
Example 37
(E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide
[0378] Yield: 29%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.79 (s, 1H), 9.02 (s, 1H), 8.67-8.68 (d, 1H, J=3 Hz), 8.34 (s, 1H), 8.12-8.21 (m, 2H), 8.00-8.05 (m, 3H), 7.89-7.94 (m, 2H), 7.77-7.82 (t, 1H, J=7.8 Hz), 7.59-7.63 (m, 1H), 3.31 (s, 3H); MS: m/z 460 (M+1) + .
Example 38
(E)-4-bromo-2,6-dichloro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0379] Yield: 8%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.29 (s, 1H), 8.78 (s, 1H), 8.69-8.70 (d, 1H, J=4.5 Hz), 8.35 (s, 1H), 8.06 (s, 1H), 7.97-7.99 (d, 1H, J=8.1 Hz), 7.85-7.88 (m, 3H), 7.77-7.80 (m, 1H), 7.57-7.61 (m, 1H), 3.54 (s, 3H); MS: m/z 537 (M+1) + .
Example 39
(E)-3-chloro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0380] Yield: 48%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.73 (s, 1H), 9.04 (s, 1H), 8.68-8.69 (d, 1H, J=4.8 Hz), 8.35 (s, 1H), 8.01-8.19 (m, 1H), 8.11 (s, 1H), 7.89-7.95 (m, 2H), 7.73-7.83 (m, 3H), 7.63-7.65 (m, 2H), 3.35 (s, 3H); MS: m/z 426 (M+1) + .
Example 40
(E)-2-chloro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-4-(trifluoromethyl)benzenesulfonohydrazide
[0381] Yield: 32%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.28 (s, 1H), 8.81-8.82 (d, 1H, J=2.1 Hz), 8.72-8.74 (dd, 1H, J=1.2, 4.5 Hz), 8.38 (s, 1H), 8.22-8.25 (d, 1H, J=8.1 Hz), 8.12 (s, 1H), 8.02-8.06 (m, 2H), 7.82-7.88 (m, 2H), 7.62-7.67 (dd, 1H, J=4.8, 7.8 Hz), 7.47-7.50 (d, 1H, J=8.4 Hz), 3.56 (s, 3H); MS: m/z 494 (M+1) + .
Example 41
(E)-2-chloro-4-fluoro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0382] Yield: 36%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.35 (s, 1H), 8.84-8.85 (d, 1H, J=2.1 Hz), 8.71-8.73 (dd, 1H, J=1.5, 4.8 Hz), 8.34 (s, 1H), 8.08-8.11 (m, 1H), 8.04-8.07 (m, 2H), 7.80-7.88 (m, 2H), 7.69-7.73 (dd, 1H, J=2.4, 8.7 Hz), 7.63-7.67 (m, 1H), 6.97-7.04 (m, 1H), 3.52 (s, 3H); MS: m/z 444 (M+1) + .
Example 42
(E)-N, 1,2-trimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-1H-imidazole-4-sulfonohydrazide
[0383] Yield: 44%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 8.99 (s, 1H), 9.09 (s, 1H), 8.64-8.66 (d, 1H, J=4.5 Hz), 8.29 (s, 2H), 8.01 (s, 1H), 7.85-7.94 (m, 2H), 7.71 (s, 1H), 7.56-7.60 (dd, 1H, J=4.8, 7.8 Hz), 3.47 (s, 3H), 3.29 (s, 3H), 2.10 (s, 3H); MS m/z 410 (M+1) + .
Example 43
(E)-4-chloro-N, 2,5-trimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0384] Yield: 35%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.64 (s, 1H), 8.96-8.73 (d, 1H, J=2.1 Hz), 8.68-8.70 (dd, 1H, J=1.5, 4.8 Hz), 8.31 (s, 1H), 8.12-8.16 (m, 1H), 8.04 (s, 1H), 7.87-7.88 (d, 2H, J=1.2 Hz), 7.77 (s, 1H), 7.60-7.64 (m, 1H), 7.48 (s, 1H), 3.39 (s, 3H), 2.52 (s, 3H), 1.95 (s, 3H); MS: m/z 454 (M+1) + .
Example 44
(E)-2,5-difluoro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0385] Yield: 57%; 1 H NMR (300 MHz, CDCl 3 ): δ 9.65 (s, 1H), 8.93-8.94 (d, 1H, J=1.8 Hz), 8.72-8.74 (dd, 1H, J=1.2, 4.8 Hz), 8.02-8.03 (m, 1H), 7.99-8.00 (m, 1H), 7.95 (s, 1H), 7.82-7.85 (m, 1H), 7.64-7.68 (dd, 1H, J=1.8, 9.3 Hz), 7.58-7.63 (m, 1H), 7.50-7.55 (m, 1H), 7.11-7.19 (m, 2H), 3.51 (s, 3H); MS: m/z 428 (M+1) + .
Example 45
(E)-5-fluoro-2-methoxy-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0386] Yield: 51%; 1 H NMR (300 MHz, CDCl 3 ): δ 9.57 (s, 1H), 8.91 (s, 1H), 8.74-8.75 (d, 1H, J=3.6 Hz), 7.97-8.00 (d, 1H, J=7.5 Hz), 7.92 (s, 2H), 7.81-7.84 (d, 1H, J=9 Hz), 7.54-7.70 (m, 3H), 7.10-7.16 (m, 1H), 6.87-6.91 (m, 1H), 3.86 (s, 3H), 3.56 (s, 3H); MS: m/z 440 (M+1) + .
Example 46
(E)-4-Iodo-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0387] Yield: 25%; 1 H NMR (300 MHz, DMSO-d 6 ): 9.70 (s, 1H), 8.99 (s, 1H), 8.68 (s, 1H), 8.33 (s, 1H), 8.15 (m, 2H), 7.90 (m, 3H), 7.61 (m, 3H), 3.25 (s, 3H); MS: m/z 518 (M+1) +
Example 47
(E)-2′-Fluoro-N-methyl-N′-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5′-(trifluoromethyl)biphenyl-4-sulfonohydrazide
[0388] Yield: 53%; 1 H NMR (300 MHz, DMSO-d 6 ): 9.78 (s, 1H), 9.01 (s, 1H), 8.65 (s, 1H), 8.37 (s, 1H), 8.20 (m, 11H), 3.32 (s, 3H); MS: m/z 554 (M+1) + .
Example 48
4-Methyl-3-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)benzoic acid
[0389] Yield: 13%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 12.6-13.8 (bs, 1H), 9.64 (s, 1H), 8.90 (s, 1H), 8.61-8.62 (d, 1H, J=7.5 Hz), 8.38 (s, 1H), 8.31 (s, 1H), 8.04-8.07 (d, 1H, J=4.8 Hz), 7.97-8.01 (m, 2H), 7.85 (s, 2H), 7.50-7.55 (m, 2H), 3.34 (s, 3H), 2.61 (s, 3H); MS: m/z 450 (M+1) + .
Example 49
4-Methoxy-3-(1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinylsulfonyl)benzamide
[0390] Yield: 14.56%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.60 (s, 1H), 8.94 (s, 1H), 8.62-8.63 (d, 1H, J=4.2 Hz), 8.44-8.45 (d, 1H, J=1.8 Hz), 8.23 (s, 1H), 8.04-8.07 (dd, 1H, J=5.7 Hz, 1.8 Hz), 7.98 (bs, 3H), 7.80-7.87 (m, 2H), 7.61-7.65 (m, 1H), 7.35 (s, 1H), 7.23-7.26 (d, 1H, J=8.7 Hz), 3.84 (s, 3H), 3.42 (s, 3H); MS: m/z 434(M+1) + .
Example 50
(E)-N, 2,5-trimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0391] Yield: 40%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.75 (s, 1H), 8.94 (s, 1H), 8.72-8.73 (d, 1H, J=3.9 Hz), 8.05-8.09 (m, 1H), 7.91-7.96 (m, 2H), 7.82-7.86 (d, 1H, J=9.3 Hz), 7.73 (s, 1H), 764-7.67 (dd, 1H, J=1.8 & 9.3 Hz), 7.52-7.55 (m, 1H), 7.13-7.15 (m, 2H), 3.46 (s, 3H), 2.52 (s, 3H), 1.95 (s, 3H); MS: m/z 420 (M+1) + .
Example 51
(E)-2,5-dibromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0392] Yield: 25%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.60 (s, 1H), 8.95 (s, 1H), 8.73-8.74 (d, 1H, J=3.9 Hz), 8.20-8.21 (d, 1H, J=2.4 Hz), 8.05-8.08 (m, 1H), 7.97 (s, 1H), 7.93 (s, 1H), 7.81-7.84 (d, 1H, J=9.3 Hz), 7.64-7.68 (dd, 1H, J=1.8 & 9.3 Hz), 7.55-7.70 (m, 1H), 7.51-7.54 (d, 1H, J=8.4 Hz), 7.36-7.40 (dd, 1H, J=2.4 & 8.4 Hz), 3.65 (s, 3H); MS: m/z 549.9 (M+1) + .
Example 52
(E)-2,5-dimethoxy-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0393] Yield: 40%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.73 (s, 1H), 8.93-8.94 (d, 1H, J=1.8 Hz), 8.69-8.71 (dd, 1H, J=1.5 & 4.8 Hz), 8.04-8.08 (m, 1H), 7.88-7.92 (m, 2H), 7.77-7.80 (d, 1H, J=9.6 Hz), 7.60-7.64 (dd, 1H, J=1.8 & 9.3 Hz), 7.53-7.57 (m, 1H), 7.43-7.44 (d, 1H, J=3 Hz), 6.93-6.97 (dd, 1H, J=3 & 9 Hz), 6.85-6.88 (d, 1H, J=9 Hz), 3.83 (s, 3H), 3.55 (s, 3H), 3.37 (s, 3H); MS: m/z 452.1 (M+1) + .
Example 53
(E)-N, 2-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0394] Yield: 42%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.46 (s, 1H), 8.84-8.85 (d, 1H, J=1.8 Hz), 8.74-8.76 (dd, 1H, J=1.5 & 4.8 Hz), 7.90-8.00 (m, 4H), 7.77-7.80 (m, 1H), 7.50-7.59 (m, 2H), 7.31-7.37 (m, 1H), 7.22-7.26 (m, 1H), 6.87-6.92 (m, 1H), 3.49 (s, 3H), 1.65 (s, 3H); MS: m/z 406 (M+1) + .
Example 54
(E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide
[0395] Yield: 42%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.38 (s, 1H), 8.84-8.85 (d, 1H, J=1.8 Hz), 8.76-8.78 (m, 1H), 8.06-8.09 (dd, 1H, J=1.5 & 8.1 Hz), 7.97-8.00 (m, 1H), 7.95 (s, 1H), 7.92 (s, 1H), 7.78-7.81 (d, 1H, J=9.3 Hz), 7.47-7.58 (m, 3H), 7.32-7.35 (m, 1H), 6.98-7.03 (m, 1H), 3.57 (s, 3H); MS: m/z 476 (M+1) + .
Example 55
(E)-5-chloro-2-methoxy-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0396] Yield: 19.90%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.65 (s, 1H), 8.95-8.96 (d, 1H, J=2.1 Hz), 8.72-8.74 (m, 1H), 8.04-8.08 (m, 1H, J=9.3 Hz), 7.89-7.91 (m, 3H), 7.87-7.88 (m, 1H), 7.78-7.81 (d, 1H, J=9.3 Hz), 7.63-7.66 (dd, 1H, J=1.8 & 9.3 Hz), 7.56-7.60 (m, 1H), 7.34-7.37 (dd, 1H, J=2.7 & 9 Hz), 3.87 (s, 3H), 3.55 (s, 3H); MS: m/z 456 (M+1) + .
Example 56
(E)-4-bromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide
[0397] Yield: 36%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.39 (s, 1H), 8.87-8.88 (d, 1H, J=2.1 Hz), 8.78-8.80 (dd, 1H, J=1.2 & 4.5 Hz), 7.92-7.99 (m, 4H), 7.80-7.83 (d, 1H, J=9 Hz), 7.53-7.61 (m, 2H), 7.47 (s, 1H), 7.14-7.17 (dd, 1H, J=1.5 & 8.4 Hz), 3.56 (s, 3H); MS: m/z 554 (M+1) + .
Example 57
(E)-2-bromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide
[0398] Yield: 25%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.62 (s, 1H), 8.92-8.93 (d, 1H, J=2.1 Hz), 8.72-8.74 (dd, 1H, J=1.5 & 4.8 Hz), 8.32-8.33 (d, 1H, J=1.8 Hz), 8.02-8.06 (m, 1H), 8.00 (s, 1H), 7.93 (s, 1H), 7.80-7.85 (m, 2H), 7.64-7.68 (dd, 1H, J=1.8 & 9.3 Hz), 7.50-7.55 (m, 2H), 3.66 (s, 3H); MS: m/z 538 (M+1) + .
Example 58
(E)-N-methyl-2-nitro-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0399] Yield: 50%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.52 (s, 1H), 8.88-8.89 (d, 1H, J=2.1 Hz), 8.77-8.79 (dd, 1H, J=1.5 & 4.8 Hz), 8.12-8.15 (m, 1H), 8.02-8.06 (m, 1H), 8.01 (s, 1H), 7.97 (s, 1H), 7.83-7.86 (d, 1H, J=9.3 Hz), 7.63-7.68 (m, 2H), 7.60-7.61 (d, 1H, J=1.8 Hz), 7.54-7.58 (dd, 1H, J=5.1&8.1 Hz), 7.30-7.33 (m, 1H), 3.55 (s, 3H); MS: m/z 437 (M+1) + .
Example 59
(E)-N-methyl-2-(methylsulfonyl)-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0400] Yield: 43%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.42 (s, 1H), 8.91-8.92 (d, 1H, J=1.8 Hz), 8.80-8.81 (m, 1H), 8.29-8.33 (m, 2H), 8.02-8.05 (m, 1H), 7.92 (s, 2H), 7.80-7.83 (d, 1H, J=9 Hz), 7.55-7.67 (m, 3H), 7.13-7.16 (m, 1H), 3.58 (s, 3H), 3.42 (s, 3H); MS: m/z 470 (M+1) + .
Example 60
(E)-N-methyl-2-phenoxy-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0401] Yield: 46.94%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.56 (s, 1H), 8.86 (s, 1H), 8.85 (s, 1H), 7.58-7.89 (m, 2H), 7.89 (s, 2H), 7.76-7.79 (d, 1H, J=9.3 Hz), 7.55-7.59 (m, 2H), 7.24-7.28 (m, 3H), 7.12 (s, 1H), 6.87-6.89 (d, 2H, J=7.8 Hz), 6.76-6.83 (m, 2H), 3.50 (s, 3H); MS: m/z 484 (M+1) + .
Example 61
(E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hexane-1-sulfonohydrazide
[0402] Yield: 51%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.89 (s, 1H), 8.96-8.97 (d, 1H, J=2.4 Hz), 8.67-8.69 (dd, 1H, J=1.2&4.5 Hz), 8.03-8.07 (m, 2H), 7.97 (s, 1H), 7.85-7.88 (d, 1H, J=9.3 Hz), 7.69-7.73 (dd, 1H, J=1.8&9.3 Hz), 7.44-7.49 (dd, 1H, J=4.8&8.1 Hz), 3.44 (s, 3H), 3.19-3.24 (m, 2H), 1.77-1.87 (m, 2H), 1.32-1.39 (m, 2H), 1.18-1.27 (m, 4H), 0.80-0.84 (m, 2H); MS: m/z 400 (M+1) + .
Example 62
(E)-N-methyl-2-morpholino-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide
[0403] Yield: 33%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.69 (s, 1H), 9.01-9.02 (d, 1H, J=2.1 Hz), 8.65-8.68 (dd, 1H, J=3.3&4.8 Hz), 8.11-8.22 (m, 2H), 7.92-8.02 (m, 2H), 7.85-7.91 (m, 3H), 7.57-7.67 (m, 2H), 3.79 (s, 4H), 3.56 (s, 3H), 3.02 (s, 4H); MS: m/z 545 (M+1) + .
Example 63
(E)-N,2-dimethyl-5-(methylsulfonyl)-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0404] Yield: 52.58%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.74 (s, 1H), 8.98-8.99 (d, 1H, J=2.1 Hz), 8.66-8.67 (m, 1H), 8.31-8.36 (m, 2H), 8.15-8.17 (dd, 1H, J=1.5 &5.7 Hz), 8.07 (s, 2H), 7.88-7.97 (m, 2H), 7.69-7.72 (d, 1H, J=8.1 Hz), 7.58-7.63 (dd, 1H, J=4.8 &7.8 Hz), 3.13 (s, 3H), 2.67 (s, 3H), 2.50 (s, 3H); MS: m/z 484 (M+1) + .
Example 64
(E)-2-bromo-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0405] Yield: 47%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.31 (s, 1H), 8.76-8.86 (m, 2H), 8.16-8.19 (dd, 1H, J=1.5 &7.8 Hz), 7.91-7.97 (m, 3H), 7.78-7.81 (d, 1H, J=9.3 Hz), 7.61-7.65 (dd, 1H, J=7.5& 8.1 Hz), 7.52-7.56 (m, 2H), 7.30 (s, 1H), 6.93-6.98 (m, 1H), 3.64 (s, 3H); MS: m/z 471 (M+1) + .
Example 65
(E)-2-chloro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-(trifluoromethyl)benzenesulfonohydrazide
[0406] Yield: 39%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.62 (s, 1H), 8.96 (s, 1H), 8.67 (s, 1H), 8.36 (s, 1H), 8.14 (m, 2H), 8.03 (s, 1H), 7.88-7.95 (m, 4H), 7.59 (s, 1H), 3.56 (s, 3H); MS: m/z 494 (M+1) + .
Example 66
(E)-N-methyl-6-morpholino-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) pyridine-3-sulfonohydrazide
[0407] Yield: 45%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.86 (s, 1H), 8.96 (s, 1H), 8.70 (s, 1H), 8.57 (s, 1H), 8.07-8.10 (m, 2H), 7.94 (s, 1H), 7.68-7.87 (m, 3H), 7.51 (s, 1H), 6.46-6.49 (d, 1H, J=8.4 Hz), 3.75 (s, 4H), 3.59 (s, 4H), 3.28 (s, 3H); MS: m/z 478 (M+1) + .
Example 67
(E)-Methyl 1-methyl-5-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)-1H-pyrrole-2-carboxylate
[0408] Yield: 39%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.91 (s, 1H), 8.96 (s, 1H), 8.68-8.69 (d, 1H, J=3 Hz), 8.09-8.10 (d, 1H, J=4.5 Hz), 8.06 (s, 1H), 7.93 (s, 1H), 7.83-7.85 (d, 1H, J=5.7 Hz), 7.68-7.70 (d, 1H, J=5.7 Hz), 7.48-7.50 (dd, 1H, J=2.7&4.2 Hz), 7.15 (s, 1H), 7.05 (s, 1H), 3.76 (s, 3H), 3.71 (s, 3H), 3.28 (s, 3H); MS: m/z 453 (M+1) + .
Example 68
(E)-N,4-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-7-sulfonohydrazide
[0409] Yield: 44%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.84 (s, 1H), 9.03 (s, 1H), 8.67 (d, 1H), 8.30 (d, 1H), 8.19-8.21 (d, 1H, J=6.9 Hz), 8.05 (s, 2H), 7.92 (s, 2H), 7.61 (s, 1H), 7.08 (s, 1H), 4.10 (s, 2H), 3.47 (s, 3H), 3.22 (s, 3H), 3.02 (s, 2H); MS: m/z 464 (M+1) + .
Example 69
(E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) pyridine-3-sulfonohydrazide
[0410] Yield: 44%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.78 (s, 1H), 9.05 (s, 1H), 8.96 (s, 1H), 8.73-8.77 (m, 2H), 8.06-8.10 (m, 3H), 7.97 (s, 1H), 7.69-7.88 (m, 2H), 7.36-7.52 (m, 2H), 3.34 (s, 3H); MS: m/z 393 (M+1) + .
Example 70
(E)-N-methyl-4-phenoxy-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0411] Yield: 40%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.87 (s, 1H), 8.96 (s, 1H), 8.67 (s, 1H), 8.03-8.08 (m, 2H), 7.93 (s, 1H), 7.83-7.86 (d, 1H, J=9 Hz), 7.67-7.67-7.76 (m, 3H), 7.36-7.45 (m, 3H), 7.28 (m, 1H), 6.99-7.01 (d, 2H, J=7.2 Hz), 6.85-6.88 (d, 2H, J=8.1 Hz), 3.31 (s, 3H); MS: m/z 484 (M+1) + .
Example 71
(E)-Methyl 3-(1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)thiophene-2-carboxylate
[0412] Yield: 48%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.53 (s, 1H), 8.89 (s, 1H), 8.68 (s, 1H), 8.34 (s, 1H), 8.06 (s, 2H), 7.87 (s, 2H), 7.75-7.77 (d, 1H, J=4.5 Hz), 7.61 (s, 1H), 7.40-7.42 (d, 1H, J=4.5 Hz), 3.80 (s, 3H), 3.49 (s, 3H); MS: m/z 456 (M+1) + .
Example 72
(E)-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) biphenyl-4-sulfonohydrazide
[0413] Yield: 46%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.77 (s, 1H), 9.01-9.02 (d, 1H, J=2.1 Hz), 8.65-8.67 (dd, 1H, J=1.5 &4.8 Hz), 8.33 (s, 1H), 8.17 (s, 1H), 8.04 (s, 2H), 7.89 (s, 2H), 7.86 (s, 1H), 7.76-7.78 (d, 1H, J=8.4 Hz), 7.72 (s, 1H), 7.59-7.64 (m, 3H), 7.41-7.45 (m, 3H), 3.29 (s, 3H); MS: m/z 468 (M+1) + .
Example 73
(E)-Methyl 5-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl) furan-2-carboxylate
[0414] Yield: 32%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.82 (s, 1H), 8.96 (s, 1H), 8.68-8.69 (d, 1H, J=3.9 Hz), 8.08-8.11 (m, 2H), 7.95 (s, 1H), 7.82-7.85 (d, 1H, J=9.3 Hz), 7.68-7.72 (dd, 1H, J=1.8 &9.3 Hz), 7.45-7.49 (dd, 1H, J=5.1& 7.8 Hz), 7.07-7.12 (m, 2H), 3.72 (s, 3H), 3.48 (s, 3H); MS m/z 440 (M+1) + .
Example 74
(E)-4-chloro-N-methyl-3-nitro-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0415] Yield: 34%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.72 (s, 1H), 8.98-8.99 (d, 1H, J=2.1 Hz), 8.64-8.66 (dd, 1H, J=1.5 &4.8 Hz), 8.42-8.43 (d, 1H, J=2.1 Hz), 8.37 (s, 1H), 8.14-8.17 (m, 1H), 8.03-8.07 (m, 2H), 7.90-7.94 (m, 3H), 7.55-7.60 (dd, 1H, J=4.8 &7.8 Hz), 3.29 (s, 3H); MS: m/z 471 (M+1) + .
Example 75
(E)-5-bromo-2-methoxy-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0416] Yield: 47.5%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.68 (s, 1H), 8.95 (s, 1H), 8.72-8.95 (m, 1H), 8.06-8.10 (m, 1H), 7.97-7.98 (d, 1H, J=2.4 Hz), 7.88-7.89 (d, 2H, J=3.9 Hz), 7.78-7.81 (d, 1H, J=9.6 Hz), 7.63-7.67 (dd, 1H, J=1.8, 9.3 Hz), 7.56-7.60 (m, 1H), 7.46-7.49 (dd, 1H, J=2.4, 8.7 Hz), 6.79-6.82 (d, 1H, J=8.7 Hz), 3.85 (s, 3H), 3.53 (s, 3H); MS: m/z 500 (M+1) + .
Example 76
(E)-3-chloro-N, 2-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0417] Yield: 45%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.38 (s, 1H), 8.84 (s, 1H), 8.5 (s, 1H), 7.91-7.95 (m, 4H), 7.78-7.81 (d, 1H, J=9.3 Hz), 7.42-7.58 (m, 3H), 6.77-6.82 (m, 1H), 3.49 (s, 3H), 2.59 (s, 3H); MS: m/z 439 (M+1) + .
Example 77
(E)-5-chloro-2-fluoro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0418] Yield: 38%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.68 (s, 1H), 8.95 (s, 1H), 8.72-8.95 (m, 1H), 8.06-8.10 (m, 1H), 7.97-7.98 (d, 1H, J=2.4 Hz), 7.88-7.89 (d, 2H, J=3.9 Hz), 7.78-7.81 (d, 1H, J=9.6 Hz), 7.63-7.67 (dd, 1H, J=1.8, 9.3 Hz), 7.56-7.60 (m, 1H), 7.46-7.49 (dd, 1H, J=2.4, 8.7 Hz), 6.79-6.82 (d, 1H, J=8.7 Hz), 3.53 (s, 3H); MS m/z 443 (M+1) + .
Example 78
(E)-4-Fluoro-N, 2-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0419] Yield: 48%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.45 (s, 1H), 8.88 (s, 1H), 8.77 (s, 1H), 7.80-8.05 (m, 4H), 7.81-7.84 (d, 1H, J=9.3 Hz), 7.51-7.61 (m, 2H), 6.92-6.96 (dd, 1H, J=2.4& 9 Hz), 6.55-6.61 (m, 1H), 3.52 (s, 3H), 2.55 (s, 3H); MS: m/z 423 (M+1) + .
Example 79
(E)-2-methoxy-N, 6-dimethyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0420] Yield: 51%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.72 (s, 1H), 8.96-8.97 (d, 1H, J=1.8 Hz), 8.72-8.74 (dd, 1H, J=1.2&4.5 Hz), 8.10-8.14 (m, 1H), 7.78-7.88 (m, 3H), 7.64-7.70 (dd, 2H, J=2.1&16.8 Hz), 7.55-7.61 (m, 1H), 7.16-7.19 (dd, 1H, J=1.8&8.4 Hz), 6.79-6.82 (d, 1H, J=8.4 Hz), 3.84 (s, 3H), 3.55 (s, 3H), 1.81 (s, 3H); MS: m/z 435 (M+1) + .
Example 80
(E)-4-Bromo-2-chloro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0421] Yield: 31%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.38 (s, 1H), 8.79-8.87 (m, 2H), 7.86-8.02 (m, 5H), 7.54-7.63 (m, 3H), 7.07-7.11 (dd, 1H, J=1.8 & 8.4 Hz), 3.61 (s, 3H); MS: m/z 506 (M+1) + .
Example 81
(E)-2-chloro-N-methyl-N′-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0422] Yield: 46%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.39 (s, 1H), 8.34 (s, 1H), 8.78-8.79 (d, 1H, J=3.9 Hz), 8.14-8.17 (dd, 1H, J=1.2&7.8 Hz), 7.97-8.01 (m, 1H), 7.94 (s, 2H), 7.83-7.86 (d, 1H, J=9.3 Hz), 7.54-7.61 (m, 2H), 7.43-7.46 (dd, 1H, J=1.2&8.1 Hz), 7.35-7.40 (m, 1H), 6.99 (s, 1H), 3.63 (s, 3H); MS: m/z 426 (M+1) + .
Example 82
(E)-N-(4-(1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) hydrazinylsulfonyl)phenyl)acetamide
[0423] Yield: 48%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 10.31 (s, 1H), 9.75 (s, 1H), 9.00-9.01 (d, 1H, J=2.1 Hz), 8.67-8.69 (dd, 1H, J=1.5&4.8 Hz), 8.28 (s, 1H), 8.15 (s, 1H), 8.03 (s, 1H), 7.88-7.90 (m, 2H), 7.74 (s, 1H), 7.71 (s, 1H), 7.60-7.65 (m, 3H), 3.24 (s, 3H), 2.02 (s, 3H); MS: m/z 447 (M+1) + .
Example 83
N′-((6-(6-fluoropyridine-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-n, 2-dimethyl-5-nitrobenzenesulfonohydrazide
[0424] The title compound was prepared by following the procedure as described for example 1, using Intermediate 2, methyl hydrazine and 2-methyl-5-nitrobenzene-1-sulfonyl chloride.
[0425] Yield: 25%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.47 (s, 1H), 8.51-8.54 (d, 2H, J=9 Hz), 8.25-8.34 (m, 3H), 7.99-8.03 (d, 1H, J=9 Hz), 7.68-7.88 (m, 3H), 7.36-7.40 (dd, 1H, J=2.1, 8.4 Hz), 3.43 (s, 3H), 2.65 (s, 3H); MS: m/z 469 (M+1) + .
Example 84
(E)-N-ethyl-2-methyl-5-nitro-N′-((6-(pyridin-3-ypimidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0426] To a solution of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (Intermediate 1, 100 mg, 0.444 mmol) in ethanol (10 mL) was added ethyl hydrazine oxalate (120 mg, 0.7998 mmol) at RT. The reaction was heated at 80° C. for 4 h. EtOH was evaporated. Pyridine (5 mL) was added to this residue, followed by addition of 2-methyl-5-nitro benzene sulfonylchloride (126 mg, 0.533 mmol). The reaction mixture was stirred at RT overnight. Pyridine was evaporated. Water was added to this residue and extracted with dichloromethane. Organic layer was dried over sodium sulphate and evaporated.The crude product was purified by column chromatography (silica gel, 1.5% methanol in chloroform) to obtain the title compound. Yield: 15 mg (7%); 1 HNMR (CDCl 3 ; 300 MHz): δ 9.57 (s, 1H), 8.75 (s, 1H), 8.69 (m, 2H), 8.31 (s, 1H), 8.18 (dd, 1H, J=8.4, 2.1 Hz), 7.99 (s, 1H), 7.91 (d, 1H, J=8.1 Hz), 7.82 (d, 1H, J=9.3 Hz), 7.63 (dd, 1H, J=9, 1.5 Hz), 7.46 (t, 2H, J=8.1 Hz), 3.90 (q, 2H, J=7.2 Hz), 2.70 (s, 3H), 1.32 (t, 3H, J=6.9 Hz); MS: m/z 463 (M−1) + .
[0427] The compounds of Examples 85 and 86 were prepared by following the procedure as described for Example 1, using 6-(pyridin-4-yl)imidazo[1,2-a]pyridine-3-carbaldehyde, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 85
N, 2-dimethyl-5-nitro-N′-((6-(pyridine-4-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0428] Yield: 21%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 0.78 (s, 1H), 8.69-8.71 (d, 2H, J=5.7 Hz), 8.56-8.57 (d, 1H, J=2.1 Hz), 8.35 (s, 1H), 8.29-8.33 (dd, 1H, J=2.4, 8.7 Hz), 8.04 (s, 1H), 7.85-7.95 (m, 2H), 7.72-7.74 (d, 2H, J=6 Hz), 7.69 (s, 1H), 3.42 (s, 3H), 2.67 (s, 3H); MS: m/z 451 (M+1) + .
Example 86
5-Fluoro-N, 2-dimethyl-N′-((6-(pyridine-4-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0429] Yield: 27%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.67 (s, 1H), 8.70-8.72 (d, 2H, J=6 Hz), 8.32 (s, 1H), 8.04 (s, 1H), 7.85 (s, 2H), 7.65-7.68 (m, 2H), 7.62-7.63 (d, 1H, J=2.7 Hz), 7.37-7.46 (m, 2H), 3.43 (s, 3H), 2.48 (s, 3H); MS: m/z 424 (M+1) + .
[0430] The compounds of Example 87-98 were prepared by following the procedure as described for Example 1, using Intermediate 3, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 87
(E)-5-Fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide
[0431] Yield: 48%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.40 (s, 1H), 8.34-8.36 (d, 1H, J=4.8 Hz), 8.29 (s, 1H), 8.08-8.15 (m, 1H), 8.04 (s, 1H), 7.83-7.87 (d, 1H, J=9.6 Hz), 7.66-7.69 (d, 1H, J=9.3 Hz), 7.52-7.59 (m, 2H), 7.37-7.42 (m, 1H), 7.30-7.34 (m, 1H), 3.42 (s, 3H), 2.43 (s, 3H); MS: m/z 442 (M+1) + .
Example 88
(E)-5-Fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide
[0432] Yield: 54%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.32 (s, 1H), 8.38 (s, 1H), 8.26 (s, 1H), 8.09-8.12 (m, 1H), 8.04 (s, 1H), 7.79-7.87 (m, 1H), 7.67-7.70 (d, 1H, 9 Hz), 7.61 (s, 1H), 7.41 (s, 2H), 7.20 (s, 1H), 3.82 (s, 3H), 3.47 (s, 3H); MS: m/z 458 (M+1) + .
Example 89
(E)-3-fluoro-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide
[0433] Yield: 55%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.76 (s, 1H), 8.33-8.35 (d, 1H, J=4.8 Hz), 8.04-8.11 (m, 2H), 7.97 (s, 1H), 7.86-7.89 (d, 1H, J=9.3 Hz), 7.68-7.72 (d, 1H, J=9.3 Hz), 7.59-7.62 (d, 1H, J=7.8 Hz), 7.50-7.60 (m, 1H), 7.36-7.46 (m, 2H), 7.23-7.26 (m, 1H), 3.33 (s, 3H); MS: m/z 428 (M+1) + .
Example 90
(E)-5-chloro-2-fluoro-N′-((6-(2-fluoropyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide
[0434] Yield: 36.9%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.64 (s, 1H), 8.34-8.36 (d, 1H, J=7.5 Hz), 8.09 (s, 1H), 8.01 (s, 1H), 7.96 (s, 1H), 7.77-7.85 (m, 2H), 7.72 (s, 1H), 7.43-7.49 (m, 2H), 7.09-7.13 (d, 1H, J=9.3 Hz), 3.51 (s, 3H); MS: m/z 462 (M+1) + .
Example 91
(E)-5-bromo-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide
[0435] Yield: 53%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.60 (s, 1H), 8.34-8.36 (m, 1H), 8.09-8.13 (m, 1H), 7.90-7.92 (m, 2H), 7.77-7.80 (d, 1H, J=9.3 Hz), 7.70-7.72 (m, 1H), 7.49-7.56 (m, 3H), 6.81-6.84 (d, 1H, J=8.7 Hz), 3.88 (s, 3H), 3.55 (s, 3H); MS: m/z 518 (M+1) + .
Example 92
(E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2,5-dimethoxy-N-methylbenzenesulfonohydrazide
[0436] Yield: 54.9%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.60 (s, 1H), 8.32-8.33 (d, 1H, J=1.5 Hz), 8.04-8.10 (m, 1H), 7.89 (s, 2H), 7.76-7.79 (m, 1H), 7.59-7.72 (m, 1H), 7.48-7.52 (m, 1H), 7.35-7.36 (d, 1H, J=3 Hz), 6.93-6.97 (dd, 1H, 3&9 Hz), 6.88-6.90 (d, 1H, J=6.9 Hz), 3.83 (s, 3H), 3.58 (s, 3H), 3.55 (s, 3H); MS: m/z 470 (M+1) + .
Example 93
(E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N, 2-dimethyl-5-(methylsulfonyl)benzenesulfonohydrazide
[0437] Yield: 47%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.56 (s, 1H), 8.34 (s, 2H), 8.27-8.28 (d, 1H, J=1.8 Hz), 8.14-8.21 (m, 1H), 8.05 (s, 1H), 8.02-8.03 (d, 1H, J=2.1 Hz), 7.86-7.89 (d, 1H, J=9.3 Hz), 7.66-7.76 (m, 2H), 7.54-7.59 (m, 1H), 3.37 (s, 3H), 3.13 (s, 3H), 2.64 (s, 3H); MS: m/z 502 (M+1) + .
Example 94
(E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylhexane-1-sulfonohydrazide
[0438] Yield: 61%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.85 (s, 1H), 8.28-8.29 (dd, 1H, J=1.5&3.6 Hz), 8.07-8.08 (d, 1H, J=1.8 Hz), 8.04 (s, 1H), 7.98 (s, 1H), 7.84-7.87 (d, 1H, J=9.3 Hz), 7.66-7.70 (m, 1H), 7.37-7.41 (m, 1H), 3.43 (s, 3H), 3.22-3.27 (m, 2H), 1.78-1.86 (m, 2H), 1.30-1.45 (m, 2H), 1.22-1.27 (m, 4H), 0.82-0.86 (m, 2H); MS: m/z 418 (M+1) + .
Example 95
(E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N, 4-dimethylbenzenesulfonohydrazide
[0439] Yield: 52%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.40 (s, 1H), 8.39-8.41 (d, 1H, J=3.6 Hz), 8.02-8.07 (m, 1H), 7.89 (s, 1H), 7.86 (s, 1H), 7.70-7.80 (d, 1H, J=9 Hz), 7.66-7.69 (d, 1H, J=8.1 Hz), 7.48-7.52 (m, 2H), 6.69 (s, 1H), 6.24-6.26 (d, 1H, J=7.8 Hz), 3.84 (s, 3H), 3.54 (s, 3H), 2.31 (s, 3H); MS: m/z 454 (M+1) + .
Example 96
(E)-2-bromo-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide
[0440] Yield: 44.77%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.26 (s, 1H), 8.40-8.42 (d, 1H, J=4.2 Hz), 8.08-8.10 (d, 1H, J=7.8 Hz), 7.97-8.02 (m, 1H), 7.93 (s, 2H), 7.78-7.81 (d, 1H, J=9.3 Hz), 7.64-7.67 (d, 1H, J=7.8 Hz), 7.48-7.57 (m, 2H), 7.23-7.28 (m, 1H), 6.81-6.86 (m, 1H), 3.64 (s, 3H); MS: m/z 490 (M+1) + .
Example 97
(E)-2-cyano-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N-methylbenzenesulfonohydrazide
[0441] Yield: 41%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.39 (s, 1H), 8.37-8.38 (d, 1H, J=3.6 Hz), 8.09-8.12 (d, 1H, J=8.1 Hz), 8.06 (s, 1H), 7.97-8.03 (m, 2H), 7.80-7.83 (d, 2H, J=8.1 Hz), 7.56-7.64 (m, 2H), 7.39-7.49 (m, 2H), 3.60 (s, 3H); MS: m/z 435 (M+1) + .
Example 98
(E)-N′-((6-(2-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N,5-dimethylbenzenesulfonohydrazide
[0442] Yield: 50%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.67 (s, 1H), 8.34-8.36 (m, 1H), 8.12-8.18 (m, 1H), 7.88 (s, 2H), 7.75-7.83 (m, 1H), 7.58-7.67 (m, 2H), 7.49-7.53 (m, 1H), 7.18-7.21 (dd, 1H, J=2.1&8.4 Hz), 6.79-6.82 (d, 1H, J=8.7 Hz), 3.86 (s, 3H), 3.54 (s, 3H), 1.87 (s, 3H); MS: m/z 454 (M+1) + .
Example 99
N, 2-Dimethyl-5-nitro-N′-((6-(quinolin-3-yl) imidazo[1,2-a]pyridine-3-yl)methylene) benzenesulfonohydrazide
[0443] The title compound was prepared by following the procedure as described for example 1, using Intermediate 4, methyl hydrazine and 2-methyl-5-nitrobenzene-1-sulfonyl chloride.
[0444] Yield: 60%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.83 (s, 1H), 9.20-9.21 (d, 1H, J=3 Hz), 8.72-8.73 (d, 1H, J=3 Hz), 8.55-8.56 (d, 1H, J=3 Hz), 8.37 (s, 1H), 8.23-8.27 (dd, 1H, J=3, 3 Hz), 8.03-8.10 (m, 4H), 7.90-7.93 (d, 1H, J=9 Hz), 7.81 (m, 1H), 7.66-7.71 (m, 2H), 3.41 (s, 3H), 2.67 (s, 3H); MS: m/z 501 (M+1) + .
Example 100
(E)-5-Fluoro-N,2-dimethyl-N′-((8-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0445] To a solution of 8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (Intermediate 5, 80 mg, 0.337 mmol) in ethanol (10 mL) was added methyl hydrazine (0.035 mL, 0.675 mmol) at RT. The reaction mixture was heated at 80° C. for 4 hours. Ethanol was evaporated. Pyridine (5 mL) was added to this residue, followed by addition 2-methyl-5-fluoro benzene sulfonylchloride (105 mg, 0.506 mmol). The reaction mixture was stirred at RT overnight. Pyridine was evaporated. Water was added to this residue and extracted with dichloromethane. Organic layer was dried over sodium sulfate and evaporated.The crude product was purified by column chromatography (silica gel, 1.5% methanol in chloroform) to obtain the title compound. Yield: 50 mg (27%); 1 H NMR (CDCl 3 ; 300 MHz): δ 9.41(s, 1H), 8.59 (s, 1H), 8.71 (d, 1H, J=3.9 Hz), 7.99 (s, 1H), 7.97 (m, 1H), 7.94 (s, 1H), 7.66 (dd, 1H, J=8.4, 2.7 Hz), 7.47 (m, 1H), 7.43 (s, 1H), 7.21 (m, 1H), 7.07 (m, 1H), 3.47 (s, 3H), 2.73 (s, 3H), 2.53 (s, 3H); MS: m/z 438 (M+1) + .
[0446] The compounds of Examples 101-114 were prepared by following the procedure as described for Example 100, using Intermediate 5, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 101
(E)-3,5-Difluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-ypimidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0447] Yield: 28%; 1 H NMR (CDCl 3 , 300M Hz): 9.59 (s, 1H), 8.91 (s, 1H) 8.68 (s, 1H), 8.09 (s, 1H,), 7.99 (d, 1H, J=7.5 Hz), 7.93 (s, 1H), 7.49-7.45 (m, 2H), 7.32 (s, 2H), 7.04 (t, 1H, J=10 Hz), 3.33 (s, 3H), 2.74 (s, 3H); MS: m/z 442(M+1) + .
Example 102
(E)-4-Bromo-2,6-difluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0448] Yield: 22% 1 H NMR (CDCl 3 , 500M Hz): −9.37 (s, 1H), 8.89 (s, 1H) 8.09 (s, 1H), 8.15 (s, 1H), 7.97 (m, 2H), 7.46 (t, 1H, J=6.5 Hz), 7.39 (s, 1H), 7.24 (d, 1H, J=7.5 Hz), 6.72 (t, 1H, J=8.5 Hz), 3.56 (s, 3H), 2.71 (s, 3H); MS: m/z 520(M+1) + .
Example 103
(E)-N,3-dimethyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0449] Yield: 30%; 1 H NMR (CDCl 3 , 300M Hz): 9.72 (s, 1H), 8.96 (s, 1H) 8.71 (d, 1H, J=4.2 Hz), 8.11 (d, 1H, J=7.8 Hz), 8.02 (s, 1H), 7.90 (s, 1H), 7.61 (m, 4H), 7.32 (m, 2H), 3.32 (s, 3H), 2.75 (s, 3H), 2.15 (s, 3H); MS: m/z 420(M+1) + .
Example 104
(E)-2-cyano-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0450] Yield: 40 mg (28%); 1 H NMR (CDCl 3 , 300M Hz): 9.19 (s, 1H), 8.76 (m, 2H), 8.17 (d, 1H, J=7.8 Hz), 8.06 (s, 1H), 7.96 (m, 2H), 7.81 (d, 1H, J=7.8 Hz), 7.62 (t, 1H, J=7.5 Hz), 7.54 (m, 3H), 3.62 (s, 3H), 2.72 (s, 3H); MS: m/z 431(M+1) + .
Example 105
(E)-3-cyano-4-fluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0451] Yield: 23%; 1 H NMR (CDCl 3 ; 300M Hz): 9.56 (s, 1H), 8.92 (d, 1H, J=1.5 Hz), 8.73 (d, 1H, J=4.5 Hz), 8.13 (s, 1H), 8.08 (m, 3H), 7.97 (s, 1H), 7.51 (m, 2H), 7.28 (m, 1H), 3.335 (s, 3H), 2.770 (s, 3H); MS: m/z 449(M+1) + .
Example 106
(E)-3-cyano-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0452] Yield: 27.58%; 1 H NMR (CDCl 3 ; 300M Hz): 9.57 (s, 1H), 8.91 (d, 2H, J=2.1 Hz), 8.73 (dd, 1H, J=4.8 Hz, 1.5 Hz), 8.11 (s, 1H), 8.07 (m, 3H), 7.95 (s, 1H), 7.81 (d, 1H, J=7.8 Hz), 7.53 (m, 3H), 3.33 (s, 3H), 2.76 (s, 3H); MS: m/z 431(M+1) + .
Example 107
(E)-4-Bromo-N,3-dimethyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0453] Yield: 38%; 1 H NMR (CDCl 3 ; 300M Hz): 9.69 (s, 1H), 8.98 (d, 1H, J=2.1 Hz), 8.72 (d, 1H, J=4.8 Hz), 8.08 (m, 2H), 7.92 (s, 1H), 7.61 (s, 1H), 7.53 (m, 4H), 3.31 (s, 3H), 2.76 (s, 3H), 2.17 (s, 3H); MS: m/z 498 (M+1) + .
Example 108
(E)-3-Methoxy-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0454] Yield: 31%; 1 H NMR (CDCl 3 ; 300M Hz): 9.77 (s, 1H), 8.95 (d, 1H, J=2.1 Hz), 8.70 (dd, 1H, J=2.1 Hz, 1.5 Hz), 8.121 (m, 1H), 7.91 (s, 1H), 7.52 (m, 2H), 7.40 (d, 1H, J=7.8 Hz), 7.29 (m, 2H), 7.05 (dd, 1H, J=2.4 Hz, 8.4 Hz), 3.56 (s, 3H), 3.31 (s, 3H), 2.78 (s, 3H); MS: m/z 436 (M+1) + .
Example 109
(E)-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-nitrobenzenesulfonohydrazide
[0455] Yield: 34%; 1 H NMR (CDCl 3 ; 300M Hz): 9.60 (s, 1H), 8.92 (d, 1H, J=1.8 Hz), 8.72 (dd, 1H, J=4.8 Hz, 1.2 Hz), 8.63 (d, 1H, J=1.8 Hz), 8.39 (dd, 1H, J=8.4 Hz, 1.2 Hz), 8.16 (m, 3H), 7.951 (s, 1H), 7.62 (t, 1H, J=8.1 Hz), 7.51 (m, 2H), 3.55 (s, 3H), 2.76 (s, 3H); MS: m/z 451 (M+1) + .
Example 110
(E)-3-Chloro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0456] Yield: 31%; 1 H NMR (CDCl 3 ; 300M Hz): 9.63 (s, 1H), 8.94 (d, 1H, J=1.8 Hz), 8.72 (d, 1H, J=4.8 Hz), 8.08 (m, 2H), 7.93 (s, 1H), 7.77 (s, 1H), 7.71 (d, 1H, J=7.8 Hz), 7.52 (t, 3H, J=6.3 Hz), 7.33 (m, 1H), 3.32 (s, 3H), 2.76 (s, 3H); MS: m/z 440 (M+1) + .
Example 111
(E)-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide
[0457] Yield: 34%; 1 H NMR (CDCl 3 ; 300M Hz): 9.64 (s, 1H), 8.93 (s, 1H), 8.70 (s, 1H), 8.08 (m, 5H), 7.79 (d, 1H, J=7.2 Hz), 7.51 (s, 3H), 3.33 (s, 3H), 2.76 (s, 3H); MS: m/z 474 (M+1) + .
Example 112
(E)-2-Bromo-4,6-difluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-ypimidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0458] Yield: 53%; 1 H NMR (CDCl 3 ; 300M Hz): 9.39 (s, 1H), 8.83 (d, 1H, J=1.8 Hz), 8.71 (dd, 1H, J=4.8 Hz, 1.5 Hz), 7.99 (s, 1H), 7.96 (t, 1H, J=1.8 Hz), 7.93 (s, 1H), 7.49 (m, 1H), 7.41 (s, 1H), 7.26 (m, 1H), 6.77 (m, 1H), 3.58 (s, 3H), 2.73 (s, 3H); MS: m/z 522(M+2) + .
Example 113
(E)-4-Chloro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-3-nitrobenzenesulfonohydrazide
[0459] Yield: 20.7%; 1 H NMR (CDCl 3 ; 300M Hz): 9.57 (s, 1H), 8.94 (d, 1H, J=2.1 Hz), 8.72 (d, 1H, J=4.5 Hz), 8.28 (d, 1H, J=2.1 Hz), 8.13 (s, 1H), 8.03 (m, 3H), 7.58 (d, 1H, J=8.4 Hz), 7.52 (m, 2H), 3.34 (s, 3H), 2.76 (s, 3H; MS: m/z 485(M+1) + .
Example 114
(E)-2-Bromo-4-fluoro-N-methyl-N′-((8-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0460] Yield: 45%; 1 H NMR (CDCl 3 , 300M Hz): 9.15 (s, 1H), 8.83 (d, 1H, J=1.8 Hz), 8.78 (d, 1H, J=3.9 Hz), 8.24 (m, 1H), 7.94 (d, 3H, J=9.9 Hz), 7.55 (m, 1H), 7.39 (d, 1H, J=2.4 Hz), 7.36 (s, 1H), 6.69 (m, 1H), 3.63 (s, 3H), 2.71 (s, 3H); MS: m/z 502(M+1) + .
Example 115
(E)-N′-((6-(1H-indol-2-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide
[0461] To a solution of 6-(1H-indol-2-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (Intermediate 6, 115 mg, 0.3691 mmol) in ethanol (10 mL) was added methyl hydrazine (0.04 mL, 0.7395 mmol) at RT. The reaction mixture was heated at 80° C. for 4 h. Ethanol was evaporated. Pyridine (5 mL) was added to this residue, followed by addition of 2-methyl-5-fluoro benzene sulfonylchloride (0.07 mL, 0.5535 mmol). The reaction mixture was stirred at RT overnight. Pyridine was evaporated. Water was added to this residue and extracted with dichloromethane. Organic layer was dried over sodium sulfate and evaporated. The crude product was purified by column chromatography (Silica gel, 1.5% methanol in chloroform) to obtain the title compound. Yield: 28 mg (17%); 1 H NMR (DMSO-d 6 ; 500 MHz): δ 11.83 (s, 1H), 9.09 (s, 1H), 9.81 (s, 1H), 8.34 (s, 1H), 8.27 (d, 1H, J=9.5 Hz), 8.08 (d, 1H, J=9.5 Hz), 7.74 (d, 1H, J=6.5 Hz), 7.61 (d, 1H, J=8 Hz), 7.43 (m, 3H), 7.18 (t, 1H, J=8), 7.07 (t, 1H, J=7.5 Hz), 6.91 (s, 1H), 3.48 (s, 3H); MS: m/z 460 (M−1) + .
Example 116
(E)-5-fluoro-N,2-dimethyl-N′-((6-(1-methyl-1H-indol-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0462] To a solution of N′-((6-(1H-indol-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide (50 mg, 1084 mmoles) in DMF (3 ml) was added NaH (6.5 mg, 0.1626 mmoles). The solution was stirred for 15 minutes and then methyl iodide was added to it. The reaction was quenched with methanol. The reaction mixture was evaporated to dryness. The residue obtained was dissolved in EtOAc washed with water and brine. EtOAc layer was separated, dried over sodium sulfate and evaporated. Crude material was purified by column chromatography (100-200 mesh size silica gel, 1.0% MeOH in CHCl 3 ). Yield: 25 mg (49%) 1 H NMR (CDCl 3 , 500 MHz): δ 9.28 (s, 1H), 8.01 (s, 1H) 7.91 (s, 1H), 7.77 (d, 1H, J=9 Hz), 7.70 (d, 1H, J=7.5 Hz), 7.59 (d, 1H, J=8 Hz), 7.49 (d, 1H, J=9.5 Hz), 7.42 (d, 1H, J=8 Hz), 7.33 (t, 1H, J=7 Hz), 7.21 (t, 1H, J=6 Hz), 7.07 (m, 1H), 6.84 (m, 1H), 6.57 (s, 1H), 3.75 (s, 3H), 3.44 (s, 3H), 2.71 (s, 3H); MS: m/z 476(M+1) +
[0463] The compounds of Examples 117-124 were prepared by following the procedure as described for Example 1, using Intermediate 7, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 117
2-Cyano-N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0464] Yield: 24.62%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 8.83 (s, 1H), 8.75-8.77 (dd, 1H, J=4.8 Hz, 1.5 Hz), 8.60 (s, 1H), 8.40 (s, 1H), 8.02 (s, 2H), 7.88-7.92 (m, 1H), 7.81-7.84 (d, 1H, J=8.1 Hz), 7.76-7.79 (dd, 1H, J=7.5 Hz, 0.6 Hz), 7.73 (s, 1H), 7.61-7.65 (dd, 1H, J=7.8 Hz, 5.1 Hz), 7.48-7.43 (m, 1H), 3.44 (s, 3H), 2.27 (s, 3H); MS: m/z 431.1 (M+1)
Example 118
5-Fluoro-N, 2-dimethyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0465] Yield: 38%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 8.98 (s, 1H), 8.70-8.72 (dd, 1H, J=4.8 Hz, 1.5 Hz), 8.607-8.612 (d, 1H, J=10.5 Hz), 7.97 (s, 1H), 7.85-7.87 (m, 2H), 7.71 (s, 1H), 7.55-7.60 (dd, 1H, J=7.5 Hz, 4.8 Hz), 7.42-7.34 (m, 3H), 3.39 (s, 3H), 2.41 (s, 3H), 2.28 (s, 3H); MS: m/z 438.1(M+1) + .
Example 119
N, 3-dimethyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0466] Yield: 34%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.20 (s, 1H), 8.73-8.75 (m, 2H), 8.26 (s, 1H), 7.97-8.02 (m, 1H), 7.97 (s, 1H), 7.74 (s, 1H), 7.61-7.65 (dd, 1H, J=8.1 Hz, 5.1 Hz), 7.47 (s, 1H), 7.41-7.43 (m, 2H), 7.20-7.25 (t, 1H, J=7.5 Hz), 3.24 (s, 3H), 2.33 (s, 3H), 2.20 (s, 3H); MS: m/z 420.1(M+1)
Example 120
3-Fluoro-N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0467] Yield: 51.48%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.15 (s, 1H), 8.71-8.74 (m, 2H), 8.31 (s, 1H), 7.99 (s, 1H), 7.96-7.97 (m, 1H), 7.75 (s, 1H), 7.61-7.64 (dd, 1H, J=7.8 Hz, 2.4 Hz), 7.46-7.50 (m, 4H), 3.27 (s, 3H), 2.32 (s, 3H); MS: m/z 424.1(M+1) + .
Example 121
3-Chloro-N-methyl-N′-((7-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0468] Yield: 40%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.18 (s, 1H), 8.72-8.74 (m, 2H), 8.30 (s, 1H), 7.98-8.01 (m, 2H), 7.76 (s, 1H), 7.70-7.72 (d, 1H, J=8.1 Hz), 7.60-7.67 (m, 3H), 7.41-7.47 (m, 1H), 3.26 (s, 3H), 2.33 (s, 3H); MS: m/z 440.1(M+1) + .
Example 122
N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-3-(trifluoromethyl)benzenesulfonohydrazide
[0469] Yield: 23%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.21 (s, 1H), 8.71-8.73 (m, 2H), 8.30 (s, 1H), 8.02-8.05 (d, 1H, J=8.1 Hz), 7.99 (s, 1H), 7.97 (s, 1H), 7.92 (s, 1H), 7.47 (s, 1H), 7.76 (s, 1H), 7.66-7.72 (t, 1H, J=7.8 Hz, 7.5 Hz), 7.58-7.62 (dd, 1H, J=7.8 Hz, 4.8 Hz), 3.24 (s, 3H), 2.34 (s, 3H).
Example 123
3-Bromo-N-methyl-N′-((7-methyl-6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0470] Yield: 26%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 8.79-8.80 (dd, 1H, J=4.8 Hz, 1.2 Hz), 8.72 (s, 1H), 8.56-8.57 (d, 1H, J=2.1 Hz), 8.26 (s, 1H), 7.96 (s, 1H), 7.86-7.89 (m, 1H), 7.76-7.79 (d, 1H, J=8.1 Hz), 7.72-7.75 (dd, 1H, J=7.8 Hz, 1.2 Hz), 7.69 (s, 1H), 7.64-7.67 (m, 1H), 7.36-7.41 (m, 1H), 6.81-6.86 (t, 1H, J=7.8 Hz, 7.5 Hz), 3.52 (s, 3H), 2.25 (s, 3H); MS: m/z 483.6(M+1) + .
Example 124
5-Fluoro-N, 2-dimethyl-N′-((7-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0471] Yield: 42.57%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 8.96 (s, 1H), 8.66-8.68 (dd, 1H, J=4.8 Hz, 1.5 Hz), 8.539-8.544 (d, 1H, J=1.5 Hz), 8.440-8.448 (d, 1H, J=2.4 Hz), 8.32 (s, 1H), 8.26-8.32 (dd, 1H, J=8.4 Hz, 2.4 Hz), 7.98 (s, 1H), 7.83-7.87 (m, 1H), 7.72 (s, 1H), 7.62-7.65 (d, 1H, J=9 Hz), 7.51-7.55 (dd, 1H, J=7.8 Hz, 4.8 Hz), 2.59 (s, 3H), 2.26 (s, 3H), 2.50 (s, 3H); MS: m/z 465.1(M+1) + .
Example 125
N′-((6-(2,4-dimethoxypyrimidin-5-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N, 2-dimethylbenzenesulfonohydrazide
[0472] The title compound was prepared by following the procedure as described for example 1, using Intermediate 8, methyl hydrazine and 2-methyl-5-fluorobenzene-1-sulfonyl chloride.
[0473] Yield: 7%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.21-9.22 (d, 1H, J=0.6 Hz), 8.39 (s, 1H), 8.29 (s, 1H), 8.02 (s, 1H), 7.78-7.81 (d, 1H, J=9.6 Hz, 0.6 Hz), 7.58-7.61 (dd, 1H, J=9.3 Hz, 1.8 Hz), 7.49-7.53 (dd, 1H, J=8.7 Hz, 3 Hz), 7.41-7.43 (m, 1H), 7.34-7.39 (m, 1H), 4.00 (s, 3H), 3.99 (s, 3H), 3.42 (s, 3H), 2.44 (s, 3H); MS: m/z 485.2 (M+1) + .
[0474] The compounds of Examples 126 and 127 were prepared by following the procedure as described for Example 1, using Intermediate 9, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 126
(E)-5-Fluoro-N,2-dimethyl-N′-((5-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0475] Yield: 24%; 1 H NMR (CDCl 3 ; 300M Hz): δ 8.71 (m, 1H), 8.62 (d, 1H, J=1.8 Hz), 8.34 (s, 1H), 8.01 (s, 1H), 7.75 (dd, 1H, J=8.4 Hz, 2.7 Hz), 7.68 (m, 2H), 7.47 (m, 1H), 7.33 (m, 3H), 3.37 (s, 3H), 2.64 (s, 3H), 2.63 (s, 3H); MS: m/z 438(M+1) + .
Example 127
(E)-N,3-dimethyl-N′-((5-methyl-6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0476] Yield: 17%; 1 H NMR (CDCl 3 ; 300 MHz): δ 8.71 (m, 1H), 8.64 (d, 1H, J=1.5 Hz), 8.62 (s, 1H), 8.12 (s, 1H), 7.71 (m, 5H), 7.47 (m, 3H), 7.26 (d, 1H, J=9 Hz), 3.20 (s, 3H), 2.73 (s, 3H), 2.45 (s, 3H); MS: m/z 420(M+1) + .
[0477] The compounds of Examples 128-131 were prepared by following the procedure as described for Example 1, using Intermediate 10, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 128
(E)-5-fluoro-N,2-dimethyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0478] Yield: 38%; 1 H NMR (CDCl 3 ; 300M Hz): δ 9.50 (s, 1H), 8.74 (s, 1H), 7.99 (s, 1H), 7.91 (s, 1H), 7.87 (dd, 1H, J=8.1 Hz, 2.4 Hz), 7.78 (d, 1H, J=9 Hz), 7.71 (dd, 1H, J=8.4 Hz, 2.7 Hz), 7.59 (dd, 1H, J=9.6 Hz, 1.8 Hz), 7.35 (d, 1H, J=8.1 Hz), 7.25 (m, 1H), 7.08 (m, 1H), 3.45 (s, 3H), 2.68 (s, 3H), 2.53 (s, 3H); MS: m/z 438 (M+1) + .
Example 129
(E)-N-methyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-2-(trifluoromethoxy)benzenesulfonohydrazide
[0479] Yield: 22%; 1 H NMR (CDCl 3 ; 300M Hz): δ 9.36 (s, 1H), 8.72 (s, 1H), 8.10 (dd, 1H, J=7.8 Hz, 1.8 Hz), 7.94 (s, 1H), 7.90 (m, 2H), 7.79 (d, 1H, J=9 Hz), 7.57 (m, 2H), 7.41 (d, 1H, J=7.8 Hz), 7.34 (m, 1H), 7.04 (m, 1H), 3.57 (s, 3H), 2.72 (s, 3H); MS: m/z 490 (M+1) + .
Example 130
(E)-5-Fluoro-2-methoxy-N-methyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0480] Yield: 22%; 1 H NMR (CDCl 3 ; 300 MHz): δ 9.50 (s, 1H), 8.773 (s, 1H), 7.91 (s, 1H), 7.88 (m, 2H), 7.79 (d, 1H, J=9 Hz), 7.71 (dd, 1H, J=7.8 Hz, 2.7 Hz), 7.61 (dd, 1H, J=9.3 Hz, 1.8 Hz), 7.42 (d, 1H, J=8.1 Hz), 7.13 (m, 1H), 6.90 (m, 1H), 3.85 (s, 3H), 3.55 (s, 3H), 2.69 (s, 3H); MS m/z 454(M+1) + .
Example 131
(E)-N,2-dimethyl-N′-((6-(6-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0481] Yield: 24%; 1 H NMR (CDCl 3 ; 300 MHz): δ 9.45 (s, 1H), 8.73 (s, 1H), 8.01 (d, 1H, J=7.5 Hz), 7.95 (s, 1H), 7.89 (m, 2H), 7.79 (d, 1H, J=9.3 Hz), 7.58 (dd, 1H, J=9.3 Hz, 1.8 Hz), 7.39 (m, 2H), 7.25 (m, 1H), 6.93 (m, 1H), 3.47 (s, 3H), 2.70 (s, 3H), 2.56 (s, 3H); MS m/z 420 (M+1) + .
[0482] The compounds of Examples 132 and 133 were prepared by following the procedure as described for Example 1, using Intermediate 11, methyl hydrazine and an appropriate sulfonylchloride derivative.
Example 132
(E)-5-fluoro-N′-((6-(5-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-N, 2-dimethylbenzenesulfonohydrazide
[0483] Yield: 37%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.63 (s, 1H), 8.72 (s, 1H), 8.58-8.59 (d, 1H, J=2.4 Hz), 7.86-8.00 (m, 3H), 7.59-7.70 (m, 3H), 7.28 (s, 1H), 7.09-7.12 (m, 1H), 3.48 (s, 3H), 2.55 (s, 3H); MS: m/z 441 (M+1) + .
Example 133
(E)-5-Fluoro-N′-((6-(5-fluoropyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)-2-methoxy-N-methylbenzenesulfonohydrazide
[0484] Yield: 54%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.62 (s, 1H), 8.75 (s, 1H), 8.60-8.61 (d, 1H, J=2.7 Hz), 7.91 (s, 2H), 7.68-7.83 (m, 3H), 7.58-7.61 (dd, 1H, J=1.8 & 9.3 Hz), 7.09-7.16 (m, 1H), 6.90-6.91 (m, 1H), 3.86 (s, 3H), 3.56 (s, 3H); MS m/z 457 (M+1) + .
Example 134
(E)-5-Fluoro-N′-((6-(6-fluoro-5-methylpyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide
[0485] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 12 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0486] Yield: 40 mg (26%); 1 H NMR (CDCl 3 ; 300 MHz): δ 9.62 (s, 1H), 8.25 (s, 1H), 7.97 (m, 3H), 7.81 (d, 1H, J=9.6 Hz), 7.64 (m, 2H), 7.26 (m, 1H), 7.11 (m, 1H), 3.46 (s, 3H), 2.54 (s, 3H); MS: m/z 456(M+1) + .
Example 135
(E)-N′-((6-(6-Chloropyridins-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide
[0487] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 13 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0488] Yield: 26%; 1 H NMR (CDCl 3 ; 300M Hz): δ 9.60 (s, 1H), 8.63 (s, 1H), 7.97 (m, 3H), 7.83 (d, 1H, J=9 Hz), 7.67 (m, 1H), 7.59 (t, 2H, J=10.5 Hz), 7.24 (m, 1H), 7.12 (m, 1H), 3.47 (s, 3H), 2.53 (s, 3H); MS m/z 457(M+1) + .
Example 136
(E)-V-((6-(1H-Pyrrol-2-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-5-fluoro-N,2-dimethylbenzenesulfonohydrazide
[0489] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 14 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0490] Yield: 20%; 1 H NMR (CDCl 3 , 300M Hz): δ 9.89 (s, 1H), 8.97 (s, 1H), 8.19 (m, 6H), 6.96 (s, 2H), 6.35 (s, 1H), 3.38 (s, 3H), 2.77 (s, 3H); MS m/z 412M+1) + .
Example 137
(E)-5-fluoro-N′-((6-(6-methoxypyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N,2-dimethylbenzenesulfonohydrazide
[0491] The title compound was prepared by following the procedure as described for Example 1, using 6-(6-methoxypyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde, and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0492] Yield: 23%; 1 H NMR (CDCl 3 ; 300M Hz): 9.48 (s, 1H), 8.389 (s, 1H), 7.98 (s, 1H), 7.91 (bs, 1H), 7.85 (m, 2H), 7.73 (m, 1H), 7.59 (m, 1H), 7.25 (m, 1H), 7.11 (m, 1H), 6.96 (d, 1H, J=8.4 Hz), 4.04 (s, 3H), 3.47 (s, 3H), 2.53 (s, 3H); MS m/z 454(M+1) + .
Example 138
(E)-5-Fluoro-N-((6-(2-methoxypyrimidin-5-yl) imidazo[1,2-a]pyridine-3-yl)methylene)-N, 2-dimethylbenzenesulfonohydrazide
[0493] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 15 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0494] Yield: 47%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.49 (s, 1H), 8.75 (s, 2H), 7.99 (s, 1H), 7.94 (s, 1H), 7.83-7.86 (d, 1H, J=9.3 Hz), 7.67-7.70 (dd, 1H, J=2.7 &8.4 Hz), 7.51-7.55 (dd, 1H, J=1.8 &9.3 Hz), 7.23-7.26 (m, 1H), 7.08-7.14 (m, 1H), 4.15 (s, 3H), 3.48 (s, 3H), 2.54 (s, 3H); MS: m/z 455 (M+1) + .
Example 139
(E)-5-fluoro-N, 2-dimethyl-N′-((6-(5-(trifluoromethyl)pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene) benzenesulfonohydrazide
[0495] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 16 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0496] Yield: 40%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.72 (s, 1H), 9.09 (s, 1H), 8.99 (s, 1H), 8.24 (s, 1H), 7.96-7.99 (d, 2H, J=9.6 Hz), 7.85-7.88 (d, 1H, J=9 Hz), 7.59-7.65 (m, 2H), 7.21-7.23 (m, 1H), 7.06-7.09 (m, 1H), 3.48 (s, 3H), 2.54 (s, 3H); MS: m/z 513 (Na + ).
Example 140
(E)-5-Fluoro-N, 2-dimethyl-N′-((6-(pyrimidin-5-yl)imidazo[1,2-a]pyridin-3-yl)methylene)benzenesulfonohydrazide
[0497] The title compound was prepared by following the procedure as described for Example 1, using Intermediate 17 and 5-fluoro-2-methylbenzene-1-sulfonyl chloride.
[0498] Yield: 47.87%; 1 H NMR (300 MHz, DMSO-d 6 ): δ 9.62 (s, 1H), 9.34 (s, 1H), 9.01 (s, 2H), 8.00 (s, 1H), 7.96 (s, 1H), 7.85-7.88 (d, 1H, J=9.6 Hz), 7.64-7.67 (dd, 1H, J=2.7& 8.4 Hz), 7.56-7.60 (dd, 1H, J=1.8 & 9.3 Hz), 7.23-7.25 (m, 1H), 7.09-7.10 (m, 1H), 3.48 (s, 3H), 2.55 (s, 3H); MS: m/z 425 (M+1) + .
Example 141
(E)-N-benzyl-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide
[0499] Methyl hydrazine (41.25 mg, 0.8968 mmoles) was added to ethanolic solution of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (100 mg, 0.4484 mmoles) at RT. The reaction mixture was heated at 85° C. for 1.5 hours. The solvent was then evaporated. The residue was dissolved in ethanol (5 ml), followed by addition of benzyl isocyanate (140.58 mg, 0.6726 mmoles). The reaction mixture was refluxed for 2 hours, then the solvent was evaporated. Water was poured into the residue and the aqueous solution was extracted with chloroform. Organic layer was separated, washed with water and brine and dried over sodium sulfate. The crude product was purified by column chromatography (100-200 mesh size silica gel, 1.5% methanol in chloroform). Yield: 41%; 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.48 (s, 1H), 9.05 (s, 1H), 8.58 (s, 1H), 8.21 (m, 3H), 7.98 (s, 1H), 7.80 (s, 2H), 7.29 (m, 6H), 4.39 (d, 2H, J=4.2 Hz), 3.35 (s, 3H); MS: m/z 384 (M+1) + .
Example 142
(E)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)-N-p-tolylhydrazinecarboxamide
[0500] The title compound was prepared according to the procedure as set forth in example 141, except that 1-isocyanato-4-methylbenzene was used in place of benzyl isocyanate to yield 51% of the title compound. 1 H NMR (DMSO-d 6 ; 300 MHz): δ 9.56 (s, 1H), 9.23 (s, 1H), 9.05 (s, 1H), 8.61 (s, 1H), 8.30 (m 3H), 7.84 (s, 1H), 7.49 (m, 3H), 7.11 (d, 1H, J=7.2 Hz), 3.41 (s, 3H), 2.28 (s, 3H); MS: m/z 385 (M+1) + .
Example 143
(E)-N-(2-fluoro-5-methylphenyl)-1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide
[0501] The title compound was prepared according to the procedure as set forth in example 141, except that 1-fluoro-2-isocyanato-4-methylbenzene was used in place of benzyl isocyanate to yield 35% of the title compound. 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.46 (s, 1H), 8.99 (d, 2H, J=6.3 Hz), 8.60 (s, 1H), 8.34 (s, 1H), 8.19 (s, 1H), 7.84 (m, 3H), 7.40 (s, 1H), 7.02 (m, 2H), 3.43 (s, 3H), 2.298 (s, 3H); MS: m/z 403(M+1) + .
Example 144
(E)-N-(5-fluoro-2-methylphenyl)-1-methyl-2-((6-(pyridin-3-yl) imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarboxamide
[0502] The title compound was prepared according to the procedure as set forth in example 141, except that 4-fluoro-2-isocyanato-1-methylbenzene was used in place of benzyl isocyanate to yield 28% of the title compound. 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.43 (s, 1H), 9.00 (d, 2H, J=19.5 Hz), 8.61 (s, 1H), 8.36 (s, 1H), 8.20 (m, 2H), 7.83 (m, 2H), 7.62 (d, 1H, J=10.5 Hz)), 7.42 (s, 1H), 7.17 (s, 1H), 6.85 (s, 1H), 3.45 (s, 3H), 2.03 (s, 3H); MS: m/z 403(M+1) + .
Example 145
N-benzyl-2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methylhydrazinecarboxamide
[0503] 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde (step 1 of Intermediate 1, 100 mg, 0.44 mmoles) was dissolved in ethanol followed by addition of methyl hydrazine (41.25 mg, 0.89 mmoles) at RT. The reaction mixture was heated at 85° C. for 1.5 hours. Solvent was evaporated. The residue so obtained was dissolved in ethanol (5 ml), followed by addition of benzyl isocyanate (140.58 mg, 0.67 mmoles). The reaction was refluxed for 2 hours and then the solvent was evaporated. Water was poured into the residue and the aqueous solution was extracted with chloroform. Organic layer was washed with water and brine, separated and dried over sodium sulfate. The crude product was purified by column chromatography (100-200 mesh size silica gel, 1.5% MeOH in CHCl 3 ). Yield: 70 mg (40.93%); 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.36 (s, 1H), 8.14-8.15 (d, 2H, J=5.4 Hz), 7.93 (bs, 1H), 7.65-7.68 (d, 1H, J=9 Hz), 7.48-7.51 (d, 1H, J=9 Hz), 7.23-7.35 (m, 5H), 4.39-4.41 (d, 2H, J=5.1 Hz), 3.35 (s, 3H); MS: m/z 386.8(M+1) + .
Example 146
(6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-N-(2-fluoro-5-methylphenyl)-1-methylhydrazinecarboxamide
[0504] The title compound was prepared according to the procedure as set forth in example 145, except that 1-fluoro-2-isocyanato-4-methylbenzene was used in place of benzyl isocyanate to yield 19.55% of the title compound. 1 HNMR (DMSO-d 6 ; 500 MHz): δ 9.35 (s, 1H), 8.95 (s, 1H), 8.28 (s, 1H), 8.16 (s, 1H), 7.78-7.79 (d, 1H, J=7 Hz), 7.71-7.73 (d, 1H, J=9.5 Hz), 7.55-7.58 (dd, 1H, J=9.5 Hz, 1.5 Hz), 7.14-7.18 (m, 1H), 6.93-6.94 (m, 1H), 3.42 (s, 3H), 2.30 (s, 3H); MS: m/z 404(M+1) + .
Example 147
(6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-N-(5-fluoro-2-methylphenyl)-1-methylhydrazinecarboxamide
[0505] The title compound was prepared according to the procedure as set forth in example 145, except that 4-fluoro-2-isocyanato-1-methylbenzene was used in place of benzyl isocyanate to yield 33.52% of the title compound. 1 H NMR (DMSO-d 6 ; 500 MHz): δ 9.36 (s, 1H), 8.86 (s, 1H), 8.27 (s, 1H), 8.14 (s, 1H), 7.67-7.79 (m, 2H), 7.51-7.55 (dd, 1H, J=9.6 Hz, 1.8 Hz), 7.21-7.26 (t, 1H, J=7.8 Hz), 6.81-6.87 (m, 1H), 3.41 (s, 3H), 2.30 (s, 3H); MS: m/z 404 (M+1)-F.
Example 148
(E)-1-methyl-N-(2-morpholinoethyl)-2-((6-(pyridin-3-ypimidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide
[0506] Methyl hydrazine (41.25 mg, 0.8968 mmoles) was added to ethanolic solution of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde (100 mg, 0.4484 mmoles) at RT. The reaction mixture was heated at 85° C. for 1.5 hours. The solvent was then evaporated. The residue was dissolved in ethanol (5 ml), followed by addition of 4-(2-isothiocyanatoethyl) morpholine (114.83 mg, 0.6726 mmoles). The reaction mixture was refluxed for 2 hours, then the solvent was evaporated. Water was poured into the residue and the aqueous solution was extracted with chloroform. Organic layer was separated, washed with water and brine and dried over sodium sulfate. The crude product was purified by column chromatography (100-200 mesh size silica gel, 1.5% MeOH in CHCl 3 ). Yield: 21%; 1 HNMR (CDCl 3 ; 300 MHz): δ 9.39 (s, 1H), 8.91 (s, 1H), 8.71 (s, 1H), 8.11 (m, 3H), 7.93 (m, 1H), 7.67 (d, 1H, J=9 Hz), 7.48 (s, 1H), 4.01 (s, 3H), 3.76 (s, 2H), 3.33 (s, 2H), 2.47 (s, 2H), 2.06 (s, 4H); MS: m/z 424(M+1) + .
Example 149
(E)-N-(4-cyanophenyl)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide
[0507] The title compound was prepared according to the procedure as set forth in example 148, except that 4-isothiocyanatobenzonitrile was used in place of 4-(2-isothiocyanatoethyl) morpholine to yield 25% of the title compound. 1 HNMR (CDCl 3 ; 300 MHz): δ 9.77 (s, 1H), 9.29 (s, 1H), 8.87 (s, 1H), 8.17 (s, 1H), 8.20 (d, 2H, J=19.5 Hz), 7.96 (m, 2H), 7.83 (m, 5H), 4.07 (s, 3H); MS: m/z 412 (M+1) + .
Example 150
(E)-N-(4-methoxyphenyl)-1-methyl-2-((6-(pyridin-3-yl)imidazo[1,2-a]pyridin-3-yl)methylene)hydrazinecarbothioamide
[0508] The title compound was prepared according to the procedure as set forth in example 148, except that 1-isothiocyanato-4-methoxybenzene was used in place of 4-(2-isothiocyanatoethyl)morpholine to yield 25% of the title compound. 1 HNMR (CDCl 3 ; 300 MHz): δ 9.38 (s, 1H), 8.87 (s, 1H), 8.62 (s, 1H), 8.16 (d, 2H, J=20.7 Hz), 7.92 (d, 1H, J=9.3 Hz), 7.76 (m, 2H), 7.37 (d, 2H, J=8.1 Hz), 7.11 (s, 1H), 6.92 (d, 2H, J=7.8 Hz), 4.07 (s, 3H), 3.86 (s, 3H); MS: m/z 417(M+1) + .
Example 151
2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methyl-N-(2-morpholinoethyl) hydrazinecarbothioamide
[0509] The title compound was prepared according to the procedure as set forth in example 148, except that 4-(2-isothiocyanatoethyl)morpholine was used in place of benzyl isocyanate and 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde was used in place of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde to yield 27% of the title compound. 1 HNMR (DMSO-d 6 ; 300 MHz): δ 9.36 (s, 1H), 8.74 (s, 1H), 8.36 (s, 1 Hz), 8.21 (s, 1H), 7.70-7.73 (d, 1H, J=9 Hz), 7.55-7.58 (d, 1H, J=9 Hz), 3.84 (s, 3H), 3.70-3.71 (m, 2H), 3.55 (s, 4H), 2.60 (s, 2H), 2.45 (s, 4H); MS: m/z 425(M+1) + .
Example 152
2-((6-bromoimidazo[1,2-a]pyridin-3-yl)methylene)-1-methyl-N-(4-(trifluoromethyl)phenyl) hydrazinecarbothioamide
[0510] The title compound was prepared according to the procedure as set forth in example 148, except that 1-isothiocyanato-4-(trifluoromethyl)benzene was used in place of benzyl isocyanate and 6-bromoimidazo[1,2-a]pyridine-3-carbaldehyde was used in place of 6-(pyridin-3-yl)imidazo[1,2-a]pyridine-3-carbaldehyde to yield 35% of the title compound.
[0511] Yield: 35%; 1 H NMR (DMSO-d 6 ; 300 MHz): δ 10.58 (s, 1H), 9.48 (s, 1H), 8.51 (s, 1H), 8.33 (s, 1H), 7.93-7.96 (d, 2H, J=7.8 Hz), 7.73-7.76 (m, 3H), 7.58-7.61 (d, 1H, J=9 Hz), 3.94 (s, 3H); MS: m/z 457(M+2) + .
Pharmacology
[0512] The efficacy of the present compounds can be determined by a number of pharmacological assays well known in the art, such as described below. The exemplified pharmacological assays, which follow herein below, have been carried out with the compounds of the present invention.
Example 153
Protocol for kinase assay (PI3Kα)
[0513] The assay was designed as in the reference, Cell, 2006, 125, 733-47 (Supplemental Data), the disclosure of which is incorporated by reference for the teaching of the assay.
[0514] The kinase reaction was carried out in a 25 μL volume in a 1.5 mL microcentrifuge tube. The reaction mixture consisted of kinase buffer (10 mM Hepes, pH 7.5, 50 mM MgCl 2 ), 20 ng PI3Kα kinase (Millipore, USA), 12.5 μg phosphotidylinositol (PI), 10 μM ATP and 1 μCi 32 γ P dATP. Representative compounds of present invention were added at concentrations (stock solution was prepared in DMSO and subsequent dilutions were made in kinase buffer) as mentioned in the table 1. The reactions were incubated at 30° C. for 20 minutes and were terminated by adding 1:1 mixture of MeOH and CHCl 3 . The tube contents were mixed on a vortex mixer and centrifuged at 10000 rpm for 2 minutes. 10 μL of the organic (lower) phase was spotted on to a TLC plate (silica, mobile phase: n-propanol and 2 M glacial acetic acid in 65:35 ratio). The plates were dried and exposed to an X-ray film. The bands appearing as a result of 32 γ P incorporation in PI were quantitated using the Quantityl)ne (BioRad, USA) densitometry program. PI-103 (Calbiochem, USA) was used as a standard.
[0515] Results: Table 1 depicts the IC 50 values (μM) of the representative compounds of present invention for PI3K inhibition.
[0000]
TABLE 1
Example No.
IC 50 (μM)
Example No.
IC 50 (μM)
5
+
6
+
7
++
11
++
14
++
15
+
16
+
17
++
18
++
20
++
21
++
22
++
23
++
25
++
26
++
27
++
84
++
100
++
115
++
Standard
80% inhibition
PI-103
at 100 nM
IC 50 Ranges
+ 1 ≧ IC 50 > 0.5
++ 0.5 ≧ IC 50 > 0.01
Example 154
mTOR Activity Assay
[0516] The assay was designed as in the reference, Biochemical Journal, 2000, 350, 717-722, the disclosure of which is incorporated by reference for the teaching of the assay.
[0517] Seed cells (Ovarian cell line A2780, ATCC) were plated in a 96 well microtitre plate at a density of 50,000 cells/cm 2 in appropriate complete cell culture medium. The cells were allowed to adhere for 18-24 hours. The cells were allowed to starve for 24 hours. The cells were pretreated (in triplicates) with the representative compounds of the present invention (refer table 2a and 2b) (stock solution was prepared in DMSO and subsequent dilutions were made in kinase buffer) at a concentration of 10 μM for one hour. Then the cells were stimulated with 20% FCS for 30 minutes. A typical assay would consist of a set of unstimulated cells, a set of stimulated cells and a set of cells treated with compounds of present invention and a set of cells treated with the stimulator. The medium was discarded. The cells were fixed with 100 μL of 3.7% formaldehyde for 15 minutes. The formaldehyde was discarded by inverting the plate and tapping it on a thick tissue paper layer to remove traces. The cells were washed and permeabilized with 200 μL PBS+Triton-X 100 solution (hereafter referred to as PBS-Triton, containing 0.1% triton-X 100 in 1×PBS) three times, incubating the cells each time for 5 minutes. 100 μL blocking solution (10% FCS in PBS-Triton) was added and incubated for 1 hour at 25° C. The blocking solution was discarded and cells were incubated with the primary antibody in PBS-Triton at a dilution of 1:500 for 1 hour at RT (25° C.). [The primary antibody is Phospho-AKT (Ser 473); Cell Signaling; Cat. No. 9271]. The primary antibody solution was discarded and the cells were washed 3 times with PBS-Triton solution and incubated with the HRP-conjugated secondary antibody in PBS-Triton at a dilution of 1:500 for 1 hour at RT (25° C.). The cells were washed 3 times with PBS-Triton followed by two washes with PBS (to remove traces of triton-X 100). The OPD (o-phenylene diamine dihydrochloride) substrate was prepared for detection of the signal by dissolving one tablet set (two tablets) of SigmaFast OPD (Sigma, Cat No. P9187) in 20 mL distilled water. It should be protected from light. 100 μL OPD solutions was added to the wells and the plate was incubated in the dark for 3-5 minutes (depending upon the development of the color). The reaction was stopped by adding 50 μL 2 N H 2 SO 4 . The absorbance was measured at 490 nm. The values were expressed in the treated samples, in terms of percentage or fold decrease in AKT phosphorylation with respect to the induced sample. PI-103 (Calbiochem, USA) was used as a standard.
[0518] Results: % inhibition of mTOR at 1 μM and 10 μM is indicated in Table 2a.
[0519] IC 50 values of representative compounds for mTOR activity assay are indicated in Table 2b
[0000]
TABLE 2a
Example
% Inhibition of mTOR
Example
% Inhibition of mTOR
No.
activity at 1 μM
No.
activity at 1 μM
6
+
7
+
8
+
11
+
15
+
16
+
17
+
20
+
23
+
84
+
Standard
50
(PI-103)
% Inhibition of mTOR activity at 10 μM
26
++
% Inhibition Ranges
+ 50% ≧ % Inhibition ≧ 30%
++ % Inhibition > 50%
[0000]
TABLE 2b
Example No.
mTOR IC 50 (μM)
Example No.
mTOR IC 50 (μM)
5
++
21
++
25
++
115
+
Standard
50% inhibition at 1 μM
(PI-103)
IC 50 Ranges in μM
+ 10 ≧ IC 50 > 5
++ 5 ≧ IC 50 ≧ 1
Example 155
Cytotoxicity Assay
[0520] Propidium Iodide Assay
[0521] The assay was designed as in the reference, Anticancer Drugs, 2002, 13, 1-8, the disclosure of which is incorporated by reference for the teaching of the assay.
[0522] Cells from cell lines as mentioned in the table given below were seeded at a density of 3000 cells/well in a white opaque 96-well plate. Following incubation at 37° C./5% CO 2 for a period of 18-24 hours, the cells were treated with various concentrations (stock solution was prepared in DMSO and subsequent dilutions were made in media as per ATCC guidelines) of the representative compounds of present invention (refer table 3) for a period of 48 hours. At the end of treatment, the spent culture medium was discarded, the cells were washed with 1×PBS and 200 μl of 7 μg/ml propidium iodide was added to each well. The plates were frozen at −70° C. for at least 24 hours. For analysis, the plates were brought to RT, allowed to thaw and were read in PolarStar fluorimeter with the fluorescence setting. The percentage of viable cells in the non treated set of wells was considered to be 100 and the percentage viability following treatment was calculated accordingly. IC 50 values were calculated from graphs plotted using these percentages. Results for representative compounds of present invention in individual cell lines are shown in Table 3 and 4.
[0523] The abbreviations for the Cell Lines as used in Table 3 are:
[0000]
Type of Cancer
Abbreviation
Cell Line
Abbreviation
Lung
C1
A549
C1a
H460
C1b
Prostate
C2
PC3
C2a
Ovarian
C3
A2780
C3a
SKOV3
C3b
OVCAR 3
C3c
Colon
C4
HT29
C4a
HCT116
C4b
Pancreatic
C5
PANC 1
C5a
CAPAN1
C5b
Breast
C6
MDA MB 231
C6a
MDA MB 468
C6b
MCF7
C6c
BT 549
C6d
T47D
C6e
Multiple Myeloma
C7
U266B1
C7a
RPMI 8226
C7b
Glioblastoma
C8
U 373
C8a
U 87 MG
C8b
Human melanoma
C9
G361
C9
Cervical
C10
HeLA S3
C10
Hypopharyngeal
C11
FaDu
C11
[0000]
TABLE 3
Example No.
Cell Lines
1
2
3
5
6
7
9
10
11
C1
C1a
++
++
++
++
++
+
++
++
+
C1b
++
++
++
−−
−−
+
++
++
+
C2
C2a
++
++
++
−−
−−
+
++
++
+
C3
C3a
++
++
++
++
++
−−
++
++
+
C3b
−−
−−
−−
++
−−
−−
−−
−−
−−
C3c
++
−−
++
++
++
−−
−−
++
−−
C4
C4a
−−
+
−−
−−
−−
−−
−−
−−
−−
C4b
++
−−
++
++
++
−−
−−
++
−−
C5
C5a
++
−−
−−
++
++
−−
−−
−−
−−
C5b
++
−−
−−
++
++
−−
−−
−−
−−
C6
C6a
−−
++
−−
−−
−−
−−
−−
−−
−−
C6b
−−
−−
−−
−−
−−
+
++
−−
+
C6c
−−
−−
−−
−−
−−
+
−−
−−
−−
C6d
−−
−−
−−
−−
−−
−−
++
−−
+
C6e
−−
−−
−−
+
+
−−
−−
−−
−−
C9
C9a
−−
−−
−−
−−
−−
+
−−
−−
−−
C11
C11a
−−
−−
−−
++
++
−−
−−
−−
−−
Example No.
Cell Lines
12
18
20
21
23
24
25
26
27
C1
C1a
++
+
+
++
++
++
++
++
+
C1b
++
+
+
++
++
++
++
++
+
C2
C2a
++
+
+
++
−−
++
++
−−
+
C3
C3a
++
−−
+
++
++
++
++
++
−−
C3b
−−
−−
−−
++
−−
−−
++
++
−−
C3c
++
−−
−−
++
−−
−−
++
++
−−
C4
C4a
−−
−−
−−
−−
−−
−−
−−
−−
−−
C4b
++
−−
+
++
−−
+
++
−−
−−
C5
C5a
−−
−−
−−
++
−−
−−
++
++
−−
C5b
−−
−−
−−
++
−−
−−
++
++
−−
C6
C6a
−−
−−
−−
++
−−
−−
++
−−
−−
C6b
−−
+
−−
++
−−
−−
−−
−−
+
C6c
−−
+
−−
++
−−
−−
++
−−
+
C6d
−−
−−
−−
++
−−
−−
++
−−
−−
C6e
−−
−−
−−
−−
−−
−−
++
−−
−−
C7
C7a
−−
−−
−−
++
−−
−−
−−
−−
−−
C7b
−−
−−
−−
++
−−
−−
−−
−−
−−
C8
C8a
−−
−−
+
++
−−
++
−−
−−
−−
C8b
−−
−−
+
++
−−
++
−−
−−
−−
C9
C9a
−−
+
−−
++
−−
−−
−−
−−
+
Example No.
Cell Lines
28
29
30
31
45
53
54
65
C1
C1a
+
++
+
++
++
++
++
++
C1b
+
++
+
++
++
++
++
++
C2
C2a
+
++
+
++
−−
−−
−−
−−
C3
C3a
+
++
−−
++
−−
−−
−−
−−
C3b
−−
−−
−−
−−
−−
−−
−−
−−
C3c
−−
++
−−
−−
−−
−−
−−
−−
C4
C4a
+
−−
−−
+
−−
−−
−−
−−
C4b
−−
++
−−
−−
−−
−−
−−
−−
C5
C5a
−−
−−
−−
−−
−−
−−
−−
−−
C5b
−−
−−
−−
−−
−−
−−
−−
−−
C6
C6a
+
−−
−−
++
−−
−−
−−
−−
C6b
−−
−−
+
−−
−−
−−
−−
−−
C6c
−−
−−
+
−−
−−
−−
−−
−−
C9
C9a
−−
−−
+
−−
−−
−−
−−
−−
Example No.
Cell Lines
83
85
88
99
100
132
C1
C1a
+
++
++
++
++
++
C1b
+
++
++
++
++
++
C2
C2a
+
++
−−
++
−−
−−
C3
C3a
++
++
−−
++
++
−−
C3b
−−
−−
−−
−−
−−
−−
C3c
−−
−−
−−
++
−−
−−
C4
C4a
+
+
−−
−−
−−
−−
C4b
−−
−−
−−
++
−−
−−
C5
C5a
−−
−−
−−
−−
−−
−−
C5b
−−
−−
−−
−−
−−
−−
C6
C6a
++
++
−−
−−
−−
−−
C6b
−−
−−
−−
−−
−−
−−
C6c
−−
−−
−−
−−
−−
−−
C9
C9a
−−
−−
−−
−−
−−
−−
IC 50 Ranges in μM
+ IC 50 > 5
++ 5 ≧ IC 50 ≧ 0.01
−− Not Done
[0000]
TABLE 4
% inhibition at 1 μM
Example No.
Cell Lines
91
142
143
144
146
149
150
152
C2
C2a
++
+
+
+
++
+
+
+
C3
C3a
++
+
+
+
++
+
+
+
% Inhibition Ranges
+ 50% ≧ % Inhibition ≧ 30%
++ % Inhibition >50%
Example 156
STAT3 Bioassay
[0524] Hela STAT3 Assay
[0525] Cells were seeded (Hela Stat3-luc, ATCC P/N 30-2002) in a white 96 well plate (Nunc cat.no.136101) at a density of 20,000cells/well in 179 μl volume per well (DMEM from Sigma containing 10% FCS). The plate was incubated for 24 hours at 37° C./5% CO 2 . The cells (wells in triplicates) were then treated with 1 μl/well of 200× stock of the desired compound concentration prepared in 100% DMSO. Curcumin was used as a standard or positive control, added 10 μg/ml in triplicate. DMSO was used as medium control (1 μl/well added in triplicates). The plate was incubated at 37° C./5% CO 2 for 1 hour. 20 μl/well Oncostatin M (Oncostatin M, Human, Recombinant, E. coli , Cat.No. 496260, 10 μg from Calbiochem) was added to treated wells, induction control (in triplicate) (1000 ng/ml stock prepared in serum free medium to get final concentration 100 ng/ml). The plate was then incubated for 7-8 hours at 37° C./5% CO 2 for induction. A typical assay would consist of triplicate of medium control, triplicate of induction control, triplicate of positive/standard control and test compounds at desired concentration in triplicates. For termination Luciferase assay protocol was followed where the culture medium was removed from all the wells.
Luciferase Assay
[0526] 200 μl well of PBS was added to remove traces of medium and compound. The PBS was discarded. 40 μl/well of 1× lysis buffer was added to all the wells. The plate was incubated at RT for 20 minutes with intermittent shaking. 100 μl/well of LAB reagent was added to all the wells in dark. {LAB reagent for 1 plate=8 ml Luciferase assay buffer (LAB)+1 ml Coenzyme A (Sigma cat no. C3019) (2.1 mg/ml stock in LAB)+530 μL of ATP (Sigma cat.no.A2383) (5.85 mg/ml stock in LAB)+1 ml luciferin reagent (Promega cat no.245355) (2 mg/ml stock in LAB, protect from light)}.
[0527] The luminescence was immediately read on polar star. The values were expressed as percentage inhibition, in terms of treated values to that STAT3 (induction control). IC 50 values were calculated from graphs using these percentages. Results for representative compounds of present invention are shown in Table 5.
1× Lysis Buffer
[0528]
[0000]
Final concentration
Stock
Quantity for 100 ml
125 mM Tris phosphate buffer pH 7.8
0.2M
12.5
ml
10 mM DTT
0.2M
155
mg
50% glycerol
100%
10
ml
5% Triton X-100
100%
1
ml
Distilled water
To make volume 100 ml
1M Tris Phosphate Buffer:
[0529] Dissolve 12.114 gm tris(hydroxymethyl)aminomethane (Trizma, Sigma Aldrich) in 70 ml distilled water and adjust pH to 7.8 using ortho-phosphoric acid and then make up the volume 100 ml with distilled water.
Luciferase Assay Buffer
[0530]
[0000]
Final concentration
1000
ml
20 mM Tricine (pH 7.8)
3.58
gm
1.07 mM Mg•ALBA
520
mg
2.67 mM MgSO 4
657
mg
0.1 mM EDTA
37
mg
33.3 mM DTT
5.1
gm
[0000]
TABLE 5
Results for STAT3 activity
Example No.
IC 50 (μM)
Example No.
IC 50 (μM)
1
++
2
++
4
+++
5
+++
6
++
8
+++
9
++
10
+++
13
++
14
++
15
+++
16
++
20
+++
21
++
22
+++
24
+
25
+++
26
+++
28
+
115
++
IC 50 Ranges in μM
+ IC 50 > 10
++ 10 ≧ IC 50 > 5
+++ 5 ≧ IC 50 ≧ 0.1
Example 157
In Vitro Screening to Identify Inhibitors of IL-6 and TNF-α
Human Monocyte Assay
[0531] The assay was designed as in the reference, Physiol. Res., 2003, 52, 593-598, the disclosure of which is incorporated by reference for the teaching of the assay.
[0532] Peripheral blood mononuclear cells (hPBMC) were harvested from human blood and suspended in RPMI 1640 culture medium containing 10% FCS, 100 U/mL penicillin and 100 mg/mL streptomycin (assay medium). Monocytes in the hPBMCs were counted using a Coulter Counter following which the cells were resuspended at 2×10 5 monocytes/mL. A cell suspension containing 2×10 4 monocytes was aliquoted per well of a 96-well plate. Subsequently, the hPBMCs were incubated for 4-5 hours at 37° C., 5% CO 2 (During the incubation, the monocytes adhered to the bottom of 96-well plastic culture plate). Following the incubation, the non-adherent lymphocytes were washed with assay medium and the adherent monocytes re-fed with assay medium. After a 48-hour incubation period (37° C., 5% CO 2 ), monocytes were pretreated with various concentrations of representative compounds of present invention (refer to table 6 and 7) (prepared in DMSO) or vehicle (0.5% DMSO) for 30 minutes and stimulated with 1 μg/ml LPS ( Escherchia coli 0111:B4, Sigma Chemical Co., St. Louis, Mo.). The incubation was continued for 5 hours at 37° C., 5% CO 2 . Supernatants were harvested, assayed for IL-6 and TNF-α by ELISA as described by the manufacturer (BD Biosciences, USA). Dexamethasone (10 μM) was used as standard for this assay. The 50% inhibitory concentration (IC 50 ) values were calculated by a nonlinear regression method. Biological results for both IL-6 and TNFα are indicated in Table 6 and Table 7 respectively.
[0000]
TABLE 6
Example No.
IL-6 (IC 50 μM)
1
++
2
++
3
+
4
++
5
++
6
++
9
++
10
++
11
+
13
++
14
++
16
++
17
++
19
++
21
++
22
+
23
++
25
++
26
++
28
++
30
+
34
++
35
++
36
+
39
++
40
++
41
++
42
+
43
+
44
++
45
++
46
+
47
+
50
++
51
++
52
++
53
++
54
++
55
++
56
++
57
++
58
++
59
++
60
++
61
++
62
++
63
++
64
++
65
++
66
++
67
++
68
++
69
++
70
++
72
+
73
+
74
++
84
++
87
++
88
++
99
++
101
++
104
+
105
++
106
+
107
++
109
+
110
+
112
+
113
++
114
+
115
+
117
+
118
+
127
+
128
++
129
+
130
++
131
+
134
++
135
++
137
+
138
+
139
+
141
++
142
+
143
++
144
+
145
++
146
+
148
+
149
+
150
+
151
++
152
++
IC 50 Ranges in μM
+ IC 50 ≧ 5
++ 5 > IC 50 ≧ 0.001
[0000]
TABLE 7
Example No.
TNF-α
Example No.
TNF- α
1
++
4
++
5
+
6
++
10
++
13
++
14
++
16
++
19
++
21
++
45
++
105
++
IC 50 Ranges in μM
+ 15 ≧ IC 50 > 1
++ 1 ≧ IC 50 > 0.001
Example 158
Inhibition of Production of Cytokines
Synovial Tissue Assay
[0533] The assay was designed as in the reference, Lancet, 2(8657), 244-7, Jul. 29 (1989), the disclosure of which is incorporated by reference for the teaching of the assay.
Stock Solution:
[0534] Compounds of the present invention were dissolved in DMSO to obtain a stock solution of 20 mM.
[0535] Synovial tissue was obtained from rheumatoid arthritis patients undergoing knee replacement surgery. The tissue was minced into small pieces and digested in RPMI medium containing 100 U/ml penicillin-G, 100 μg/ml streptomycin, 50 ng/ml amphotericin B (GIBCO; USA), 1.33 mg/ml collagenase Type I (Worthington Biochemical Corporation, New Jersey), 0.5 μg/ml DNAse Type I (Sigma Aldrich; St. Louis, Mo.) and 8.33 U/ml heparin (Biological E. Limited, India) for 3 hours at 37° C., 5% CO 2 . The digested tissue was filtered through a membrane (mesh size 70 micron; Sigma Aldrich). Subsequently, the cells were washed 3 times and resuspended in complete medium (RPMI supplemented with 5% FBS and 5% human serum-AB+) at a concentration of 1×10 6 cells/ml. All cell washes in this assay were performed using Rosewall Park Memorial Institute (RPMI)-1640 medium (JRH; Australia). For the experiment, 100 μl of cell suspension was added to the wells of a 96-well culture plate. Following cell plating, 100 μl of the culture medium and 1 μl of various concentrations (0.01, 0.03, 0.1, 0.3, 1, 3, 10, 30 and 100 μM) of the compounds of present invention dissolved in DMSO were added to the cells. The final concentration of DMSO was adjusted to 0.5%. For experimental purposes, 1 μl of 20× concentrated solution of the compounds of present invention were dissolved in 200 μl cell suspension to achieve a final concentration of 0.01, 0.03, 0.1, 0.3, 1, 3, 10, 30 and 100 μM. The vehicle (0.5% DMSO) was used as control. 10 μM dexamethasone (Sigma Aldrich) or 1 μM 7-hydroxyfluorinide (7HF) were used as standards for the experiments. The plates were incubated for 16 hours at 37° C., 5% CO 2 . Subsequently, the supernatants were harvested and stored at −70° C. The amounts of TNF-α, IL-6 and interleukin-8 (IL-8) in the supernatants were assayed using OptiEIA ELISA sets, (BD BioSciences Pharmingen). The protocol followed was as per manufacturers instructions. The 50% inhibitory concentration (IC 50 ) values were calculated by a nonlinear regression method using the GraphPad software (Prism 3.03). The cytotoxicity of test compounds in synovial cells was assessed by MTS assay. Absorbance was measured at 490 nm. Percent cytotoxicity was calculated by the equation:
[0000] % Cytotoxicity=(A−B)/A×100
[0000] where, A is the absorbance of cells treated with DMSO alone and B is the absorbance of cells treated with the test article.
Results:
[0536] Compounds of the present invention inhibited the spontaneous production of IL-6 and/or TNF-α and/or IL-β and/or IL-8 from freshly isolated synovial tissue cells from rheumatoid arthritis patients. The IC 50 of IL-6, TNF-α and IL-8 inhibition are provided in the Table 8.
[0000]
TABLE 8
Example
Synovial tissue (IC 50 μM)
No.
IL-6
TNF-α
IL-8
4
++
++
+
5
++
++
+
6
+
++
+
9
++
++
+
13
++
++
+
14
++
++
+
16
++
++
+
19
+
+
+
21
++
++
++
25
++
++
+
IC 50 Ranges in μM
+ 3 ≧ IC 50 > 0.3
++ 0.3 ≧ IC 50 > 0.01
In-Vivo Studies
[0537] All experiments were carried out in accordance with the guidelines of the Committee for the Purpose of Control and Supervision of Experiments on Animals (CPCSEA), Tamil Nadu, India. Procedures using laboratory animals were approved by the Institutional Animal Ethics Committee (IAEC) of Piramal Life Sciences Limited, Mumbai, India.
Example 159
Ulcerative Colitis
[0538] The efficacy of compounds of the present invention on the gross pathology of colitis and proinflammatory mediators was determined by following the method described in Am. J. Physiol. Gastrointest. Liver Physiol. 295 (6): G1237-45 (2008), the disclosure of which is incorporated by reference for the teaching of the assay.
Induction of Colitis
[0539] C57BL/6J mice (6 weeks of age, weighing 18-22 gms) were obtained from Jackson Laboratories (Bar Harbor, Me.) and housed in individually ventilated cage (IVC) system. Colitis was induced in mice by replacing drinking water with 3% (w/v) DSS (molecular weight 35-50 kDa, ICN Biomedicals, Aurora, Ohio, US) in water. This solution was made available to the experimental animals ad libitum, from day 0 to day 10. A batch of six nai{umlaut over (v)}e animals received water instead of DSS during this period.
[0540] DSS-induction of colitis was manifested with increase in clinical disease activity index associated with weight loss and presence of blood in feces.
Treatment
[0541] The animals were weighed every day and the record of body weights was maintained. The compound of Example 25 (10 mg/kg, prepared at a concentration of 1 mg/mL in 0.5% (w/v) CMC after mixing a drop of Tween 20) was administered orally daily to the colitis induced animals. This treatment was initiated on day 6 and continued up to day 10. During this period, DSS control animals received DSS, positive control animals received 5-aminosalicylic acid (5-ASA, 25 mg/kg, p.o.) and naïve animals received 0.5% CMC once daily.
Evaluation:
[0542] At the end of DSS treatment period, mice were humanely euthanized with 15% urethane (i.p.). The whole colon (i.e., including ceacum, proximal colon and distal colon) was excised. The colon was macrosopically assessed by determining
[0000] a) Rectal bleeding/blood in faeces
b) Stool consistency
c) Blood in colon
d) Colon length
e) % weight loss
f) Blood hemoglobin concentration
Disease Activity Index:
[0543] various features were scored as delineated in the following table. Disease activity index is the sum of scores of all features.
[0000]
Feature scored
Score
Description
% Weight loss
0
No change/increase
1
0-5% Reduction
2
5-10% Reduction
3
10-15% Reduction
4
10-20% Reduction
Rectal Bleeding
0
Absent
1
Slightly present
2
Heavy
Stool Consistency
0
Normal
1
Slightly loose
2
Loose
3
Diarrhoea
Blood in Colon
0
Absent
1
Slightly present
2
Markedly present
Results:
[0000]
1. DSS-induction of colitis was manifested with significant increase in clinical disease activity index associated with weight loss, decrease in colon length, reduction in hematocrit, increased rectal bleeding, increase in colon blood and loose stools ( FIGS. 1-6 ).
2. Compound of Example 25 attenuated DSS-induced body weight loss ( FIG. 1 )
3. Compound of Example 25 inhibited DSS-induced (i) shortening of colon, and (ii) decrease in hematocrit ( FIGS. 2 and 3 )
4. Compound of Example 25 improved rectal bleeding index ( FIG. 4 )
5. Compound of Example 25 attenuated the DSS-induced colon bleeding ( FIG. 5 )
6. Compound of Example 25 reduced DSS-induced disease activity index ( FIG. 6 )
[0550] It should be noted that, as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0551] All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains.
[0552] The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention. | The present invention relates to compounds of formula (I),
wherein R a , R b , R c , R d , R e and R f are as defined in the specification, processes for their preparation, pharmaceutical compositions containing them and their use in the treatment of diseases mediated by phosphatidylinositol-3-kinase (PI3K), mammalian target of rapamycin (mTOR), Signal transducer and activator of transcription 3 (STAT 3), tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6) or a combination thereof particularly in the treatment of cancer and inflammation. | 2 |
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/330,370, filed on Dec. 19, 2011, which is a divisional of U.S. application Ser. No. 12/171,588, filed on Jul. 11, 2008, which is a continuation of U.S. application Ser. No. 10/677,947, filed on October 2, the entire contents of each of which are hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to implantable prosthetic valves. More particularly, the invention relates to a valve prosthesis for cardiac implantation or for implantation in other body ducts where the prosthesis has improved flow characteristics,
BACKGROUND OF THE INVENTION
[0003] Several prosthetic valves are known. See, for example, U.S. Pat. No. 5,411,552 (Andersen et al.), entitled VALVE PROSTHESIS FOR IMPLANTATION IN THE BODY AND CATHETER FOR IMPLANTING SUCH VALVE PROSTHESIS, which discloses a valve prosthesis comprising a stent made from an expandable cylinder-shaped thread structure comprising several spaced apices. See, also, U.S. Pat. No. 6,168,614 (Andersen et al.), entitled VALVE PROSTHESIS FOR IMPLANTATION IN THE BODY, U.S. Pat. No. 5,840,081 (Andersen et al.), entitled SYSTEM AND METHOD FOR IMPLANTING CARDIAC VALVES, and PCT Application No. PCT/EP97/07337 (Letac, Cribier et al.), published as WO 98/29057, entitled VALVE PROSTHESIS FOR IMPLANTATION IN BODY CHANNELS, all of which are incorporated herein by reference.
[0004] In the development of stented valves, a highly desirable, and often preferred design utilizes a cylindrical stent platform of either balloon expandable or self-expanding metal designs. Usually these stents follow the cellular designs which tend to have higher radial strength and less foreshortening than wire-wound platforms.
[0005] Such cylindrical stents offer a stable and reproducible expansion platform for attaching valves and may be manufactured from a variety of biocompatible metals including stainless steels, titanium alloys, platinum-iridium, nickel-titanium alloys, chromium alloys, or tantalum.
[0006] Polymeric, bovine venous, pericardial, and porcine valve constructs have lead the early development efforts of stent-valve designs. All of the early designs have utilized either bicuspid or tricuspid valve designs.
[0007] One of the key factors that determines the long term functionality of stented valves is the retrograde flow characteristics. The retrograde flow characteristics, along with the stiffness characteristics of the valve material, will determine leakage and closing pressure requirements. The retrograde flow characteristics are most important in low flow/low pressure systems where the valve leaflets may thrombose in the presence of poor retrograde laminar flow.
[0008] Stented valves are passive devices. The valves function as a result of changes in pressure and flow. An aortic stented valve opens passively when the pressure in the left ventricle exceeds the pressure in the aorta (plus any resistance required to open the valve). The valve closes when the pressure in the left ventricle is less than the pressure in the aorta. However, the flow characteristics are critical to effect the closing of the aortic valve, otherwise regurgitation will ensue.
[0009] Laminar flow is the normal condition found in most of the circulatory system. It is characterized by concentric layers of blood moving in parallel down the length of the blood vessel. The highest velocity is found in the middle of the blood vessel while the lowest is found along the wall. The flow is parabolic in a long straight vessel under steady flow conditions.
[0010] Non-laminar, or turbulent, flow is useful to the circulatory system. For example, the aortic valve opens into the sinus of Valsalva at the inferior aspect of the ascending aorta. This sinus has two key functions: First, it maximizes the flow characteristics so that the aortic valve closes during diastole. And second, it optimizes coronary sinus flow and perfusion.
[0011] Laminar flow makes the retrograde flow characteristics of valves mounted in cylindrical stents problematic as the flow along the wall is least, which is central to the closing of a valve. Such laminar flow with its attendant drawbacks is a characteristic of known stented valves. There is a need to have stented valves where the retrograde flow characteristics will be non-laminar, which will be advantageous with regard to valve closing.
SUMMARY OF THE INVENTION
[0012] According to the invention, a valve prosthesis device suitable for implantation in body ducts comprises:
[0013] a support stent having support beams; and
[0014] a valve assembly comprising a flexible conduit having an inlet end and an outlet end, made of pliant material attached to the support beams,
[0015] wherein when flow is allowed to pass through the valve prosthesis device from the inlet end to the outlet end, the valve assembly is kept in an open position; wherein a reverse flow is prevented as portions of the valve assembly collapse inwardly providing blockage to the reverse flow; and wherein the device is configured so that retrograde flow will be altered from laminar flow and directed towards the leaflets to effect closing.
[0016] In accordance with a preferred embodiment of the present invention, a valve prosthesis device suitable for implantation in body ducts comprises:
[0017] a support stent, comprised of a deployable construction adapted to be initially crimped in a narrow configuration suitable for catheterization through the body duct to a target location and adapted to be deployed by exerting substantially radial forces from within by means of a deployment device to a deployed state in the target location, the support stent provided with a plurality of longitudinally generally rigid support beams of fixed length; and
[0018] a valve assembly comprising a flexible conduit having an inlet and an outlet, made of pliant material attached to the support beams providing collapsible slack portions of the conduit at the outlet,
[0019] wherein when flow is allowed to pass through the valve prosthesis device from the inlet to the outlet, the valve assembly is kept in an open position; wherein a reverse flow is prevented as the collapsible slack portions of the valve assembly collapse inwardly providing blockage to the reverse flow; and wherein the device is configured so that retrograde flow will be altered from laminar flow and directed towards the leaflets to effect closing.
[0020] Furthermore, in accordance with another preferred embodiment of the present invention, the support stent comprises an annular frame.
[0021] Furthermore, in accordance with another preferred embodiment of the present invention, the expanded prosthesis comprises a sinus area adjacent the valve assembly.
[0022] Furthermore, in accordance with another preferred embodiment of the invention, the support stent comprises an annular frame wherein the middle portion of the expanded annular frame extends radially to create a sinus adjacent the valve assembly.
[0023] Furthermore, in accordance with another preferred embodiment of the present invention, the support stent comprises an annular frame with a valve assembly arranged therein to redirect flow towards the valve assembly.
[0024] Furthermore, in accordance with another preferred embodiment of the present invention, said valve assembly has a tricuspid configuration.
[0025] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is made from biocompatible material.
[0026] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is made from pericardial tissue, or other biological tissue.
[0027] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is made from biocompatible polymers.
[0028] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is made from materials selected from the group consisting of polyurethane and polyethylene terephthalate (PET).
[0029] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly comprises a main body made from PET (polyethylene terephthalate) and leaflets made from polyurethane.
[0030] Furthermore, in accordance with another preferred embodiment of the present invention, the support stent is made from nickel titanium.
[0031] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams are substantially equidistant and substantially parallel so as to provide anchorage for the valve assembly.
[0032] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams are provided with bores so as to allow stitching or tying of the valve assembly to the beams.
[0033] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams are chemically adhered to the support stent.
[0034] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is riveted to the support beams.
[0035] Furthermore, in accordance with another preferred embodiment of the present invention, said valve assembly is sutured to the support beams.
[0036] Furthermore, in accordance with another preferred embodiment of the present invention, the beams are manufactured by injection using a mold, or by machining.
[0037] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is rolled over the support stent at the inlet.
[0038] Furthermore, in accordance with another preferred embodiment of the present invention, the valve device is manufactured using forging or dipping techniques.
[0039] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly leaflets are longer than needed to exactly close the outlet, thus when they are in the collapsed state substantial portions of the leaflets fall on each other creating better sealing.
[0040] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly is made from coils of a polymer, coated by a coating layer of same polymer.
[0041] Furthermore, in accordance with another preferred embodiment of the present invention, the polymer is polyurethane.
[0042] Furthermore, in accordance with another preferred embodiment of the present invention, the support stent is provided with heavy metal markers to enable tracking and determining the valve device position and orientation.
[0043] Furthermore, in accordance with another preferred embodiment of the present invention, the heavy metal markers are selected from the group consisting of gold, platinum-iridium, and tantalum.
[0044] Furthermore, in accordance with another preferred embodiment of the present invention, the valve assembly leaflets are provided with radio-opaque material at the outlet, to help tracking the valve device operation in vivo.
[0045] Furthermore, in accordance with another preferred embodiment of the present invention, the radio-opaque material comprises gold thread.
[0046] Furthermore, in accordance with another preferred embodiment of the present invention, the diameter of the support stent, when fully deployed, is in the range of from about 19 to about 26 mm.
[0047] Furthermore, in accordance with another preferred embodiment of the present invention, the diameter of the support stent may be expanded from about 4 to about 25 mm.
[0048] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams are provided with bores and wherein the valve assembly is attached to the support beams by means of U-shaped rigid members that are fastened to the valve assembly and that are provided with extruding portions that fit into matching bores on the support beams.
[0049] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams comprise rigid support beams in the form of frame construction, and the valve assembly pliant material is inserted through a gap in the frame and a fastening rod is inserted through a pocket formed between the pliant material and the frame and holds the valve in position.
[0050] Furthermore, in accordance with another preferred embodiment of the present invention, the main body of the valve assembly is made from coiled wire coated with coating material.
[0051] Furthermore, in accordance with another preferred embodiment of the present invention, the coiled wire and the coating material is made from polyurethane.
[0052] Furthermore, in accordance with another preferred embodiment of the present invention, a strengthening wire is interlaced in the valve assembly at the outlet of the conduit so as to define a fault line about which the collapsible slack portion of the valve assembly may flap.
[0053] Furthermore, in accordance with another preferred embodiment of the present invention, the strengthening wire is made from nickel titanium alloy.
[0054] Furthermore, in accordance with another preferred embodiment of the present invention, there is provided a valve prosthesis device suitable for implantation in body ducts, the device comprising a main conduit body having an inlet and an outlet and pliant leaflets attached at the outlet so that when a flow passes through the conduit from the inlet to the outlet the leaflets are in an open position allowing the flow to exit the outlet, and when the flow is reversed the leaflets collapse so as to block the outlet, wherein the main body is made from PET and collapsible leaflets are made from polyurethane.
[0055] Furthermore, in accordance with another preferred embodiment of the present invention, support beams made from polyurethane are provided on the main body and wherein the leaflets are attached to the main body at the support beams.
[0056] Furthermore, in accordance with another preferred embodiment of the present invention, said support beams are chemically adhered to the main body.
[0057] Furthermore, in accordance with another preferred embodiment of the present invention, there is provided a valve prosthesis device suitable for implantation in body ducts, the device comprising:
[0058] a support stent, comprised of a deployable construction adapted to be initially crimped in a narrow configuration suitable for catheterization through the body duct to a target location and adapted to be deployed by exerting substantially radial forces from within by means of a deployment device to a deployed state in the target location, the support stent provided with a plurality of longitudinally rigid support beams of fixed length;
[0059] a valve assembly comprising a flexible conduit having an inlet end and an outlet, made of pliant material attached to the support beams providing collapsible slack portions of the conduit at the outlet; and
[0060] substantially equidistant rigid support beams interlaced or attached to the slack portion of the valve assembly material, arranged longitudinally,
[0061] wherein the device is configured so that retrograde flow will be altered from laminar flow and directed towards the leaflets to effect closing.
[0062] Furthermore, in accordance with another preferred embodiment of the present invention, there is provided a crimping device for crimping the valve device described above or in the claims below, the crimping device comprising a plurality of adjustable plates that resemble a typical SLR (Single Lens Reflex) camera variable restrictor, each provided with a blade, that are equally dispersed in a radial symmetry but each plate moves along a line passing off an opening in the center, all plates equidistant from that center opening.
[0063] Furthermore, in accordance with another preferred embodiment of the present invention, the multiple plates are adapted to move simultaneously by means of a lever and transmission.
[0064] Furthermore, in accordance with another preferred embodiment of the present invention, there is provided a method for deploying an implantable prosthetic valve device from the retrograde approach (approaching the aortic valve from the descending aorta) or from the antegrade approach (approaching the aortic valve from the left ventricle after performing a trans-septal puncture) at the natural aortic valve position at the entrance to the left ventricle of a myocardium of a patient. This method is described in co-pending, commonly assigned U.S. patent application Ser. No. 09/975,750, filed Oct. 11, 2001, and Ser. No. 10/139,741, filed May 2, 2002, each of which is incorporated herein by reference in its entirety.
[0065] Furthermore, in accordance with another preferred embodiment of the present invention, a valve prosthesis device suitable for implantation in body ducts comprises:
[0066] an expandable support frame, the support frame provided with a plurality of longitudinally rigid support beams of fixed length; and
[0067] a valve assembly comprising a flexible conduit having an inlet end and an outlet, made of pliant material attached to the support beams providing collapsible slack portions of the conduit at the outlet,
[0068] wherein when flow is allowed to pass through the valve prosthesis device from the inlet to the outlet, the valve assembly is kept in an open position; wherein a reverse flow is prevented as the collapsible slack portions of the valve assembly collapse inwardly providing blockage to the reverse flow; and wherein the device is configured so that retrograde flow will be altered from laminar flow and directed towards the leaflets to effect closing.
[0069] Furthermore, in accordance with another preferred embodiment of the present invention, the support frame comprises a deployable construction adapted to be initially crimped in a narrow configuration suitable for catheterization through the body duct to a target location and adapted to be deployed by exerting substantially radial forces from within by means of a deployment device to a deployed state in the target location.
[0070] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams have a U-shaped cross section.
[0071] Furthermore, in accordance with another preferred embodiment of the present invention, a holder is used to secure the plaint material to the support beams.
[0072] Furthermore, in accordance with another preferred embodiment of the present invention, the support frame comprises three segments that form a circular assembly when assembled.
[0073] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams point inwardly with respect to a central longitudinal axis of the device.
[0074] Furthermore, in accordance with another preferred embodiment of the present invention, the device is further provided with a restricting tapered housing, for housing it in a crimped state.
[0075] Furthermore, in accordance with another preferred embodiment of the present invention, hooks are provided to secure the device in position after it is deployed.
[0076] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams comprise longitudinal bars having a narrow slit used as the commissural attachment so that extensions the pliant material are tightly inserted through it.
[0077] Furthermore, in accordance with another preferred embodiment of the present invention, the extensions of the pliant material are wrapped about rigid bars serving as anchorage means.
[0078] Furthermore, in accordance with another preferred embodiment of the present invention, extensions of the pliant material are sutured to each other at the rigid bars.
[0079] Furthermore, in accordance with another preferred embodiment of the present invention, a bottom portion of the pliant material is attached to the inlet.
[0080] Furthermore, in accordance with another preferred embodiment of the present invention, the support beams are each provided with a rounded pole, forming a loop through which the pliant material is inserted.
[0081] Furthermore, in accordance with another preferred embodiment of the present invention, the pliant material is provided with longitudinal bars attached to the pliant material at positions assigned for attachment to the support frame, in order to prevent localized stress from forming.
[0082] Furthermore, in accordance with another preferred embodiment of the present invention, the device is further provided with longitudinal bars having protrusions that are inserted in bores in the pliant material, a sheet of PET and through bores provided on the support beams.
[0083] Furthermore, in accordance with another preferred embodiment of the present invention, pliant material is sutured leaving the slack portions free of sutures.
[0084] Furthermore, in accordance with another preferred embodiment of the present invention, a connecting member with a split portion is used to connect leaflets of the pliant material to the support beams, the split connecting member compressing the pliant material in position.
[0085] Furthermore, in accordance with another preferred embodiment of the present invention, a portion of the connecting member is perpendicular to the split portion.
[0086] Furthermore, in accordance with another preferred embodiment of the present invention, the support frame is provided with metallic members coupled to the stent and rigid members are positioned on two opposite sides of the metallic member and held against each other holding portion of the pliant material between them, sutured, the metallic members wrapped with PET.
[0087] Furthermore, in accordance with another preferred embodiment of the present invention, the device is further provided with spring in order to reduce wear of the pliant material.
[0088] Furthermore, in accordance with another preferred embodiment of the present invention, the spring is provided with a spiral.
[0089] Furthermore, in accordance with another preferred embodiment of the present invention, the spring is made from stainless steel.
[0090] Furthermore, in accordance with another preferred embodiment of the present invention, the spring is attached to slots provided on the support frames.
[0091] Furthermore, in accordance with another preferred embodiment of the present invention, the pliant material is sutured to the support frame forming pockets.
[0092] Furthermore, in accordance with another preferred embodiment of the present invention, attachment bars are provided on the stent support at a portion of the stent close to the outlet, onto which the pliant material is coupled, and wherein the pliant material is attached circumferentially to the inlet, leaving slack pliant material.
[0093] Furthermore, in accordance with another preferred embodiment of the present invention, the outlet is tapered with respect to the inlet.
[0094] Furthermore, in accordance with another preferred embodiment of the present invention, the support frame at the outlet is wider in diameter than the pliant material forming the outlet.
[0095] Furthermore, in accordance with another preferred embodiment of the present invention, the pliant material is reinforced using PET.
[0096] Furthermore, in accordance with another preferred embodiment of the present invention, the support frame is a tube having an inner wall, having sinusoidal fold lines, wherein the pliant material is sutured to the inner wall of the tube along suture lines.
[0097] Furthermore, in accordance with another preferred embodiment of the present invention, additional piece of PET is added below the suture lines.
[0098] Furthermore, in accordance with another preferred embodiment of the present invention, the device is incorporated with an angioplasty balloon.
[0099] Finally, in accordance with another preferred embodiment of the present invention, balloon has a central longitudinal axis that runs along a flow path through the device, and a perimeter, the balloon comprising four inflatable portions, one portion located along a central axis and the other three located on the perimeter, the pliant material in the form of leaflets is distributed about the perimeter.
BRIEF DESCRIPTION OF THE FIGURES
[0100] To better understand the present invention and appreciate its practical applications, the following Figures are provided and referenced hereafter. It should be noted that the Figures are given as examples only and in no way limit the scope of the invention as defined in the appended claims.
[0101] FIG. 1 represents an oblique view of an embodiment of the invention:
[0102] FIG. 2 represents a cross-sectional view across line 2 - 2 of the embodiment shown in FIG. 1 ;
[0103] FIG. 3 represents an oblique, partly cross-sectional view of another embodiment of the invention; and
[0104] FIG. 4 represents a cross-sectional view across line 4 - 4 of the embodiment shown in FIG. 3 .
DETAILED DESCRIPTION OF THE INVENTION
[0105] A main aspect of the present invention is the introduction of several novel designs for an implantable prosthetic valve. Another aspect of the present invention is the disclosure of several manufacturing methods for implantable prosthetic valves in accordance with the present invention. A further aspect of the present invention is the provision of novel deployment and positioning techniques suitable for the valve of the present invention.
[0106] Basically the implantable prosthetic valve of the present invention comprises a leaflet-valve assembly, preferably tricuspid but not limited to tricuspid valves only, consisting of a conduit having an inlet end and an outlet, made of pliant material arranged so as to present collapsible walls at the outlet. The valve assembly is mounted on a support structure or frame such as a stent adapted to be positioned at a target location within the body duct and deploy the valve assembly by the use of deploying means, such as a balloon catheter or similar devices. In embodiments suitable for safe and convenient percutaneous positioning and deployment the annular frame is able to be posed in two positions, a crimped position where the conduit passage cross-section presented is small so as to permit advancing the device towards its target location, and a deployed position where the frame is radial extended by forces exerted from within (by deploying means) so as to provide support against the body duct wall, secure the valve in position and open itself so as to allow flow through the conduit.
[0107] The valve assembly can be made from biological matter, such as a natural tissue, pericardial tissue or other biological tissue. Alternatively, the valve assembly may be made form biocompatible polymers or similar materials. Homograph biological valves need occasional replacement (usually within 5 to 14 years), and this is a consideration the surgeon must take into account when selecting the proper valve implant according to the patient type. Mechanical valves, which have better durability qualities, carry the associated risk of long-term anticoagulation treatment.
[0108] The frame can be made from shape memory alloys such as nickel titanium (nickel titanium shape memory alloys, or NiTi, as marketed, for example, under the brand name Nitinol), or other biocompatible metals. The percutaneously implantable embodiment of the implantable valve of the present invention has to be suitable for crimping into a narrow configuration for positioning and expandable to a wider, deployed configuration so as to anchor in position in the desired target location.
[0109] The support stent is preferably annular, but may be provided in other shapes too, depending on the cross-section shape of the desired target location passage.
[0110] Manufacturing of the implantable prosthetic valve of the present invention can be done in various methods, by using pericardium or, for example, by using artificial materials made by dipping, injection, electrospinning, rotation, ironing, or pressing.
[0111] The attachment of the valve assembly to the support stent can be accomplished in several ways, such as by sewing it to several anchoring points on the support frame or stent, or riveting it, pinning it, adhering it, or welding it, to provide a valve assembly that is cast or molded over the support frame or stent, or use any other suitable way of attachment.
[0112] To prevent leakage from the inlet it is optionally possible to roll up some slack wall of the inlet over the edge of the frame so as to present rolled-up sleeve-like portion at the inlet.
[0113] Furthermore, floating supports may be added to enhance the stability of the device and prevent it from turning inside out.
[0114] An important aspect of certain embodiments of the present invention is the provision of rigid support beams incorporated with the support stent that retains its longitudinal dimension while the entire support stent may be longitudinally or laterally extended.
[0115] The aforementioned embodiments as well as other embodiments, manufacturing methods, different designs and different types of devices are discussed and explained below with reference to the accompanying drawings. Note that the drawings are only given for the purpose of understanding the present invention and presenting some preferred embodiments of the present invention, but this does in no way limit the scope of the present invention as defined in the appended claims.
[0116] FIGS. 1 and 2 illustrate a general tricuspid implantable prosthetic valve 10 in accordance with a preferred embodiment of the present invention, suitable for percutaneous deployment using an expandable stent or similar deploying means, shown in its deployed position. Valve 10 comprises a valve assembly 20 having an inlet 22 and an outlet 24 , the outlet walls consisting of collapsible pliant leaflet material 26 that is arranged to collapse in a tricuspid arrangement. Valve assembly 20 is attached to an annular support stent 32 , the one in this figure being a net-like frame designed to be adapted to crimp evenly so as to present a narrow configuration and be radially deployable so as to extend to occupy the passage at the target location for implantation in a body duct. Support beams 34 are provided on annular support stent 32 to provide anchorage to valve assembly 20 . Support beams 34 are optionally provided with bores 36 to allow stitching of valve assembly 20 to support beams 34 by thread, wire, or other attachment means.
[0117] The proximal portion 38 of support stent 32 is snuggly fit or fastened to the proximal portion of valve assembly 20 so that any flow is only into inlet 22 . In the particular embodiment depicted, the proximal portion of the valve assembly 20 is rolled over the support stent 32 at the inlet 22 , thereby forming a rolled-up sleeve-like portion 21 that prevents leakage. Optionally the radial sections 23 of each leaflet 26 are closed by stitching, gluing or other means to narrow outlet 24 while leaving the slack portions 25 free. The distal portion 42 of support stent 32 is narrower than proximal portion 38 . The combination of the effect on flow characteristics due to the narrowing of support stent 32 and the narrowing of outlet 24 is sufficient to engender the desired effect or flow characteristics, namely, non-laminar retrograde flow that will assist in the closing of leaflets 26 .
[0118] Another embodiment of the invention is shown in FIGS. 3 and 4 . A prosthetic valve 50 comprises a valve assembly 52 positioned within a support stent 54 . The proximal 56 and distal 58 portions of support stent 54 are narrow as compared to the mid-portion 60 of support stent 54 , where valve assembly 52 is positioned. Within support stent mid-portion 60 valve assembly 52 is preferably positioned co-axially and at a small distance, for example, from 0.5 to 3 cm, from the interior surface 64 of support stent 54 . Valve assembly 52 is attached by connecting membrane 66 to stent supports 68 , which optimally have holes or projections 70 to anchor said membranes 66 . Any annular space between interior surface 64 and valve assembly 52 is filled with appropriate material to prevent flow around valve assembly 52 . Valve leaflets are shown in closed 72 and open 74 positions.
[0119] The effective cross-sectional area of valve assembly 52 will preferably be from about 40 to 80% of the cross-sectional area across support stent midsection 60 .
[0120] The preferred embodiments representing an implantable prosthetic valve in accordance with the present invention are relatively easy to manufacture as they are generally flat throughout most of the production process and only at the final stage of mounting the other elements of the valve assembly on the support frame, a three dimensional form is established.
[0121] A typical size of an aortic prosthetic valve is from about 19 to about 26 mm in diameter. A maximal size of a catheter inserted into the femoral artery should be no more than 9 mm in diameter. The present invention introduces a device, which has the ability to change its diameter from about 4 mm to about 26 mm. Artificial valves are not new; however, artificial valves in accordance with the present invention posses the ability to change shape and size for the purpose of delivery and as such are novel. These newly designed valves require new manufacturing methods and technical inventions and improvements, some of which were described herein.
[0122] As mentioned earlier, the material of which the valve is made from can be either biological or artificial. In any case new technologies are needed to create such a valve.
[0123] To attach the valve to the body, the blood vessels determine the size during delivery, and the requirements for it to work efficiently, there is a need to mount it on a collapsible construction which can be crimped to a small size, be expanded to a larger size, and be strong enough to act as a support for the valve function. This construction, which is in somewhat similar to a large “stent”, can be made of different materials such as Nitinol, biocompatible stainless steel, polymeric material or a combination of all. Special requirement for the stent are a subject of some of the embodiments discussed herein.
[0124] The mounting of the valve onto a collapsible stent is a new field of problems. New solutions to this problem are described herein.
[0125] Another major aspect of the design of the valve of the present invention is the attachment to the body.
[0126] In the traditional procedure the valve is sutured in place by a complicated suturing procedure. In the case of the percutaneous procedure there is no direct access to the implantation site therefore different attachment techniques are needed.
[0127] Another new problem that is dealt herein is the delivery procedure, which is new and unique. Positioning of the device in the body in an accurate location and orientation requires special marking and measuring methods of the device and surgical site as was disclosed herein.
[0128] Artificial polymer valves require special treatment and special conditions when kept on a shelf, as well as a special sterilization procedure. One of the consequences of the shelf treatment is the need to crimp the valve during the implantation procedure. A series of devices and inventions to allow the crimping procedure are disclosed herein.
[0129] It should be clear that the description of the embodiments and attached Figures set forth in this specification serves only for a better understanding of the invention, without limiting its scope as covered by the following claims.
[0130] It should also be clear that a person skilled in the art, after reading the present specification could make adjustments or amendments to the attached Figures and above described embodiments that would still be covered by the following claims. | A valve prosthesis device and methods for deployment is disclosed. The device comprises an expandable support stent and a valve assembly comprising a flexible conduit having an inlet end and an outlet, made of pliant material attached to the support beams providing collapsible slack portions of the conduit at the outlet. Flow is allowed to pass through the valve prosthesis device from the inlet to the outlet, but reverse flow is prevented as the collapsible slack portions of the valve assembly collapse inwardly. The device is configured so that retrograde flow will be altered from laminar flow and directed towards the leaflets to effect closing. The device can be deployed in a native heart valve position using a deployment catheter advanced through a body lumen such as a blood vessel, including an aorta. | 0 |
BACKGROUND
The claimed inventions relate generally to locking mechanisms, particularly those for doors, and more particularly, to safe or security doors. The claimed inventions concern mechanisms that improve the ability of such doors and their locking systems to withstand external forces intended to disable the locking systems and allow unauthorized entry.
BRIEF SUMMARY
Disclosed herein are various exemplary mechanisms by which external forces applied to doors and their locking mechanisms are deflected or directed away from the critical components of the locking system thereby preserving the integrity of the locking system and preventing unauthorized entry. Detailed information on various example embodiments of the inventions are provided in the Detailed Description below, and the inventions are defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A , 1 B, 1 C and 1 D show an exemplary force deflector with a force transfer plate, locking pins, locking pin connection plate, and single bar force transfer actuator mounted on a safe door.
FIGS. 2A , 2 B, 2 C, and 2 D show an exemplary force transfer plate with a single bar force transfer actuator, a rotational entry shaft, a force transfer shaft, and a locking mechanism.
FIGS. 3A and 3B show an exemplary single bar force actuator and force transfer pin.
FIGS. 4A and 4B show a double force deflector with two force transfer plates and a single bar force actuator and force transfer pins.
FIGS. 5A , 5 B, 5 C, and 5 D show a double force deflector with two force transfer plates and a single bar offset force actuator and force transfer pins mounted on a safe door.
Reference will now be made in detail to various systems incorporating a force deflector with a force transfer plate and force actuator bar that may include some embodiments of the claimed inventions, examples of which are illustrated in the accompanying drawings.
DETAILED DESCRIPTION
Many persons have come to rely on security devices such as safes and security doors to protect themselves and their property. To use such a security safe or security door and take advantage of its security features and protection, one must operate a locking system that allows only certain operators access to inside the safe or inside the security door. Typically, such a locking system involves the actual lock, but also a wheel or handle or other such device used, usually by turning, to disengage the latch of the safe or security door and allow the same to be opened after the actual lock has been deactivated. The operation of such a typical locking system usually involves closing the safe door or security door, turning the wheel or handle or otherwise activating a latch or series of locking pins, which engage the door frame, to prevent the safe door or security door from being opened, and then activating a lock to prevent the latch or series of pins from being deactivated without the proper entry permission parameter, such as a combination or key to the lock or locking system. When the operator correctly uses the combination or key to activate the lock and lock the safe or security door, the operator causes a physical object, sometimes referred to as a “tongue” to move into a certain position in contact or near contact with the latch or locking pins, thereby preventing the latch or locking pins from disengaging from the door frame. Accordingly, unless the operator uses the proper entry permission parameter, such as a combination or a key, the latch or locking pins will not disengage and the lock will not be deactivated and the safe or security door remains locked.
Over time those persons desiring to open a safe or security door without the proper entry permission parameter have devised numerous methods of doing so. One particularly effective and simple method of gaining such unauthorized entry involves supplying force to one or more of the latches or locking pins engaged in the door frame. Typically, this is done by drilling through the outside wall of the safe or security door frame to expose a latch or locking pin or pins. A force is then applied to the latch or locking pin, usually by striking the latch or pin with a physical object. That force is transferred through the latch or locking pin back to the lock tongue. If the applied force is great enough, the tongue is sheared or otherwise broken or disabled. As the tongue is the main component of the lock or locking system, once it is sheared off, disabled, or broken, the wheel or handle or other such device on the outside of the safe or security door can be activated to disengage the latch or locking pins from the door frame. At that point the safe or security door is opened, and access is gained to the persons or property within the safe or security door, without the use of the proper entry permission parameter combination or key.
Referring now to FIGS. 1A and 1B , an exemplary force deflector system is depicted in locked position. Door 1 resides within door frame 2 , which is connected to the sides of the safe or security door, and engages the door frame 2 by a series of locking pins or latches 3 . Door 1 opens through the operation of hinges 4 . Door 1 has attached to it a locking pin connection plate or latch plate 5 , which is likewise welded or otherwise attached to locking pins 3 . FIG. 1B shows the locking pins 3 and the safe or security door from the side view. When in the locked position as shown in FIG. 1A , the locking pins 3 extend through the side of the safe or security door 1 and behind (shown) or into (not shown) the door frame 2 and engage the door frame 2 (and the sides of the safe or security door, if desired) to prevent the door from opening.
As shown in FIG. 1A , one locking pin connection plate or bar 5 is depicted as a long narrow plate attached to the door 1 that has its long axis parallel to the long axis of the door 1 , but there may be any number of plates, and they may be of any size or shape and may or may not be attached to the door, or they may be attached indirectly or directly. Also in this example and as shown in FIG. 1A , the locking pin connection plate 5 is attached to a force transfer plate or bar 6 and a single bar force transfer actuator 7 , which is a plate or rod that, as more fully explained below, is connected directly or indirectly with the wheel or handle or other such device on the outside of the safe or security door and as the operator turns or otherwise activates the wheel or handle on the outside of the door, the single bar force transfer actuator 7 also turns or is activated.
As more specifically shown in FIGS. 1C and 1D , the locking pins 3 are welded or otherwise connected to the locking pin connection plate 5 . FIG. 1C shows the locking pins 3 , the locking pin connection plate 5 , and the force transfer plate 6 without the safe or security door. As shown, the locking pin connection plate 5 is welded or otherwise attached to the force transfer plate 6 . FIG. 1D shows the locking pins 3 , the locking pin connection plate 5 , and the force transfer plate 6 from the side view without the safe or security door.
Although FIGS. 1A and 1C show only one locking pin connection plate 5 on one side of the door and only one force transfer plate 6 and single bar force transfer actuator 7 , another locking pin connection plate 5 could be used on the other side of the door with a separate force transfer plate 6 and single bar force transfer actuator 7 . Indeed, those skilled in the art will appreciate that additional locking pin connection plates 5 may be used, on any side of the door (left, right, top, and bottom), and each such plates may interact with separate force transfer plates 6 and single bar force transfer actuators 7 , or multiple such force transfer plates and actuators.
Referring now to FIGS. 2A , 2 B, 2 C, and 2 D the components and operation of an exemplary force deflector are further described. As shown in FIGS. 2A and 2B , the force deflector includes a rotational entry shaft or pin 8 and a force transfer shaft or pin 9 , which are both welded or otherwise connected (such as by a slip collar) to the single bar force actuator 7 . The rotational entry shaft 8 is a physical object, typically cylindrical in shape, that projects through the door, from the handle or other opening mechanism on the outside, through the door itself, through an opening (described in more detail below) in the force transfer plate 6 , and finally is welded or otherwise connected to the single bar force transfer actuator 7 .
The rotational entry shaft 8 may be of any length necessary to allow communication between the wheel or handle or other opening mechanism on the outside of the door and the single bar force transfer actuator 7 on the inside of the door. Likewise, the rotational entry shaft 8 may be of any shape, including square or rectangular in cross section. The rotational entry shaft 8 is also in contact with the safe or security door, in a manner that allows the shaft to engage the door but still rotate when operated, through any one of many methods well known to those of skill in the art, such as through use of bearings.
The force transfer shaft 9 does not run through the door, but instead is welded or otherwise attached to the single bar force transfer actuator 7 on the inside of the door and projects toward the outside of the door through an opening in the force transfer plate 6 . Similar to the rotational entry shaft 8 , the force transfer shaft 9 may be of any length or shape necessary to allow communication between the single bar force transfer actuator 7 and the force transfer plate 6 .
The positions of the rotational entry shaft 8 and the force transfer shaft 9 are shown by example only, and those of skill in the art will appreciate that those positions can by varied at any point along the single bar force transfer actuator 7 to achieve many objectives, such as increased performance or ease of construction, and still fall within the present invention.
FIG. 2C is a more detailed view of the openings in the force transfer plate through which the rotational entry shaft 8 and the force transfer shaft 9 pass. In its position of communication between the handle or other opening mechanism on the outside of the safe or security door and the single bar force transfer actuator 7 on the inside of the safe or security door, the rotational entry shaft 8 passes through the rotational shaft travel slot 10 , which is an aperture or opening in the force transfer plate 6 . The rotational shaft travel slot 10 may be of any shape, but as more particularly described below, must be large enough to permit the force transfer plate 6 (and therefore the connected single bar force transfer actuator 7 and force transfer shaft 9 ) to rotate and move spatially. Likewise, in its position of attachment with the single bar force transfer actuator 7 , the force transfer shaft 9 passes through the force transfer shaft travel slot 11 , which is another aperture or opening in the force transfer plate 6 . The force transfer shaft travel slot 11 may also be of any shape, but similar to the rotational shaft travel slot 10 , and as more particularly described below, it also must be large enough to permit the force transfer plate 6 (and therefore the connected single bar force transfer actuator 7 and force transfer shaft 9 ) to rotate and move spatially.
In normal or typical operation, when an operator desires to lock the safe or security door, or in other words to secure the door from unauthorized entry, the operator activates the lock or locking mechanism 12 , and more particularly the tongue or bar of the locking mechanism 13 , which then engages the force transfer plate through slot 14 to prevent the movement of the force transfer plate, and therefore the movement of the locking pins out of the door frame. The slot 14 in the force transfer plate 6 is an aperture or opening through which the tongue 13 passes when the locking mechanism 12 is activated. Similar to the rotational shaft travel slot 10 or the force transfer travel slot 11 , the slot 14 allows an object to pass through another object. In case of slot 14 , it allows the tongue 13 to engage the force transfer plate 6 , and prevent the force transfer plate 6 from moving, when the tongue 13 passes through the slot 14 in the force transfer plate 6 .
Assuming as shown in FIG. 2A that the safe or security door is unlocked, or in other words that the locking mechanism tongue 13 is withdrawn from the tongue locking slot 14 in the force transfer plate 6 , then the safe or security door is free to open when the handle or other opening mechanism is activated. In FIG. 2A , the safe or security door is unlocked and the wheel or handle or other such mechanism on the outside of the door has been turned so as to also turn the force transfer actuator 7 , and as described in more detail below, the safe or security door is in a position to be pulled open. As shown, the force transfer plate 6 (and therefore the locking pin connection plate 5 and locking pins 3 ) have been moved spatially as a result of the tongue 13 being withdrawn from the slot 14 .
FIG. 2D is a more detailed view of the top of the force transfer plate 6 , showing the slot 14 into which the tongue 13 projects when the locking mechanism 12 is activated using the proper entry permission parameter, such as a combination or a key.
FIGS. 3A and 3B show a more detailed view of the single bar force transfer actuator 7 . As shown in FIG. 3A , the rotational entry shaft 8 is positioned between the force transfer shaft 9 and an optional secondary force transfer shaft 9 shown at position 15 . The position 15 of the secondary force transfer shaft is shown by example only, and those of skill in the art will appreciate that the position can by varied at any point along the single bar force transfer actuator 7 to achieve many objectives, such as increased performance or ease of construction, and still fall within the present invention. The operation of the additional force transfer shaft is described in more detail below.
As can be seen from FIG. 3B , both the rotational entry shaft 8 and the force transfer shaft 9 project from the single bar force transfer actuator toward the outside the door. The projected end 16 of the rotational entry shaft 8 passes through the rotational shaft travel slot 10 and through the safe or security door and engages or is connected to the wheel or handle or other opening mechanism on the outside of the safe or security door. The projected end 17 of the force transfer shaft 9 passes through the force transfer shaft travel slot 11 .
Referring again to FIG. 2A , the safe or security door and the force deflector are in the unlocked position, and as the handle or other opening mechanism of the safe or security door is turned (to open the door), the rotational entry shaft 8 rotates, but because it is merely a shaft it turns but does not move spatially. Because the rotational entry shaft 8 is welded or otherwise attached to the single bar force transfer actuator 7 , which in turn is welded or otherwise attached to the force transfer shaft 9 , the single bar force transfer actuator 7 and the force transfer shaft 9 rotate as well. During rotation, the single bar force transfer actuator 7 and the force transfer shaft 9 also move spatially, unlike the rotational entry shaft 8 that merely turns around a single point, when the handle or other opening mechanism of the safe or security door is turned. When the rotational entry shaft 8 rotates, and the single bar force transfer actuator 7 and the force transfer shaft 9 rotate and move spatially, the force transfer shaft 9 engages the force transfer plate 6 through the force transfer shaft travel slot 11 .
As the rotational shaft 8 continues to rotate, the force transfer shaft 9 continues to engage the force transfer plate 6 through the force transfer shaft travel slot 11 and as a result, causes the force transfer plate 6 to move spatially (horizontally) away from the side of the safe or security door. In FIG. 2A this is evident from the positions of the tongue 13 and the slot 14 . As shown, the tongue 13 of the locking mechanism 12 is withdrawn from slot 14 , and as the force transfer plate 6 moves spatially (horizontally) away from the side of the safe or security door, the locking mechanism 12 (and tongue 13 ) stay stationary and the slot 14 , which is part of and moving with the force transfer plate 6 , cannot be engaged by the tongue 13 .
As the rotation continues and the force transfer plate 6 continues to move away from the side of the safe or security door, the force transfer shaft 9 travels up the force transfer travel slot 11 . The force transfer travel slot 11 both allows engagement between the force transfer shaft 9 and the force transfer plate 6 and allows the force deflector plate 6 to continue to move spatially away from the side of the safe or security door as rotation continues. It is understood that the single bar force transfer actuator 7 may have two or more force transfer shafts 9 connected to it and each such force transfer shaft 9 would have a corresponding force transfer slot 11 in the force transfer plate 6 . It is also understood that the single bar force transfer actuator 7 may have an optional secondary force transfer shaft or shafts, which would operate in the same manner as the force transfer shaft or shafts 9 . Also, just as the projected end 17 of the force transfer shaft 9 passes through the force transfer shaft travel slot 11 , the projected ends of any secondary force transfer shafts 9 at position 15 would also pass through the force transfer plate 6 via force transfer shaft travel slots 11 and allow any such secondary force transfer shafts to both engage the force transfer plate 6 and allow the force deflector plate 6 to continue to move spatially away from the side of the safe or security door as rotation continues.
Again referring to FIG. 2A , at the same time as the movement of the force transfer shaft 9 and as the force deflector plate 6 moves away from the side of the safe or security door, the rotational shaft travel slot 10 provides an opening for the rotational shaft 8 to prevent the rotational shaft 8 from preventing the movement of the force deflector plate 6 . The rotational shaft travel slot 10 allows the force deflector plate 6 to continue to move away from the side of the safe or security door as rotation continues.
In other words, the force transfer travel slot 11 allows the force transfer shaft 9 to engage the force transfer plate 6 and allows the force transfer plate 6 to continue to move away from the side of the safe or security door as rotation continues, while the rotational shaft travel slot 10 allows the force transfer plate 6 to continue to move away from the side of the safe or security door as rotation continues by providing a space for the rotational entry shaft 8 to rotate without coming into contact with, and preventing the movement of, the force transfer plate 6 .
As rotation continues, because the force transfer plate 6 is connected to the locking pin connection plate 5 and the force transfer plate 6 move spatially toward the middle of the safe or security door, the locking pin connection plate 5 also moves spatially toward the middle of the safe or security door. As a result, the locking pins 3 are withdrawn from the door frame 2 and/or the sides of the safe or security door and accordingly the door may be opened.
To close the door, before the locking mechanism 12 is actuated, the handle or opening mechanism is operated, usually by turning in the opposite direction, to cause the above-described process to proceed in reverse. When reversed, the locking pin connection plate 5 and the force transfer plate 6 move spatially away from the middle of the safe or security door and toward the edge of the safe or security door. In such a manner, the locking pins 3 are inserted behind or into the door frame 2 and/or the sides of the safe or security door. In this manner the safe or security door is closed and prepared for locking.
Now referring to FIG. 2B , the safe or security door with the force deflector is shown in the closed and locked position. The tongue 13 of the lock is shown extended into the tongue lock slot 14 —the opening for the tongue—in the top of the force transfer plate 6 . The tongue 13 is separated from the edge of the force transfer plate 6 in the tongue lock slot 14 by a distance 18 .
The single bar force actuator 7 is shown in the horizontal position perpendicular to the locking pin connection plate 5 . The rotational entry shaft 8 and the force transfer shaft 9 are aligned with each other, in this case horizontally, and are aligned in a plane perpendicular to the locking pin connection plate 5 .
The force transfer shaft 9 , which engages the force transfer plate 6 through the force transfer shaft travel slot 11 , is separated from the edge of the force transfer shaft travel slot 11 by a distance 19 . Distance 19 can be any distance, including zero, which means that the force transfer shaft 9 is in contact with the force transfer plate 6 and the point of contact is the edge of the force transfer shaft 9 where it passes through the force transfer shaft travel slot 11 . Preferably, although it is not required, the distance 19 is less than the distance 18 so that with the locking mechanism 12 activated (and therefore the tongue 13 extended into the slot 14 ), the force transfer plate 6 , as it moves spatially (horizontally), would engage, or come into contact with, the force transfer shaft 9 before it would engage, or come into contact with, the tongue 13 .
If the distance 19 is more than the distance 18 so that as the force transfer plate 6 moves it engages the tongue 13 before the force transfer shaft 9 , the force deflector will still work because the tongue 13 will deflect and can absorb some movement, thereby allowing the force transfer plate 6 to engage or come into contact with the force transfer shaft 9 . Accordingly, if the distance 19 is more than the distance 18 , the tongue 13 will deform or bend to a certain extent before failing, allowing time and distance for the force transfer plate 6 to engage or come into contact with the force transfer shaft 9 .
With the safe or security door and the force deflector in the locked position, any force applied to any of the locking pins 3 is transferred to the safe or security door without damaging the tongue 13 , thereby preventing the locking mechanism from being disabled. Specifically, when a force is applied to any of the locking pins 3 , the force is transferred to the locking pin connection plate 5 . From the locking pin connection plate 5 , the force travels to the force deflector plate 6 . Because the force deflector plate 6 is in contact with, or separated by a distance of 19 from the force transfer shaft 9 , as the force transfer plate 6 comes into contact with the force transfer shaft 9 , the applied force is transferred from the force transfer plate 6 to the force transfer shaft 9 . Likewise, because the force transfer shaft 9 is welded or otherwise attached to the single bar force transfer actuator 7 , which in turn is welded or otherwise attached to the rotational entry shaft 8 , the applied force is transferred from the force transfer shaft 9 to the rotational entry shaft 8 . Finally, because the rotational entry shaft 8 is in contact or close communication with the safe or security door itself, the applied force is transferred to the safe or security door. In summary, the force applied to locking pins 3 is transferred from the force transfer shaft 9 through the single bar force transfer actuator 7 , through the rotational entry shaft 8 to the safe or security door where it is harmlessly absorbed and dissipated.
Without this system, any force applied to the locking pins 3 is transferred to the tongue 13 . Specifically, when a force is applied to any of the locking pins 3 , the force is transferred to the force deflector plate 6 through the locking pin connection plate 5 . Without the interaction described above involving the force transfer plate 6 , the single bar force transfer actuator 7 , the rotational entry shaft 8 , the force transfer shaft 9 , and the travel slots 10 and 11 , any force applied to the locking pins 3 is transferred from the force transfer plate 6 directly to the tongue 13 . Similarly, if the force deflector plate 6 is separated by a distance of 19 from the force transfer shaft 9 , but that distance 19 is greater than the distance 18 between the tongue 13 and the tongue locking slot 14 , the force transfer plate 6 , as it moves spatially (horizontally) due to any applied force, would engage the tongue 13 before it would engage the force transfer shaft 9 .
When applied to the tongue 13 , experience has shown that if the force is great enough, the tongue 13 is sheared or otherwise broken or disabled. As the tongue 13 is an important component of the locking system, and sometimes the only or main component of the locking system, once it is sheared off, disabled, or broken, the wheel or handle or other such device on the outside of the safe or security door can be activated to rotate the rotational entry shaft. As previously explained, this ultimately withdraws and disengages the locking pins 3 from the door frame 2 and/or the sides of the safe or security door. At that point the safe or security door is opened, without the use of the proper entry permission parameter combination or key. Accordingly, by deflecting the force away from the tongue 13 , the force deflector prevents a means of unauthorized entry into the safe or security door.
Those of skill in the art will appreciate that many variants of the above-described force deflector are possible and all fall within the present invention. For example, in an alternative operation, another locking pin connection plate 5 is added to the side of the door opposite from the current locking pin connection plate 5 . Those of skill in the art would appreciate that conceptually there is no limit to the number, locations, or shapes of locking pin connection plates 5 (and locking pins 3 ) and multiple such devices may be located on the sides, top, and bottom of the safe or security door. The only restraint to such devices is the physical limitation of size and placement—the locking pin connection plates and pins must be configured to allow operation of the safe or security door.
For illustration, FIGS. 4A and 4B show a force deflector using two locking pin connection plates 5 , two force transfer plates 6 , and a single bar force transfer actuator 7 . As shown in FIGS. 3A and 3B , the single bar force transfer actuator 7 may have two force transfer shafts 9 , and in this case it does. The secondary force transfer shaft 9 at position 15 allows the single bar force transfer actuator 7 to (1) engage a single force transfer plate 6 at multiple locations (through force transfer shaft travel slots 11 ), (2) engage multiple force transfer plates 6 , and (3) to engage multiple force transfer plates 6 at multiple locations.
Those of skill in the art will appreciate that the size and shape of the force transfer shafts 9 , including the secondary force transfer shaft, may be varied to achieve any number of desired goals, such as the best possible security or ease of use of the mechanism. Those of skill in the art will also appreciate that although FIG. 4A shows two locking pin connection plates 5 on one side of the door and two force transfer plates 6 , multiple locking pin connection plates 5 and multiple force transfer plate 6 could be added, and may interact with multiple single bar force transfer actuators 7 and still fall within the scope of the present invention.
In operation, the force deflector depicted in FIGS. 4A and 4B operates in a similar manner as that described above. As the handle or other opening mechanism of the safe or security door is turned (with the goal being to open the door), the rotational entry shaft 8 rotates and the single bar force transfer actuator 7 and the force transfer shafts 9 move in an arc pattern. The arc pattern of movement of the single bar force transfer actuator 7 and the force transfer shafts 9 is created because these devices rotate and at the same time move spatially as the handle or other opening mechanism of the safe or security door is turned. The force transfer shafts 9 also engage the two force transfer plates 6 through the force transfer shaft travel slots 11 (one in each force transfer plate 6 ). The force transfer travel slots 11 both allow engagement between the force transfer shafts 9 and the force transfer plates 6 and allow the force deflector plates 6 to continue to move away from the sides of the safe or security door (and toward the middle of the door) as rotation continues. Simultaneously, as the rotational entry shaft 8 rotates, the force deflector plates 6 travel along the two rotational shaft travel slots 10 (one in each force transfer plate 6 ); this allows the force deflector plates 6 to continue to move away from the side of the safe or security door as rotation continues.
As rotation continues the two locking pin connection plates 5 and the two force transfer plates 6 move spatially toward the middle of the safe or security door and toward each other. In this manner the rotation withdraws the locking pins 3 from the sides of the safe or security door and allows the door to be opened. To close the door, before the locking mechanism 12 is activated, the handle or opening mechanism is operated, usually by turning in the opposite direction, to cause the above-described process to proceed in reverse. When reversed, the locking pin connection plates 5 and the force transfer plates 6 move spatially away from the middle of the safe or security door (and away from each other) and toward the door edge and the locking pins 3 are inserted behind or into the door frame 2 and/or sides of the safe or security door. In this manner the safe or security door is closed and prepared for locking; i.e. the door is closed, the locking pins are inserted, and the locking mechanism 12 can be activated to lock the safe or security door.
The force deflector depicted in FIGS. 4A and 4B with the secondary force transfer shaft 9 depicted in FIGS. 3A , and 3 B has several unique and beneficial characteristics. Although it is understood that this force deflector will operate with a single force transfer shaft 9 (engaging both force transfer plates 6 ), more force transfer shafts offer improved performance and two such shafts are shown here (the force transfer shaft 9 and the secondary force transfer shaft at position 15 ). Because of the secondary force transfer shaft 9 and the additional force transfer plate 6 , any force applied to any of the locking pins 3 , on any side of the safe or security door, is transferred away from the tongue 13 through the force transfer shafts 9 , thereby preventing the locking mechanism from being disabled. Specifically, when a force is applied to any of the locking pins 3 , the force is transferred to one of the locking pin connection plates 5 . From the locking pin connection plate 5 , the force travels to one of the force deflector plates 6 . As the force transfer plate 6 comes into contact with one of the force transfer shafts 9 , some of the applied force is transferred from the force transfer plate 6 to the force transfer shaft and eventually to the safe or security door through the single bar force transfer actuator 7 and the rotational entry shaft 8 . Some of the force, however, is transferred from the force transfer shaft 9 through the single bar force transfer actuator 7 to the other force transfer shaft 9 . In this manner, some of the force is transferred to the second force deflector plate 6 and ultimately the side of the safe or security door. This division and distribution of the applied force necessarily prevents any one component from bearing the full applied force, improves the deflection and absorption of the applied force, and prevents a means of unauthorized entry into the safe or security door. By expanding the number of force transfer shafts and having each engage multiple force deflector plates 6 , the applied force can be further divided and distributed.
Additionally, as a result of the multiple force transfer plates 6 , the force deflector can use multiple locking mechanisms 12 positioned at different locations on door 1 . Accordingly, the safe or security door would be more secure.
An alternative modification to the force deflector depicted in FIGS. 4A and 4B involves using two single bar force transfer actuators 7 , one for each force transfer plate 6 . In operation, one of the two single bar force transfer actuators 7 engages one of the two force transfer plates 6 through the force transfer shaft travel slot 11 by way of the force transfer shaft 9 , while the second single bar force transfer actuator 7 engages the remaining force transfer plate 6 in the same fashion. As the handle or other opening mechanism is activated on the safe or security door, the two single bar force transfer actuators 7 cause the two locking pin connection plates 5 and the two force transfer plates 6 move spatially toward the middle of the safe or security door and toward each other, and ultimately the locking pins 3 to be withdrawn from the sides of the safe or security door. In this manner, the door may be opened. By expanding the number of force transfer actuators 7 and having each engage multiple force deflector plates 6 , the applied force can be further divided and distributed.
Another exemplary alternative is set forth in FIGS. 5A and 5B , which depict a double bar force transfer actuator 20 . Similar to the force deflector depicted in FIGS. 4A and 4B , the additional force transfer shaft 9 , which corresponds to a second force transfer plate 6 , transfers any force applied to any of the locking pins 3 , on any side of the safe or security door, away from the tongue 13 , thereby preventing the locking mechanism from being disabled. Again, as with the force deflector shown in the locked position in FIG. 2B , FIG. 5B shows the alternative arrangement in the locked position with the force transfer shafts 9 aligned with the rotational entry shaft 8 (in this case horizontally) and aligned in a plane perpendicular to the locking pin connection plate 5 .
One advantage of such a system results from the multiple force transfer plates 6 , which can be used in conjunction with multiple locking mechanisms 12 positioned at different locations on door 1 to improve security. Additional advantages of the force deflector shown in FIGS. 5A and 5B stem from the offset nature of the offset distance 21 or 22 between each of the force transfer ends 23 and 24 of the double bar force transfer actuator 20 . The offset distance 21 or 22 allows the size and shape of force transfer plates 6 to be changed, and by varying the offset distance 21 or 22 , additional space around the rotational entry shaft 8 and the locking mechanism 12 can be created and controlled. The additional space is beneficial for ease of manufacturing and repair, as well as because it allows additional space for optional locking mechanisms to be used.
FIGS. 5C and 5D show an another alternative arrangement with additional advantages. Two additional force transfer shafts 25 are shown, one in each of the force transfer ends 23 and 24 of the double bar force actuator 20 . Again, as with the force deflector shown in the locked position in FIG. 2B , FIG. 5D shows the alternative arrangement in the locked position with the force transfer shafts 9 aligned with the rotational entry shaft 8 (in this case horizontally) and aligned in a plane perpendicular to the locking pin connection plate 5 . Additionally, the two additional force transfer shafts 25 also aligned with the rotational entry shaft 8 (in this case vertically).
The force transfer shafts 25 correspond to two additional force transfer travel slots 26 , one in each of the force transfer plates 6 . One advantage of the force transfer shafts 25 is that any applied force is divided between four such shafts, further preventing any one component from bearing the total applied force, improving the deflection and absorption of the applied force, and preventing a means of unauthorized entry into the safe or security door.
Those of skill in the art will also appreciate that although FIGS. 5A and 5C show two locking pin connection plates 5 on one side of the door and two force transfer plates 6 , multiple locking pin connection plates 5 and multiple force transfer plate 6 could be added, and may interact with multiple double bar force transfer actuators 20 and still fall within the scope of the present invention.
Although the systems described above have been discussed in relation to a safe or security door, those systems may be adapted to other door types with minor modification, for example garage doors or access doors of many other types. The scope of use of the above described force deflector should therefore be interpreted broadly rather than restrictively.
While various systems incorporating a force deflector have been described and illustrated in conjunction with a number of specific configurations and methods, those skilled in the art will appreciate that variations and modifications may be made without departing from the principles herein illustrated, described, and claimed. The present invention, as defined by the appended claims, may be embodied in other specific forms without departing from its spirit or essential characteristics. The configurations described herein are to be considered in all respects as only illustrative, and not restrictive. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | Disclosed herein are various exemplary mechanisms by which external forces applied to doors and their locking mechanisms are deflected or directed away from the critical components of the locking system thereby preserving the integrity of the locking system and preventing unauthorized entry. Detailed information on various example embodiments of the inventions are provided in the Detailed Description below, and the inventions are defined by the appended claims. | 4 |
This invention was made with Government support under NIH Grant No. AM-14881 awarded by the Department of Health and Human Services and NSF US/Japan Cooperative Project R-MPC-0163 awarded by the National Science Foundation. The Government has certain rights in this invention.
DESCRIPTION
1. Technical Field
This invention relates to new derivatives of vitamin D 3 and to a method for their preparation.
More specifically this invention relates to 1,24-dihydroxylated-Δ 22 -vitamin D 3 compounds.
2. Background of the Invention
Since the discovery that the active hormonal form of vitamin D in the stimulation of intestinal calcium transport, intestinal phosphate transport, and bone calcium mobilization is 1,25-dihydroxyvitamin D 3 (1,25-(OH) 2 D 3 ), considerable interest in the chemical synthesis of analogs of this compound has developed with a view toward finding in such analogs either increased biological activity or specific target organ actions. The most potent analogs which have been prepared to date are 26,26,26,27,27,27-hexafluoro-1,25-dihydroxyvitamin D 3 (26,27-F 6 -1,25-(OH) 2 D 3 ) (U.S. Pat. No. 4,358,406) and 24,24-difluoro-1,25-dihydroxyvitamin D 3 (24,24-F 2 -1,25-(OH) 2 D 3 ) (U.S. Pat. No. 4,201,881). These compounds provide activity at least 10 fold that of the natural hormone. All other modifications of the side-chain appear to reduce biological activity except the ergosterol side-chain which has an unsaturation at the Δ 22 -position and a methyl group in the 24S-position. This compound appears to be equally active in binding to the chick intestinal cytosol receptor and in biological activity in mammalian species, but appears to be one-tenth as active in birds. It is of interest, therefore, to construct various analogs in which each of these modifications is examined separately. Also of interest is the fact that 1,24-dihydroxyvitamin D 3 (1,24-(OH) 2 D 3 ) is equally as active as is 1,25-(OH) 2 D 3 in binding to the chick intestinal receptor, but when given in vivo 1,24R-(OH) 2 D 3 is only one-tenth as active as 1,25-(OH) 2 D 3 and that the 1,24S-isomer is even less active than the 1,24R-isomer.
DISCLOSURE OF INVENTION
Two new vitamin D derivatives have now been prepared. These compounds are the trans-isomers of 1,24-dihydroxyvitamin D 3 (1,24-(OH) 2 D 3 ) in which a double bond has been inserted in the 22-position and an hydroxyl function substituted in the S- and R-positions on the 24-carbon atom. The compounds are respectively (22E,24S)-1,24-dihydroxy-Δ 22 -vitamin D 3 and (22E,24R)-1,24-dihydroxy-Δ 22 -vitamin D 3 .
Both of the compounds exhibit vitamin D-like activity with the 24-S compound showing the greater activity of the two and approaching, in fact, the activity of 1,25-(OH) 2 D 2 .
BEST MODE FOR CARRYING OUT THE INVENTION
The compounds of this invention can be synthesized in accordance with the following schematic diagram and description in which like compounds are identified by like numbers.
In the description which follows physico-chemical measurements were determined as follows: Melting points were determined on a hot stage microscope and were uncorrected. UV spectra were obtained in ethanol solution with a Shimadzu UV-200 double beam spectrometer. 1 H-NMR spectra were run on a Hitachi R-24A spectrometer, a JEOL PS-100 spectrometer or a JEOL FX-400 spectrometer. All NMR spectra were taken in DCDl 3 solution with tetramethylsilane as internal reference. Mass spectra were obtained with a Shimadzu LKB 9000S spectrometer at 70 eV. Column chromatography was effected with silica gel (Merck, 70-230 mesh). Preparative thin layer chromatography was carried out on precoated plates of silica gel (Merck, silica gel 60 F 254 ). The usual work-up refers to dilution with water, extraction with an organic solvent, washing to neutrality, drying over magnesium sulfate, filtration, and removal of the solvent under reduced pressure. ##STR1##
SYNTHESIS
22-Hydroxy-23,24-dinorchol-1,4,6-triene-3-one (2)
To a solution of 3β-acetoxydinorcholenic acid (1) (7.0 g, 18.04 mmole) in THF (20 mL) lithium aluminum hydride (3.0 g, 78.95 mmole) was added. This mixture was stirred at 60° C. for 14 h. To this reaction mixture water and ethyl acetate were carefully added. Filtration and removal of the solvent gave the residue (5.2 g). This in dioxane (140 mL) was treated with dichlorodicyanobenzoquinone (11.7 g, 51.54 mmole) under reflux for 14 h. After cooling to room temperature the reaction mixture was filtered and the filtrate was evaporated to leave the residue, which was applied to a column of alumina (200 g). Elution with dichloromethane provided the trienone (2) (2.8 g, 47%): mp 156°-157° (from ether). UV λ max EtOH nm (ε): 299 (13000), 252 (9200), 224 (12000), 1 H-NMR (CDCl 3 ): 0.80 (3H, s, 18-H 3 ), 1.04 (3H, d, J=6 Hz, 21-H 3 ), 1.21 (3H, s, 19-H 3 ), 3.10-3.80 (3H, m, 22-H 2 and OH), 5.90-6.40 (4H, m, 2-H, 4-H, 6-H, and 7-H), 7.05 (1H, d, J=10 Hz, 1-H), MS m/z: 326 (M + ), 311, 308, 293, 267, 112.
22-Tetrahydropyranyloxy-23,24-dinorchol-1α,2α-epoxy-4,6-dien-3-one (3)
The alcohol (2) (2.7 g, 8.28 mmole) in dichloromethane (50 mL) was treated with dihydropyrane (1.5 mL, 16.42 mmole) and p-toluenesulfonic acid (50 mg) at room temperature for 1 h. The usual work-up (ethyl acetate for extraction) gave a crude product. To a solution of this product in MeOH (70 mL), 30% H 2 O 2 (4.8 mL) and 10% NaOH/MeOH (0.74 mL) were added and this mixture was stirred at room temperature for 14 h. The usual work-up (ethyl acetate for extraction) gave a crude product, which was applied to a column of silica gel (50 g). Elution with benzene-ethyl acetate (100:1) provided the epoxide (3) (1.45 g, 41%): mp 113°-115° (hexane). UV λ max EtOH nm (ε): 290 (22000), 1 H-NMR (CDCl 3 ): 0.80 (3H, s, 18-H 3 ), 1.07 (3H, d, J= 6 Hz, 21-H 3 ), 1.18 (3H, s, 19-H 3 ), 3.38 (1H, dd, J=4 and 1.5 Hz, 1-H), 3.55 (1H, d, J=4 Hz, 2-H), 3.30-4.10 (4H, m, 22-H 2 and THP), 4.50 (1H, m, THP), 5.58 (1H, d, J=1.5 Hz, 4-H), 6.02 (2H, s, 6-H and 7-H), MS m/z: 342 (M + -DHP), 324 (M + -THPOH), 309, 283, 85.
23,24-Dinorchol-5-ene-1α,3β,22-triol-1,3-diacetate (4)
Lithium (3.25 g) was added in small portions to liquid ammonia (130 mL) at -78° C. under argon atmosphere during 30 min. After stirring for 1 h at -78° C., the epoxide (3) (1.33 g, 3.12 mmole) in dry THF (100 mL) was added dropwise at -78° C. during 30 min. and this mixture was stirred for 1 h at -78° C. To this reaction mixture anhydrous NH 4 Cl (40 g) was added in small portions at -78° C. during 1 h. After 1.5 h the cooling bath was removed and the most of ammonia was removed with bubbling argon. The usual work-up (ether for extraction) gave a crude product (1.23 g). This was treated with acetic anhydride (3 mL) and pyridine (4 mL) at room temperature for 14 h. The usual work-up (ethyl acetate for extraction) gave a crude product (1.3 g). This in methanol (4 mL) and THF (5 mL) was treated with 2 drops of 2M HCl at room temperature for 2 h. The usual work-up (ether for extraction) gave a crude product (1.1 g), which was applied to a column of silica gel (40 g). Elution with benzene-ethyl acetate (10:1) provided the 1,3-diacetate (4) (575 mg, 42%): oil, 1 H-NMR (CDCl 3 ): 0.68 (3H, s, 18-H 3 ), 1.07 (3H, s, 19-H 3 ), 1.99 (3H, s, acetyl), 2.02 (3H, s, acetyl), 3.02-3.72 (2H, m, 22-H 2 ), 4.79 (1H, m, 3-H), 4.98 (1H, m, 1-H), 5.46 (1H, m, 6-H), MS m/z: 372 (M + -CH 3 COOH), 313, 312, 297, 279, 253.
1α,3β-Diacetoxy-23,24-dinorcholan-22-al (5)
The 22-alcohol (4) (550 mg, 1.27 mmole) in dichloromethane (20 mL) was treated with pyridinium chlorochromate (836 mg, 3.85 mmole) and sodium acetate (100 mg) at room temperature for 1 h. To this reaction mixture ether (100 mL) was added and this mixture was filtrated through a short Florisil column. The filtrate was concentrated to leave the residue, which was applied to a column of silica gel (20 g). Elution with benzene-ethyl acetate (20:1) provided the 22-aldehyde (5) (448 mg, 82%): oil, 1 H-NMR (CDCl 3 ): 0.70 (3H, s, 18-H 3 ), 1.07 (3H, s, 19-H 3 ), 1.09 (3H, d, J=7 Hz, 21-H 3 ), 1.99 (3H, s, acetyl), 2.02 (3H, s, acetyl), 4.79 (1H, m, 3-H), 4.98 (1H, m, 1-H), 5.45 (1H, m, 6-H), 9.45 (1H, d, J=4 Hz, 22-H), MS m/z: 310 (M + -2×CH 3 COOH), 295, 253.
(22E)-1α,3β-Diacetoxy-cholesta-5,22-dien-24-one (6)
To a solution of the 22-aldehyde (5) (420 mg, 0.977 mmole) in dimethyl sulfoxide (30 mL) isobutyrylmethylenetriphenylphosphorane (2.03 g, 5.87 mmole) was added. This mixture was stirred at 95° C. for 72 h. The usual work-up (ether for extraction) gave a crude product, which was applied to a column of silica gel (10 g). Elution with benzene-ethyl acetate (10:1) provided the enone (6) (392 mg, 81%): oil, 1 H-NMR (CDCl 3 ): 0.71 (3H, s, 18-H 3 ), 1.08 (3H, s, 19-H 3 ), 1.09 (9H, d, J=7 Hz, 21-H 3 , 26-H 3 , and 27-H 3 ), 1.99 (3H, s, acetyl), 2.02 (3H, s, acetyl), 4.79 (1H, m, 3-H), 4.98 (1H, m, 1-H), 5.45 (1H, m, 6-H), 5.96 (1H, d, J=16 Hz, 23-H), 6.65 (1H, dd, J=16 and 8 Hz, 22-H), MS m/z: 438 (M + -CH 3 COOH), 378 (M + -2×CH 3 COOH), 363, 335, 307, 253, 43.
(22E)-1α,3β-Diacetoxy-5α,8α-(3,5-dioxo-4-phenyl-1,2,4-triazolidino)-cholesta-6,22-dien-24-one (7)
To a solution of the enone (6) (385 mg, 0.773 mmole) in carbontetrachloride (20 mL), N-bromosuccinimide (193 mg, 1.4 eq.) was added and this mixture was refluxed for 25 min under argon atmosphere. After cooling to 0° C., the resulting precipitate was filtered off. The filtrate was concentrated below 40° C. to leave the residue. This in THF (15 mL) was treated with a catalytic amount of tetra-n-butylammonium bromide at room temperature for 50 min. Then, to this reaction mixture a solution of tetra-n-butyl-ammonium fluoride in THF (3.5 mL, 3.5 mmole) was added and this mixture was stirred at room temperature for 30 min. The usual work-up (ethyl acetate for extraction) gave a crude 5,7-diene (380 mg). This in chloroform (15 mL) was treated with a solution of 1-phenyl-1,2,4-triazoline-3,5-dione (95 mg, 0.54 mmole) in chloroform (10 mL) at room temperature for 1 h. Removal of the solvent under reduced pressure gave the residue, which was applied to a column of silica gel (10 g). Elution with benzene-ethyl acetate (5:1) provided the triazoline adduct (7) (191 mg, 37%): oil, 1 H-NMR (CDCl 3 ): 0.83 (3H, s, 18-H 3 ), 1.01 (3H, s, 10-H 3 ), 1.08 (9H, d, J=7 Hz, 21-H 3 , 26-H 3 , and 27-H 3 ), 1.97 (3H, s, acetyl), 1.98 (3H, s, acetyl), 5.03 (1H, m, 1-H), 5.84 (1H, m, 3-H), 5.96 (1H, d, J=16 Hz, 23-H), 6.28 (1H, d, J=8.5 Hz, 6-H or 7-H), 6.41 (1H, d, J=8.5 Hz, 6-H or 7-H), 6.65 (1H, dd, J= 16 and 8 Hz, 22-H), 7.20-7.60 (5H, m, -ph) MC m/z: 436 (M + -phC 2 N 3 O 2 -CH 3 COOH), 376 (436-CH 3 COOH), 333, 305, 251, 43.
(22E,24R)- and(22E,24S)-1α,3β-Diacetoxy-5α,8α(3,5-dioxo-4-phenyl-1,2,4-triazolidino)-cholesta-6,22-dien-24-ol (9a and 8a)
The enone (7) (150 mg, 0.224 mmole) in THF (6 mL) and methanol (6 mL) was treated with sodium borohydride (17 mg, 0.448 mmole) at room temperature for 10 min. The usual work-up (ether for extraction) gave a crude product (150 mg), which was submitted to preparative TLC (benzene-ethyl acetate, 3:1, developed seven times). The band with an Rf value 0.53 was scraped off and eluted with ethyl acetate. Removal of the solvent under reduced pressure gave the less polar (24S)-24-alcohol (8a) (43.2 mg, 28.7%): mp 142°-144° C. (ether-hexane), MS m/z: 438 (M + -phC 2 N 3 O 2 -CH 3 COOH), 420, 378 (438-CH 3 COOH), 360, 363, 345, 335, 318, 109, 43. The band with an Rf value 0.50 was scraped off and eluted with ethyl acetate to give the more polar (24R)-24-alcohol (9a) (64.8 mg, 43.1%): mp 140°-142° C. (ether-hexane). Mass spectrum of (9a) was identical with that of (8a).
(22E,24S)-1α,3β-Diacetoxy-5α,8α-(3,5-dioxo-4-phenyl-1,2,4-triazolidino)-cholesta-6,22-dien-24-ol (+)-MTPA ester (8b)
The 24 alcohol (8a) (8.3 mg, 0.0123 mmole) in pyridine (1 mL) was treated with 3 drops of (+)-MTPA-Cl at room temperature for 1 h. The usual work-up (ethyl acetate) provided the MTPA ester (8b) (10.4 mg, 95%): 1 H-NMR (CDCl 3 , 100 MHz): 0.85 (3H, s, 18-H 3 ), 0.88 (3H, d, 7=J Hz, 26-H 3 ), 0.92 (3H, d, J=7 Hz, 27-H 3 ), 1.04 (3H, d, J=7 Hz, 21-H 3 ), 1.08 (3H, s, 19-H 3 ), 2.03 (3H, s, acetyl), 2.06 (3H, s, acetyl), 3.27 (1H, m), 3.54 (3H, s, --OCH 3 ), 6.28 (1H, d, J=8 Hz, 6-H or 7-H), 6.41 (1H, d, J=8 Hz, 6-H or 7-H), 7.24-7.56 (5H, m, -ph).
(22E,24R)-1α,3β-Diacetoxy-5α,8α-(3,5-doxo-4-phenyl-1,2,4-triazolidino)-cholesta-6,22-dien-24-ol 24-(+)-MTPA ester (9b)
The 24-alcohol (9a) (7.9 mg, 0.0117 mmole) was converted, as described for (8b), into the MTPA ester (9b) (9.3 mg, 89%): 1 H-NMR (CDCl 3 , 100 MHz): 0.83 (3H, s, 18-H 3 ), 0.88 (6H, d, J=7 Hz, 26-H 3 and 27-H 3 ), 1.04 (3H, d, J=7 Hz; 21-H 3 ), 1.08 (3H, s, 19-H 3 ), 2.03 (3H, s, acetyl), 2.05 (3H, s, acetyl), 3.27 (1H, m), 3.54 (3H, s, --OCH 3 ), 6.28 (1H, d, J=8 Hz, 6-H or 7-H), 6.41 (1H, d, J=8 Hz, 6-H or 7-H), 7.24-7.56 (5H, m, -ph).
(22E,24S)-6β -Methoxy-3α,5-cyclo-5α-cholesta-22-en-24-ol 24-(+)-MTPA ester (14b)
The known (24S)-24-alcohol (14a) (10.1 mg, 0.0244 mmole) was converted, as described for (8b), into the (24S)-MTPA ester (14b) (8.2 mg, 54%): 1 H-NMR (CDCl 3 , 100 MHz): 0.72 (3H, s, 18-H 3 ), 0.89 (3H, d, J=7 Hz, 26-H 3 ), 0.93 (3H, d, J=7 Hz, 27-H 3 ), 1.02 (3H, d, J=7 Hz, 21-H 3 ), 1.04 (3H, s, 19-H 3 ), 2.75 (1H, m, 6-H), 3.33 (3H, s, --OCH 3 ), 3.54 (3H, s, --OCH 3 .
(22E,24R)-6β-Methoxy-3α,5-cyclo-5α-cholesta-22-en-24-ol 24-(+)-MTPA ester (15b)
The known (24R)-24-alcohol (15a) (11.0 mg, 0.0266 mmole) was converted, as described for (8b), into the (24R)-MTPA ester (15b) (9.4 mg, 56%): 1 H-NMR (CDCl 3 , 100 MHz): 0.76 (3H, s, 18-H 3 ), 0.88 (6H, d, J=7 Hz, 26-H 3 and 27-H 3 ), 1.04 (3H, d, J=7 Hz, 21-H 3 ), 1.05 (3H, s, 19-H 3 ), 2.77 (1H, m, 6-H), 3.36 (3H, s, --OCH 3 ), 3.57 (3H, s, --OCH 3 ).
(22E,24R)-Cholesta-5,7,22-triene-1α,3β,24-triol (10)
The triazoline adduct (9a) (15.0 mg, 0.0223 mmole) in THF (5 mL) was treated with lithium aluminum hydride (5 mg, 0.132 mmole) under reflux for 2 h. To this reaction mixture water was added and filtered. The filtrate was concentrated under reduced pressure to leave the residue, which was submitted to preparative TLC (benzene-ethyl acetate, 1:1, developed three times). The band with an Rf value 0.35 was scraped off and eluted with ethyl acetate. Removal of the solvent provided the 5,7-diene (10) (3.3 mg, 36%), UV λ max EtOH : 294, 282, 272, MS m/z: 414 (M + ), 396, 381, 378, 363, 353, 335, 317, 287, 269, 251, 127, 109.
(22E,24S)-Cholesta-5,7,22-triene-1α,3β,24-triol (11)
The triazoline adduct (8a) (16.5 mg, 0.0245 mmole) was converted, as described for (10), to the 5,7-diene (11) (3.5 mg, 35%). The UV and MS spectra of (11) were identical with those of (10).
(22E,24R)-1α,24-Dihydroxy-Δ 22 -vitamin D 3 (12)
A solution of the (24R)-5,7-diene (10) (3.3 mg, 7.97 mole) in benzene (90 mL) and ethanol (40 mL) was irradiated with a medium pressure mercury lamp through a Vycor filter for 2.5 min. with ice-cooling under argon atmosphere. Then the reaction mixture was refluxed for 1 h under argon atmosphere. Removal of the solvent under reduced pressure gave a crude product, which was submitted to preparative TLC (benzene-ethyl acetate, 1:1, developed three times). The band with an Rf value 0.40 was scraped off and eluted with ethyl acetate. Removal of the solvent under reduced pressure provided the vitamin D 3 analogue (12) (0.59 mg, 18%). This was further purified by high performance liquid chromatography on a Zorbax-SIL column (4.6 mm×15 cm) at a flow rate of 2 ml/min with 2% methanol in dichloromethane as an eluent. The retention time of (12) was 5.2 min. UV λ max EtOH 265 nm, λ min EtOH 228 nm, MS m/z: 414 (M + ), 396, 378, 363, 360, 345, 335, 317, 287, 269, 251, 249, 152, 135, 134, 109. 1 H-NMR (CDCl 3 , 400.5 MHz): 0.57 (3H, s, 18-H 3 ), 0.87, (3H, d, J=6.7 Hz, 26-H 3 ), 0.92 (3H, d, J=6.7 Hz, 27-H 3 ), 1.04 (3H, d, J=6.6 Hz, 21-H 3 ), 2.32 (1H, dd, J=13.7 and 6.6 Hz), 2.60 (1H, dd, J=13.4 and 3.4 Hz), 2.83 (1H, dd, J=12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, bs, W 1/2 =4.3 Hz, 19-H), 5.33 (1H, bs, W 1/2 =4.3 Hz, 19-H), 5.39 (1H, dd, J=15.2 and 7.1 Hz, 22-H), 5.51 (1H, dd, J=15.2 and 8.3 Hz, 23-H), 6.01 (1H, d, J=11.4 Hz, 6-H), 6.38 (1H, d, J=11.4 Hz, 7-H).
(22E,24S)-1α,24-Dihydroxy-Δ 22 -vitamin D 3 (13)
The (24S)-5,7-diene (11) (3.5 mg, 8.45 mole) was transformed, as described for (12), into the vitamin D 3 form (13) (0.56 mg, 16%). The retention time of (13) under the above described HPLC condition was 4.7 min. The UV and MS spectra of (13) were identical with those of (12). 1 H-NMR (CDCl 3 , 400.5 MHz): 0.57 (3H, s, 18-H 3 ), 0.87 (3H, d, J=6.7 Hz, 26-H 3 ), 0.92 (3H, d, J=6.7 Hz, 27-H 3 ), 1.05 (3H, d, J=6.6 Hz, 21-H 3 ), 2.32 (1H, dd, J=13.7 and 6.6 Hz), 2.60 (1H, dd, J=13.4 and 3.4 Hz), 2.83 (1H, dd, J=12.6 and 4.0 Hz), 4.23 (1H, m, 3-H), 4.43 (1H, m, 1-H), 5.00 (1H, bs, W 1/2 =4.3 Hz, 19-H), 5.33 (1H, bs, W 1/2 =4.3 Hz, 19-H), 5.37 (1H, dd, J=15.4 and 7.5 Hz, 22-H), 5.46 (1H, dd, J=15.4 and 8.3 Hz, 23-H), 6.01 (1H, d, J=11.4 Hz, 6-H), 6.38 (1H, d, J=11.4 Hz, 7-H).
To determine the configuration at the C-24 position the 24-alcohols 8a and 9a were converted into the corresponding (+)-MPTA ester 8b and 9b. The 1 H-NMR spectra of 8b and 9b were compared with those of the (+)-MTPA esters 14b and 15b, which were derived from the known (24S)-24-alcohol 14a and its (24R)-isomer 15a, respectively. The 1 H-NMR data of methyl groups of 8b, 9b, 14b, and 15b are shown in Table 1.
As shown in Table 2, the 1 H-NMR data of C-22, and C-23 protons of the (24R)-vitamin D 3 analog 12 and those of the known (24S)-isomer 13 were in good agreement with those of the known (24R)-allylic alcohol 15a and its (24S)-isomer 14a, respectively. These 1 H-NMR data (as shown in Table 1 and 2) confirmed the assignment of the synthetic vitamin D 3 analogs 12 and 13.
TABLE 1______________________________________.sup.1 H--NMR (100 MHz) spectral data of methyl groupsin 8b, 9b, 14b, and 15bChemical shift.sup.aCom-pound 18-Me 19-Me 21-Me 26-Me and 27-Me______________________________________ 8b 0.85 1.08 1.04 (J = 7) 0.88 (J = 7), 0.92 (J = 7) 9b 0.83 1.08 1.04 (J = 7) 0.88 (J = 7)14b 0.72 1.04 1.02 (J = 7) 0.89 (J = 7), 0.93 (J = 7)15b 0.76 1.05 1.04 (J = 7) 0.88 (J = 7)______________________________________ .sup.a Shifts are given in ppm and J values in Hz
TABLE 2______________________________________.sup.1 H--NMR spectra data of C-22 and C-23 proton in12, 13 (400 MHz) and 14a, 15a (360 MHz)Chemical shift.sup.aCom-pound 22-H 23-H______________________________________12 5.39 (dd, J = 15.2, 7.1) 5.51 (dd, J = 15.2, 8.3)15a 5.374 (dd, J = 15.39, 6.80) 5.494 (dd, J = 15.40, 8.23)13 5.37 (dd, J = 15.4, 7.5) 5.46 (dd, J = 15.4, 8.3)14a 5.353 (dd, J = 15.38, 7.06) 5.448 (dd, J = 15.03, 8.20)______________________________________ .sup.a Shifts are given in ppm and J values in Hz
Biological Activity
The biological activity of the compounds of this invention was measured in accordance with well known procedures as indicated below.
Rats
Weanling male rats were purchased from Holtzman (Madison, WI) and fed either a low phosphorus (0.1%), high calcium (1.2%) vitamin D-deficient diet as described by Tanaka and DeLuca (Proc. Nat'l. Acad. Sci. USA (1974) 71, 1040) (Table 3) or a low calcium (0.02%), adequate phosphorus (0.3%) vitamin D-deficient diet as described by Suda et al (J. Nutrition (1970) 100, 1049) (Table 4) for 3 weeks.
Determination of Serum Calcium and Inorganic Phosphorus
Serum calcium was determined by atomic absorption spectrometry using samples diluted in 0.1% lanthanum chloride. The instrument used was a Perkin-Elmer atomic absorption spectrometer model 403. Serum inorganic phosphorus was determined by the method of Chen et al (Anal. Chem. (1956) 28, 1756).
Measurement of Bone Ash
Bone ash measurements were made on femurs. Connective tissue was removed, the femurs extracted successively for 24 h with 100% ethanol followed by 24 h with 100% diethyl ether using a Soxhlet extractor. The fat-free bone was dried 24 h and ashed in a muffle furnace at 650° for 24 H.
Measurement of Intestinal Calcium Transport Activity
Intestinal calcium transport was measured using the everted duodenal sac method described by Martin and DeLuca (Am. J. Physiol. (1969) 216, 1351).
Displacement of 1,25-(OH) 2 --[26,27- 3 H]D 3 from Chick Intestinal Cytosol Receptor Protein by Either Compound
Displacement of 1,25-(OH) 2 -[26,27- 3 H]D 3 from chick intestinal receptor was determined according to the method of Shepard et al (Biochem. J. (1979) 182, 55-69).
The results obtained in these measurements are shown in FIG. 1 and in Tables 3 and 4.
TABLE 3______________________________________Increase of serum inorganic phosphorus concentration and boneash in response to either (22E,24R)-1,24-(OH).sub.2 --Δ.sup.22D.sub.3,(22E,24S)-1,24-(OH).sub.2 --Δ.sup.22 -D.sub.3 or 1,25-(OH).sub.2D.sub.3. serum inorganic phosphorus bone ashcompound given (mg/100 ml) (mg)______________________________________None 2.4 ± 0.1*.sup.(a) 35.0 ± 4.6.sup.(e)1,25-(OH).sub.2 D.sub.3 3.3 ± 0.4.sup.(b) 53.2 ± 6.9.sup.(f)(22E,24R)-1,24-(OH).sub.2 -- 2.7 ± 0.4.sup.(c) 35.0 ± 6.7Δ.sup.22 -D.sub.3(22E,24S)-1,24-(OH).sub.2 -- 2.9 ± 0.4.sup.(d) 46.5 ± 4.2.sup.(g)Δ.sup.22 -D.sub.3______________________________________ Weanling male rats were fed a rachitogenic diet for 3 weeks. They were then given 32.5 ρ mol/day of either compound dissolved in a 0.1 ml mixture of 95% ethanol/propylene glycol (5/95) subcutaneously daily for 7 days. Rats in a control group were given the vehicle. Each group had 6-7, rats. *Standard deviation of the mean. Significantly different:.sup.(a) from .sup.(b) ρ<0.001.sup.(c) ρ<0.025.sup.(d) ρ<0.005.sup.(e) from .sup.(f) & .sup.(g) ρ<0.001.sup.(f) from .sup.(g) ρ<0.05______________________________________
TABLE 4______________________________________Increase of intestinal calcium transport and serum calciumconcentration in response to either (22E,24R)-1,24-(OH).sub.2 --Δ.sup.22 -D.sub.3, (22E,24S)-1,24-(OH).sub.2 --(OH).sub.2 --Δ.sup.22 -D.sub.3 or 1,25-(OH).sub.2 D.sub.3. intestinal calcium transport serum calciumcompound given (Ca serosal/Ca mucosal) (mg/100 ml)______________________________________none 2.5 ± 0.3*.sup.(a) 3.5 ± 0.1.sup.(e)1,25-(OH).sub.2 D.sub.3 6.4 ± 1.1.sup.(b) 3.8 ± 0.1.sup.(f)(22E,24R)-1,24- 3.4 ± 0.6.sup.(c) 3.4 ± 0.1(OH).sub.2 --Δ.sup.22 -D.sub.3(22E,24S)-1,24- 3.9 ± 0.4.sup.(d) 3.6 ± 0.1(OH).sub.2 --Δ.sup.22 D.sub.3______________________________________ Weanling male rats were fed a low calciumvitamin D deficient diet for 3 weeks. They were then given 32.5 ρ mol/day of either compound dissolved in a 0.1 ml mixture of 95% ethanol/propylene glycol (5/95) subcutaneously daily for 7 days. Rats in a control group received the vehicle. Each group had 7 rats. *Standard deviation of the mean. Significantly different: .sup.(a) from .sup.(b) & .sup.(d) ρ<0.001.sup.(a) from .sup.(c) ρ<0.005.sup.(b) from .sup.(c) & (d) ρ<0.001.sup.(e) from .sup.(f) ρ<0.005______________________________________
FIG. 1 demonstrates the ability of the two synthetic 1,24-(OH) 2 D 3 isomers to displace radiolabeled 1,25-(OH) 2 D 3 from the chick intestinal receptor. The results demonstrate that the 24S-isomer is equally potent as unlabeled 1,25-(OH) 2 D 3 in displacing radiolabeled 1,25-(OH) 2 D 3 from the receptor. The 24R-isomer proved to be approximately one-tenth as active as either 1,25-(OH) 2 D 3 or the S-isomer. In the stimulation of intestinal calcium transport of rats on a low calcium vitamin D-deficient diet, it is apparent that neither isomer equalled 1,25-(OH) 2 D 3 in this capacity (Table 4). This contrasts with the results obtained with the chick intestinal receptor in which the S-isomer equalled 1,25-(OH) 2 D 3 in its ability to displace radiolabeled 1,25-(OH) 2 D 3 from the receptor. Neither isomer at the doses administered was able to elicit a bone calcium mobilization response as revealed by elevation of serum calcium of rats on a low calcium diet. In contrast, 1,24-(OH) 2 D 3 did stimulate this response to a minimal degree at this dosage.
Table 3 illustrates the ability of the isomers to mineralize femur of rachitic rats. The dosage used 1,25-(OH) 2 D 3 was fully able to mineralize rachitic femur within 7 days. On the other hand, the R-isomer was unable to mineralize significant amounts of bone at this dosage level, whereas the 24S-compound was less active than 1,25-(OH) 2 D 3 but was clearly effective in this capacity.
The rise in serum inorganic phosphorus concentration in animals on a low phosphorus diet is a critical response for mineralization of bone. It is evident that all three forms of vitamin D stimulated serum inorganic phosphorus levels; however, neither isomer was equal to 1,25-(OH) 2 D 3 in this capacity.
The measured biological activity of the compounds of this invention point to their use in physiological situations where vitamin D-like activity is indicated. The 1,24S-isomer can, in fact, be regarded as a very potent 1-hydroxylated form of vitamin D that would find application where preferential effectiveness on intestine and bone mineralization, as opposed to bone mobilization, would appear to be in order.
The compounds of this invention, or combinations thereof with other vitamin D derivatives or other therapeutic agents, can be readily administered as sterile parenteral solutions by injection or intravenously, or by alimentary canal in the form of oral dosages, or trans-dermally, or by suppository. Doses of from about 0.5 micrograms to about 25 micrograms per day of the compounds, per se, or in combination with other vitamin D derivatives, the proportions of each of the compounds in the combination being dependent upon the particular disease state being addressed and the degree of bone mineralization and/or bone mobilization desired, are generally effective to practice the present invention. Although the actual amount of the compounds used is not critical, in all cases sufficient of the compound should be used to induce bone mineralization. Amounts in excess of about 25 micrograms per day of the compounds, alone, or in combination with a bone mobilization-inducing vitamin D derivative, are generally unnecessary to achieve the desired results and may not be economically sound practice. In practice the higher doses are used where therapeutic treatment of a disease state is the desired end while the lower doses are generally used for prophylactic purposes, it being understood that the specific dosage administered in any given case will be adjusted in accordance with the specific compounds being administered, the disease to be treated, the condition of the subject and the other relevant medical facts that may modify the activity of the drug or the response of the subject, as is well known by those skilled in the art.
Dosage forms of the compounds can be prepared by combining them with non-toxic pharmaceutically acceptable carriers as is well known in the art. Such carriers may be either solid or liquid such as, for example, corn starch, lactose, sucrose, peanut oil, olive oil, sesame oil and propylene glycol. If a solid carrier is used the dosage form of the compounds may be tablets, capsules, powders, troches or lozenges. If a liquid carrier is used, soft gelatin capsules, or syrup or liquid suspension, emulsions or solutions may be the dosage form. The dosage forms may also contain adjuvants, such as preserving, stabilizing, wetting or emulsifying agents, solution promoters, etc. They may also contain other therapeutically valuable substances.
It is to be understood that the acylated derivatives of compounds 10, 11, 12 and 13 are also to be considered within the scope of the present invention, certain acylates being susceptible to administration as described for compounds 12 and 13, with conversion of the acylates to the hydroxy derivatives being accomplished in vivo. Thus, the compounds have the structures ##STR2## wherein R 1 and R 2 are hydrogen or hydroxy except that when R 1 is hydrogen R 2 is hydroxy and when R 1 is hydroxy R 2 is hydrogen and
R 3 and R 4 are each hydrogen or acyl having from 1 to 4 carbon atoms.
Also, if desired, the compounds of this invention may be obtained in crystalline form by dissolution in a suitable solvent or solvent system, e.g. methanol-ether, methanol-hexane and then removing the solvent(s) by evaporation or other means as is well known.
suspension, emulsions or solutions may be the dosage form. The dosage forms may also contain adjuvants, such as preserving, stabilizing, wetting or emulsifying agents, solution promoters, etc. They may also contain other therapeutically valuable substances.
It is to be understood that the acylated derivatives of compounds 10, 11, 12 and 13 are also to be considered within the scope of the present invention, certain acylates being susceptible to administration as described for compounds 12 and 13, with conversion of the acylates to the hydroxy derivatives being accomplished in vivo. Thus, the compounds have the structures ##STR3## wherein R 1 and R 2 are hydrogen or hydroxy except that when R 1 is hydrogen R 2 is hydroxy and when R 1 is hydroxy R 2 is hydrogen and
R 3 and R 4 are each hydrogen or acyl having from 1 to 4 carbon atoms.
Also, if desired, the compounds of this invention may be obtained in crystalline form by dissolution in a suitable solvent or solvent system, e.g. methanol-ether, methanol-hexane and then removing the solvent(s) by evaporation or other means as is well known. | The invention provides new derivatives of vitamin D 3 and specifically (22E,24R)-1,24-dihydroxy-Δ 22 -vitamin D 3 and (22E,24S)-1,24-dihdroxy-Δ 22 -vitamin D 3 .
The compounds exhibit vitamin D-like activity in their ability to stimulate intestinal calcium transport, increase serum inorganic phosphorous and mineralize bone indication ready application of the compounds in the treatment of various metabolic bone diseases. The characteristic of the compounds to not mobilize bone indicates that the compositions would find ready application in combination with vitamin D and various of its derivatives to achieve controlled bone mineralization. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is being simultaneously filed with another application by the same inventors and entitled "Guidelineless Reentry System With Fixed Rollers"Ser. No. 106,838, filed Oct. 8, 1987. The same inventors have also filed a related application entitled "Guidelineless Reentry System With Retracting Rollers", Ser. No. 0.99,360, filed Sept. 21, 1987.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates in general to subsea wells, and in particular to a system for reconnecting a riser from a floating vessel to a subsea well for workover operations.
2. Description of the Prior Art
In deep water offshore oil and gas wells, the Christmas tree of the well will often be located on the subsea floor. At times, a workover operation must be performed on the subsea well. When this is required, a floating vessel is positioned over the well. A string of riser pipe is lowered down into engagement with a mandrel on the subsea tree. Once in engagement, operations can be performed on the well.
If the system is a guidelineless system, there will be no guidelines extending upward from the subsea well structure to the surface. Generally, in a guidelineless system, a large upward facing funnel is mounted permanently on the subsea tree. The funnel, with the aid of television cameras, assists in guiding the lower end of the riser onto the mandrel of the subsea well. The funnel can be quite large, up to twelve feet in diameter. A funnel of this type is expensive to construct and is only used when a workover operation is performed.
Mounting a downward facing funnel on the riser would avoid the need for a permanent upward facing funnel on each well. However, a funnel rigidly mounted to the lower end of the riser would require an extra high mandrel extending above the control mechanisms on the tree, so as to insure that the funnel did not strike any of various control mechanisms on the side of the tree. Hydraulic connections must also be made up when the riser lands on a mandrel to connect the control of the tree to the floating platform. Orienting the funnel onto the mandrel of the Christmas tree without damage to the hydraulic manifold or valve block would be a problem.
There have been proposals to make the funnel retractable. The funnel would be located on the lower end of the riser, but would be vertically movable relative to the lower end of the riser by means of hydraulic rams. The funnel is lowered in an extended position. Once proper orientation has been made, the funnel would be retracted. During retraction, the riser and mandrel connector lower down into engagement with the mandrel. While these proposals have merit, improvements are desirable.
SUMMARY OF THE INVENTION
The guidelineless reentry system of this invention utilizes a nonrotating funnel. The mandrel has a guide ring encircling it and facing upward. The riser has a funnel that faces downward. Hydraulic rams allow the mandrel connector and the riser to move downward relative to the funnel after the funnel has landed on the guide ring.
After the funnel has landed on the guide frame, a hydraulic ram pushes a plurality of latches inward. The latches grip a shoulder formed on the guide ring. Th latches aid in causing the funnel to align vertically and also secure the funnel to the guide ring. The riser is then rotated, with the funnel remaining stationary. The riser rotates until a key enters a slot in the guide ring. Then the riser and mandrel connector move downward to seat onto the mandrel.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a vertical sectional view of a guidelineless reentry system constructed in accordance with this invention.
FIG. 2 is a sectional view of the system of FIG. 1, but showing the latches engaging the guide ring.
FIG. 3 is a sectional view of the system of FIG. 1, showing the mandrel connector landed on and locked to the mandrel.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, the subsea well includes an upward extending mandrel 11. Mandrel 11 is a tubular member having a plurality of circumferential grooves 13 on its exterior near the upper end. Passages 15 extend through the mandrel 11 for communicating with the well. Normally, a cap (not shown) of some type will be located on top of the mandrel 11 and will be removed when the workover operation is beginning.
A cone seal manifold 17 is muunted to the exterior of mandrel 11. Manifold 17 is an annular member with an upward and outward facing conical exterior. Manifold 17 has a plurality of passages 19 extending through it and spaced around its circumference. Each passage 19 contains a check valve 21. The passages 19 lead to lines (not shown) which lead to various other equipment, such as control valves, on the subsea well. A cone seal manifold 17 of this type is described in more detail in pending U.S. patent application Ser. No. 941,260, filed Mar. 27, 1987, Charles E. Jennings.
A guide frame 23 is mounted to the mandrel 11. Guide frame 23 is an assembly which includes an inner annular plate 22a that extends outward from the mandrel 11. An outer annular plate 22b joins the inner plate 22a and is slightly lower. An upright annular ring or rim 24 extends upward from the outer edge of outer plate 22b, forming the periphery of the guide frame 23. Gussets 25 are spaced around the bottom of the guide frame 23 to provide support.
The assembly of guide frame 23 includes a guide ring 27, which is mounted on the upper side of the guide frame 23. Guide ring 27 is a solid annular cylindrical ring. It has a beveled surface 29 on the inner upper edge. An external shoulder 31 is located on the outer side of guide ring 27 and faces downward. The guide ring 27 is located about halfway between the rim 24 of the guide frame 23 and the mandrel 11. The diameter of the guide ring 27 is considerably greater than the diameter of the mandrel 11, but considerably less than the outer diameter of the guide frame 23.
The height of the guide ring 27 is important. The top of the guide ring 27 is lower than the grooves 13 and slightly higher than the cone seal manifold 17. The height and radial position of the guide ring 27 are selected so that a straight line extending from the upper edge of rim 24 to the upper outer edge of the mandrel 11 and to the axis of mandrel 11 would touch the upper edge of the guide ring 27. This straight line is thus tangent to the periphery of the guide frame 23, the top of the guide ring 27 and the rim of mandrel 11. If this straight line is revolved around the axis of the mandrel 11, it generates a conical surface.
A riser 33 is shown being lowered from a floating vessel (not shown). Riser 33 is made up of sections of conduit. Passages 34 extend through the riser 33 for communication with the passages 15 in the mandrel 11. A mandrel connector 35 is rigidly mounted to the lower end of the riser 33 by bolts 36. The mandrel connector 35 has a top or upper plate 37 which is adapted to land on the top of the mandrel 11. A cylindrical inner sidewall 39 extends downward from the top 37. The inner diameter of the inner sidewall 39 is slightly greater than the outer diameter of the mandrel 11, allowing the inner sidewall 39 to slide down over the mandrel 11. A cylindrical outer sidewall 41 is spaced outward from the inner sidewall 39 and depends from the top 37.
A plurality of dogs 43 are carried in windows in the inner sidewall 39. Each dog 43 has grooves on its inner face for engaging the grooves 13. Each dog 43 will move radially between an outward retracted position shown in FIGS. 1 and 2 and an inward locked position shown in FIG. 3.
The dogs 43 are moved inward by means of a cam member 45. Cam member 45 is a ring positioned in the clearance between the inner sidewall 3 and outer sidewall 41. Cam member 45 has an inclined inner face which engages the outer side of each dog 43. A plurality of hydraulic cylinders 47 (only one shown) are mounted to the top 37. Each hydraulic cylinder 47 has a shaft 48 which is connected to the cam member 45 for raising the cam member to push the dogs 43 inward.
A manifold connector 49 is rigidly mounted to the mandrel connector 35. The manifold connector 49 is a metal block having a conical inner side that faces downward and inward. A plurality of passages 51 extend through the manifold connector 49. The passages 51 are connected to lines (not shown) which lead to the floating vessel for supplying hydraulic fluid. The passages 51 are positioned to align and register with the passages 19 in the cone seal manifold 17.
An upper guide frame or funnel 53 is carried by the mandrel connector 35. Funnel 53 has an upper cylindrical portion 55. The cylindrical portion 55 is closely and slidingly carried on the outside of the mandrel connector outer sidewall 41. A lower frustoconical portion 57 extends downward from the cylindrical portion 55. The conical portion 57 faces downward. The conical portion 57 is formed at a degree so that it will contact the guide frame rim 24 and the guide ring 27. It diverges from the axis of riser 33 at the same angle as the line previously described that extends across the upper edges of the mandrel 11, guide ring 27 and the rim 24 of the guide frame 23. Conical portion 57 is considerably larger in diameter than the guide frame 23.
A plurality of hydraulic cylinders 59 (only one shown) are mounted to the top of the funnel 53. Each Hydraulic cylinder 59 has a shaft 60 that extends downward and is secured to a bracket 61. Bracket 61 is rigidly mounted to the outer sidewall 41 of mandrel connector 35. The outer sidewall 41 moves vertically with the mandrel connector 35. However, the inner sidewall 39 and top 37 are rotatable relative to the outer sidewall 41. The upper edge of the outer sidewall 41 inserts into a groove 63 in the top 37 to allow rotation of the riser 33 and the mandrel connector 35 relative to the outer sidewall 41.
A plurality of fingers 65 (only one shown) are located within the cylindrical portion 55 between the cylindrical portion 55 and the mandrel connector outer sidewall 41. The fingers 65 are evenly spaced around the funnel 53. The upper end of each finger 65 is mounted to bracket 61 for movement therewith. Each finger 65 is capable of vertical movement relative to the funnel 53 but cannot rotate relative to the funnel 53. Each finger 65 is adapted to extend downward through an aperture 69 located at the upper end of the conical portion 57.
Each finger 65 is a rectangular shaft. A pair of lugs 75 are located on the opposite sides of the lower end of each finger 65. Each lug 75 (only one shown) is a pin that protrude laterally from the finger 65 a short distance.
Each finger 65 slidingly engages a latch 77. Each latch 77 is pivotally mounted by a pin 80 to a bracket 79. Each bracket 79 is rigidly mounted to the lower end of the funnel cylindrical portion 55. Each latch 77 has a pair of spaced apart vertical ears 81 (only one shown). The ears 81 are located on the outer side of the latch 77. The finger 65 fits between the ears 81 and will slide vertically relative to the latch 77. The lugs 75 of the fingers 65 bear against the lower edges of the ears 81 when the fingers 65 are retracted as shown in FIG. 1.
Each latch 77 has a lip 83 on its lower inner edge. The lip 83 will engage the guide ring shoulder 31 when the latch 77 is pivotted inward to the locked position shown in FIGS. 2 and 3. The latch 77 pivots about the pin 80 between the retracted position shown in FIG. 1 and the locked position shown in FIGS. 2 and 3.
A key 85 is rigidly mounted to the mandrel connector 35 below the rotating outer sidewall 41. Key 85 will not rotate relative to the connector 35. It slidingly engages the beveled surface 29 of the guide ring 27 when the riser 33 is rotated, until reaching a slot 87. The slot 87 is located on the inner sidewall of the guide ring 27.
In operation, the tree cap (not shown) will first be removed from the tree mandrel 11 by various means. Then, the riser 33 is lowered from a floating vessel downward to approximately the point shown in FIG. 1. Television cameras will assist in guiding the funnel 53 over the guide ring 27 and in making an approximate orientation. The funnel 53 may be misaligned, and it may even contact the upper edge of the mandrel 11 initially. However, farther downward movement will cause it to slide down and land on the guide ring 27. When landed, as shown in FIG. 1, the conical portion 57 will be in contact with the guide ring 27 and also the rim 24 of the guide frame 23.
Then, hydraulic fluid pressure is supplied to the hydraulic cylinders 59. This results in the fingers 65 moving downward to an intermediate position shown in FIG. 2. As the fingers 65 move downward, they slide downward between the ears 81 of the latches 77. Each finger 65 serves as cam means for moving one of the latches 77 between the retracted and locked positions. The inner surface of each finger 65 pushes on the outer surface of a latch 77, causing each latch to pivot inward. The lip 83 engages the shoulder 31, latching the funnel 53 to the guide ring 27. This latching action also serves to straighten the funnel 53 on the guide frame 23.
The riser 33 and the mandrel connector 35 will move downward with the fingers 65. After the latches 77 have engaged the shoulder 31, the key 85 will contact the guide ring beveled surface 29. The key 85 will prevent any farther downward movement of the mandrel connector 35 as long as the key 85 is bearing against the beveled surface 29. This position is shown in FIG. 2. As the mandrel connector inner sidewall 39 slides over the upper part of mandrel 11, the close fit further causes the funnel 53 to straighten on the mandrel 11.
After the latches 77 have engaged the guide ring 27, and the key 85 has landed on the guide ring 27, the riser 33 is rotated in a horizontal plane perpendicular to the longitudinal axis of mandrel 11. The mandrel connector 35 and key 85 will rotate relative to the guide ring 27. The funnel 53 will not rotate. The latches 77 serve as means to restrict such rotation because of the engagement of the latches 77 with the guide ring 27. When the key 85 reaches the slot 87, then it will be free to slide into the slot 87. The weight of the mandrel connector 35 allows the riser 33 to move downward until the connector top 37 seats on the mandrel 11 as shown in FIG. 3. The passages 15 and 34 will be in alignment at this point.
Then, hydraulic fluid pressure is supplied to the hydraulic cylinders 47. This causes the cam 45 to lift, pushing the dogs 43 inward. The dogs 43 engage the grooves 13 in the mandrel 11. This causes the manifold connector 49 to tightly seal against the cone seal manifold 17 as shown in FIG. 3. Hydraulic fluid communication is thus established from the surface vessel to the controls on the well. Workover operations may then take place.
After the workover operations have been completed, the mandrel connector 35 is released by supplying hydraulic fluid to hydraulic cylinders 47 to cause them to move downward. This moves the cam 45 downward, freeing the dogs 43 to move outward. Hydraulic fluid is supplied to hydraulic cylinders 59, causing the fingers 65 to retract upward. The lugs 75 will contact the ears 81, pivotting the latches 77 outward to the retracted position. No portion of the latches 77 protrudes into the interior of funnel 53 when the latches 77 are retracted. The mandrel connector 35 moves upward with the fingers 65 to disengage from the mandrel 11. The riser 33 may then be picked up.
The invention has significant advantages. Allowing the mandrel connector to rotate relative to the funnel avoids the need for rollers for rolling on the guide ring. The latching of the funnel to the guide ring provides alignment and assures that the alignment remains while the mandrel connector is being actuated.
While the invention has been shown in only one of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention. | A guidelineless reentry system for a subsea well uses a downward facing funnel. A guide ring is mounted to the guide frame, which in turn is mounted around a mandrel on the well. A funnel and a mandrel connector are carried by the riser. Once the riser lands on the guide ring, latches are actuated to connect the funnel to the guide ring. Then, the mandrel connector is lowered relative to the funnel into engagement with the mandrel. A cam moves dogs outward to engage grooves of the mandrel to lock the mandrel connector to the mandrel. | 4 |
This is a continuation of application Ser. No. 367/541, filed June 16, 1989, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for boring a hole in the ground by the use of an excavating machine and an apparatus therefor and, more particularly, to a boring method and an apparatus therefor suitable for the use in construction of a tunnel, laying of a pipe, renewal of an existing pipeline, construction of a vertical shaft and formation of a longitudinal hole or the like.
2. Description of the Prior Art
As one of methods for boring a hole in the ground, Japanese Patent Public Disclosure (KOKAI) No. Sho 59-192193 has disclosed a press-in method using an excavating machine including a shield body and a conical rotor disposed in front of the shield body for eccentric motion about an axis of the shield body. According to this press-in method, by making a thrust act on the shield body while eccentrically moving the rotor, a hole is formed while the earth and sand in front of the shield body are thrust aside by the rotor.
As another one of methods for boring a hole in the ground, Japanese Patent Public Disclosures (KOKAI) No. Sho 60-242295 and No. Sho 61-102999 have disclosed an excavating method using an excavating machine including a shield body, excavating means disposed in front of the shield body so as to be rotatable about an axis of the shield body and means for discharging substances excavated by the excavating means to the rear of the shield body. According to this excavating method, the ground is excavated by making a thrust act on the shield body while rotating the excavating means and then a hole is formed by discharging the excavated substances onto the ground surface. The excavated substances discharged onto the ground surface are subjected to predetermined treatment and thereafter transported to a predetermined place to be dumped.
However, the former method, that is, the press-in method involves a problem in that a large thrust should be made to act on the shield body since a large reaction acts on the rotor when the shield body is propelled. 0n the contrary, the latter excavating method involves a problem in that it is high in cost since all of the excavated substances are discharged onto the ground surface.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method for boring a hole in the ground, which is low in cost and does not require that a large thrust is made to act on a body, and an apparatus therefor.
A method according to the present invention comprises the steps of advancing an excavating machine including a tubular body and excavating means supported by the body while excavating the ground by the use of the excavating means, and shifting the excavated substances to the periphery of the body.
In the boring method of the present invention, the excavated substances are preferably shifted to the periphery of the body through the inside of the body. More preferably, the excavated substances are forcibly thrust out from the inside of the body to the outside thereof and force for compressing the substances thrust out around the body is made to repeatedly act on those substances. Further, when gravels or like solid bodies are present in the excavated substances received in the excavating machine, the solid bodies are preferably crushed in the excavating machine.
An apparatus for boring a hole in the ground according to the present invention comprises an excavating machine provided with a tubular body, excavating means supported by the body so as to excavate the ground, means for shifting the excavated substances to the periphery of the body and driving means for operating the excavating means.
In the boring apparatus of the present invention, at least one hole for shifting the excavated substances from the inside of the body to the periphery thereof is preferably formed in the body. In this case, the excavating means is disposed in front of the hole, preferably on the front portion of the body.
The shifting means preferably includes a thrusting-out mechanism shifted in the radial direction of the body so as to forcibly thrust excavated substances around the periphery of the body through the hole. Further, the thrusting-out mechanism preferably includes a rotor eccentrically moved about the axis of the body so as to make compressive force for compressing the substances thrust out around the body repeatedly act on those substances. Furthermore, it is preferable that the rotor and the body constitute a crusher.
The excavating machine is advanced while excavating the ground by the use of the excavating means and the excavated substances are thrust out around the periphery of the body. Pipes, linings and piles or like members are disposed in a hole formed by the excavating machine, and these members are stably maintained by the excavated substances, therearound.
According to the excavating machine of the present invention, it is possible to advance the excavating machine with a thrust which is smaller than that in the prior art press-in method and apparatus therefor. Further, since the excavated substances are shifted to the periphery of the body, it is less liable to cause subsidence of the ground.
When all of the excavated substances are removed to the periphery of the body, the present method and apparatus may dispense with any means for discharging the excavated substances and any operation of treating the discharged substances, so that it becomes low in cost. Further, when part of the excavated substances is removed to the periphery of the body while the rest is discharged onto the ground surface, since the quantity of excavated substances to be discharged onto the ground surface is less than that in the case where all of the excavated substances are discharged onto the ground surface, the operation of treating the discharged substances on the ground such as transhipment and transportation of the discharged substances is reduced by a quantity corresponding to a reduction of the discharged substances, so that it becomes lower in cost.
According to one aspect of the invention, it is possible to shift the excavated substances to the periphery of the body without hindering the excavation by the excavating means.
According to another aspect of the invention, it is possible to securely shift the excavated substances to the periphery of the body.
According to another aspect of the invention, the substances thrust out around the body are consolidated through repetitive compression, so that the expansive force of the substances thrust out around the body is reduced. Accordingly, there is no possibility of increasing the frictional resistance between the body and the substances thrust out around the body while a great quantity of excavated substances may be shifted to the periphery of the body.
According to another aspect of the invention, since the solid bodies contained in the excavated substances are crushed, the excavated substances may be thrust out more securely.
According to another aspect of the invention, the rotor acts as means for crushing the solid bodies contained in the excavated substances, means for forcibly thrusting out the excavated substances and means for applying the repetitive compressive force to the substances thrust out around the body.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects and features of the invention will become apparent from the following description of preferred embodiments of the invention with reference to the accompanying drawings, in which:
FIG. 1 is a longitudinal cross-sectional view showing an embodiment of a boring apparatus according to the present invention;
FIG. 2 is an enlarged-scale sectional view taken along a 2--2 in FIG. 1;
FIG. 3 is a front view of the cutter assembly of the boring apparatus;
FIG. 4 is a sectional view similar to FIG. 2, showing a modification of the boring apparatus;
FIG. 5 is a longitudinal cross-sectional view showing another embodiment of the boring apparatus according to the present invention;
FIG. 6 is a front view showing a further embodiment of the boring apparatus according to the present invention; and
FIG. 7 is an enlarged-scale longitudinal cross-sectional view showing a portion of an excavating machine for the use in the boring apparatus of FIG. 6.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A boring apparatus 10 shown in FIG. 1 comprises a shield tunneling machine 12 and a basic thrust device (not shown) which is well known per se and exerting a thrust upon the tunnelling machine 12 and a plurality of pipes 14 connected to the rear of the machine. This boring apparatus is used for executing a pipe propelling method.
The shield tunnelling machine 12 includes a cylindrical shield body 16 divided into first and second bodies 16a, 16b which are coaxially butted against each other. The first and second bodies 16a, 16b are connected to each other by a plurality of jacks 18 providing directional correction.
The interior of the first body 16a is divided into two chambers 22, 24, which are spaced apart from each other in the direction extending along an axis of the shield body 16 through a partition wall 20 provided inside the first body 16a. The chamber 22 in front has a truncated conical shape with the bore gradually tapering toward the rear. The first body 16a has a plurality of window holes 26 for communicating between the chamber 22 and an outer peripheral portion of the shield body 16. Each of the window holes 26 is formed around the axis of the shield body 16 at uniform angular intervals.
The second body 16b connected to the rear portion of the first body 16a defines a chamber 28 communicating with the chamber 24 in the first body 16a. The front end portion of the second body 16b is slidably received in the rear end portion of first body 16a. A seal member is disposed between the inner surface of the rear end portion of the first body 16a and the outer peripheral surface of the front end portion of the second body 16b.
The partition wall 20 supports a crankshaft 30 such that the crankshaft 30 is rotatable about the axis of the shield body 16 through a plurality of bearings 32. The crankshaft 30 extends through the partition wall 20 along the axis of the shield body 16 so that an eccentric portion 34 of the crankshaft 30 is located on the side of the chamber 22. The crankshaft 30 is so arranged that a rotary axis of the crankshaft is coincident with a center axis of the shield body 16. The eccentric portion 34 is eccentric from the rotary axis of the crankshaft 30, that is, the axis of the shield body 16 by a distance indicated by e.
The crankshaft 30 is rotated by a drive mechanism 36 fixedly attached to the rear of the partition wall 20, that is, to the side of the chamber 24 by the use of a plurality of bolts. The drive mechanism 36 is provided with a motor 38 and a reduction gear 40. An output shaft 42 of the drive mechanism 36 is connected to the rear end portion of the crankshaft 30 so as to make relative rotation impossible, as shown in FIG. 1.
The eccentric portion 34 of the crankshaft 30 supports a rotor 44 such that the rotor 44 is rotatable about an axis of the eccentric portion 34 through a plurality of bearings 46. The rotor 44 is shaped to have a truncated conical outer surface with the diameter thereon gradually increasing from the front end toward the rear end. A seal material for maintaining the liquid tightness between the rear end surface of the rotor 44 and the front end surface of the partition wall 20 is disposed on the rear end portion of the rotor 44.
A cutter assembly 48 is fixedly attached to the front end portion of the rotor 44. As shown in FIG. 3, the cutter assembly 48 is provided with a plurality of arms 50 extending from the rotor 44 in the radial direction of the shield body 16, a circular ring 52 for interconnecting the tip end portion of each of the arms 50, a plurality of cutter bits 54 and 56 fixedly attached to each of the arms 50 and the ring 52 respectively, and a plurality of cutter bits 58 fixedly attached to the front end surface of the rotor 44.
The cutter assembly 48 is disposed in front of the shield body 16 in the illustrated embodiment. However, in the case of a boring apparatus for boring a hole in the soft ground, the cutter assembly 48 may be disposed inside the shield body 16.
To the side of the chamber 22 of the partition wall 20 is fixedly attached an external gear 60 with the axis of the shield body 16 as a center. On the contrary, to the rear end surface of the rotor 44 is fixedly attached an internal gear 62 meshing with the external gear 60. The internal gear 62 is eccentric from the external gear 60 by the same distance as the eccentricity e of the eccentric portion 34 of the crankshaft 30. Accordingly, as shown in FIG. 2, the gears 60, 62 come into mesh with each other in one diametrical portion thereof. The portion where the gears 60,62 are meshed with each other is displaced about the axis of the shield body 16 with the rotation of the crankshaft 30. The external gear 60 may be fixedly attached to the rotor 44 while the internal gear 62 may be fixedly attached to the partition wall 20.
When the crankshaft 30 is rotated, both of the rotor 44 and the cutter assembly 48 are revolved around the axis of the shield body 16 and further rotated on their own axes around the axis of the eccentric portion 34 because the internal and external gears 62 and 60 are meshed with each other. The rotor 44 constitutes a crusher together with the first body 16a. Further, a plurality of projections extending in the circumferential direction of the first body 16a and rotor 44 may be respectively provided on the inner surface of the first body 16a and the outer surface of the rotor 44, which define the chamber 22.
During an excavation operation, the tunnelling machine 12 is advanced together with the pipes 14 by the thrust given from the basic thrust device through the pipes 14. When the machine 12 is advanced, the drive mechanism 36 is operated. In consequence, the crankshaft 30 is rotated about the axis of the shield body 16, so that both of the rotor 44 and the cutter assembly 48 are revolved about the axis of the shield body 16 while being rotated about the axis of the eccentric portion 34.
As a result, the surface of a working face is excavated by the cutter assembly 48 and the excavated substances are received in the chamber 22. Since the rotor 44 revolves around the axis of the shield body and rotates around its own axis, large solid bodies contained in the excavated substances received in the chamber 22 are crushed by the rotor 44 in cooperation with the first body 16a.
The excavated substances received in the chamber 22 are forcibly thrust out of the shield body 16 through each of the window holes 26 with the revolution of the rotor 44, that is, the turning thereof. The substances 64 thrust out of the shield body 16 are discharged between the existing earth and sand 66 and the shield body 16 by compressing existing earth and sand 66 around the shield body 16, as shown in FIG. 1.
The substances 64 and earth and sand 66 around the shield body 16 are repeatedly compressed with the revolution of the rotor 44. Therefore, the substances 64 and earth and sand 66 around the shield body 16 are gradually consolidated while expansive force of the substances 64 and that of the earth and sand 66 are gradually reduced.
The ground around the shield body 16 is repeatedly subjected to compressive force produced by the substances 64 thrust out of the periphery of the shield body 16. However, the compressive force acts as force for consolidating earth and sand while reducing the expansive force the earth and sand. As a result, a great quantity earth and sand may be discharged to the periphery the shield body 16. Further, there is no possibility of increasing the resistance between the shield body 16 and pipes 14 and the earth and sand the when the shield body 16 and pipes 14 are advanced
Elevation of the ground surface may be prevented by setting between the shield body 16 and the surface to be more than a distance between the shield body 16 and the position where the compressive force with the earth pressure.
Further, the substance may be thrust out around the shield body 16 no by the rotor 44 but also by any other means. In case of a boring apparatus for the use in ground as soft ground, which is high in fluidity of the substances, means for guiding the excavated subs to each of the window holes may be provided of the rotor 44.
According to the s tunnelling machine 12, the force acting on the of the working face with the advance of the machine is not accumulated in the ground, so that it is less to cause the elevation of the ground.
Further, according shield tunnelling machine 12, since the excavated substances are thrust out of the periphery of the shield body 16 without removing any excavated substance, there is no possibility of occurrence of the ground subsidence, even if the earth and sand around each pipe 14 disposed in a spot produced after the excavation are brought into close contact with the pipe 14 due to the earth pressure with the lapse of time. Therefore, each of the pipes 14 may be stably maintained in position.
Furthermore, according to the shield tunnelling machine 12, since the excavated substances received in the chamber 22 are not shifted to the periphery of the shield body 16 unless the pressure in the chamber 22 increases to a certain degree, the pressure in the chamber 22 may be naturally rendered to maintain a predetermined value, so that the breaking of the face may be prevented without controlling the pressure in the chamber 22 with high accuracy.
Further, since the excavated substances in the chamber 22 are thrust out through each of the window holes 26, by closing at least one window hole 26 to restrict the direction of discharging the excavated substances in the chamber 22, as shown in FIG. 4, it is possible to restrict the direction of the pressure acting on the ground around the shield body 16 due to the operation of forcibly thrusting out the excavated substances.
Further, part of the excavated substances may be discharged onto the ground surface. In this case, for example, use is made of a discharge mechanism 68 provided with a tubular casing and a screw conveyor rotatably received in the casing, as shown by a two-dotted line in FIG. 1, and the excavated substances in the chamber 22 may be discharged to the side of the chamber 24 by the use of the discharge mechanism 68.
A boring apparatus 70 as shown in FIG. 5 comprises a self-travelling shield tunnelling machine 72 and is used for executing the excavation of a tunnel with a large bore. In the illustrated embodiment, the shield tunnelling machine 72 is different from the shield tunnelling machine 12 shown in FIGS. 1 through 3 in that a shield body 74 is not divided into two bodies, and this machine 72 does not include any jack for the use of directional correction but includes a plurality of propulsion jacks 78 for advancing the shield body 72 by making a reaction act on a segment ring 76 incorporated in a spot produced after the excavation by the machine 72.
However, the shield body 74 has a partition wall 20 for dividing the interior of the shield body 74 into two chambers 80, 82 spaced apart from each other in the axial direction of the shield body and a plurality of window holes 26 for communicating between the chamber 80 and the outside of the shield body 74. The chamber 80 has a truncated conical shape with the bore gradually tapering toward the rear.
The shield tunnelling machine 72 includes a crankshaft 30 supported by the partition wall 20 such that the crankshaft 30 is rotatable about an axis of the shield body 74, a drive mechanism 36 for rotating the crankshaft 30, a rotor 44 supported by an eccentric portion 34 so as to be rotatable about an axis of the eccentric portion 34 and shaped to have a truncated conical outer surface with the diameter thereof gradually increasing from the front end toward the rear end, a cutter assembly 48 fixedly attached to the front end portion of the rotor 44, an external gear 60 fixedly attached to the partition wall 20, and an internal gear 62 fixedly attached to the rotor 44 so as to be eccentric from the external gear 60 by a distance indicated by e and meshing with the external gear 60.
Further, the shield tunnelling machine 72 may be also provided with a discharge mechanism 68 as shown by a two-dotted line in FIG. 5.
While excavation is done, both the drive mechanism 36 and the jacks 78 are operated to thereby advance the tunnelling machine 72. Further, since the crankshaft 30 is rotated about the axis of the shield body 74, both of the rotor 44 and the cutter assembly 48 are revolved about the axis of the shield body 74 while being rotated about the axis of the eccentric portion 34.
As a result, the working face is excavated by the cutter assembly 48 and the excavated substances are received in the chamber 80. While the rotor 44 revolves and rotates, large solid bodies contained in the excavated substances received in the chamber 80 are crushed by the rotor 44 in cooperation with the shield body 74. The excavated substances in the chamber 80 are forcibly thrust out of the periphery of the shield body 74 through each of the window holes 26 with the revolution of the rotor 44. The substances 64 thrust out around the shield body 16 are discharged between the existing earth and sand 66 and the shield body 74 by compressing the existing earth and sand 66 around the shield body 74, as shown in FIG. 5.
The substances 64 and earth and sand 66 around the shield body 74 are repeatedly compressed by the revolution of the rotor 44. Accordingly, the substances 64 and earth and sand 66 around,, the shield body 74 are gradually consolidated while the expansive force of the substances 64 and that of the earth and sand 66 are gradually reduced. As a result, a great quantity of earth and sand may be discharged to the periphery of the shield body 74 and there is no possibility of increasing the resistance between the shield body 74 and the earth and sand therearound when the tunnelling machine 72 is advanced.
A hole excavated by the shield tunnelling machine 72 may be maintained by incorporating a new segment ring 76 therein.
A boring apparatus 90 as shown in FIG. 6 is used for forming a longitudinal hole, similar to an earth auger. The boring apparatus 90 comprises a tractor 92. The tractor 92 is a well known tractor which includes a lower structure 94 using a caterpillar and an upper structure 96 revolvingly supported by the lower structure 94. The upper structure 96 is provided with an operating section.
The front end portion of the upper structure 96 supports a strut 98 oriented as to extend in the vertical direction by an arm 100 extending from the upper structure 96. To the strut 98 is attached a rod 102 oriented in the vertical direction and annular guides 104 are attached to the rod 102. The guides 104 are spaced apart from each other in the vertical direction.
The upper end portion of the strut 98 supports a sheave mechanism 106 such that the mechanism 106 is angularly rotatable about the axis extending in the horizontal direction. The sheave mechanism 106 is provided with a seesaw 108 pivotally attached to the upper portion of the strut 98 and a sheave 110 rotatably and independently disposed on opposite ends of the seesaw 108.
Around each of the sheaves 110 is wound a wire rope 114 extending from a winch (not shown) disposed on the upper structure 96 through a roller 112 rotatably attached approximately midway along the longitudinal length of the strut 98 so as to return to the upper structure 96. An excavating machine 116 is suspended by the wire rope 114.
The excavating machine 116 includes a pulley 118 suspended by the wire rope 114. To the pulley 118 is attached a drive mechanism 120 provided with a motor and a reduction gear. The drive mechanism 120 is guided by the rod 102 so as to permit the vertical movement of the drive mechanism. To the drive mechanism 120 is connected a pipe assembly 122, which extends downward from the drive mechanism and consists of a plurality of pipes connected to each other in series, so as to be movable in the vertical direction together with the drive mechanism 120. The pipe assembly 122 slidably extends through each of the guides 104.
To an output shaft of the drive mechanism 120 is connected a rotary shaft 124 rotatably extending through the pipe assembly 122. An excavating mechanism 126 is connected to the lower end portion of the pipe assembly 122.
As shown in FIG. 7, the excavating mechanism 126 includes a cylindrical body 128 extending in the vertical direction. The upper end portion of the body 128 is connected to the lower end portion of the pipe assembly 122. The body 128 has a partition wall 20 for dividing the interior of the body 128 into two chambers 130, 132 spaced apart from each other in the axial direction of the body and a plurality of window holes 26 for communicating between the chamber 130 and the outside of the body 128. The chamber 130 has a truncated conical shape with the bore gradually tapering toward the rear.
The excavating mechanism 126 includes a crankshaft 30 supported by the partition wall 20 through a plurality of bearings 32 such that the crankshaft 30 is rotatable about an axis of the body 128, a rotor 44 supported by an eccentric portion 34 of the crankshaft 30 such that the rotor 44 is rotatable about an axis of the eccentric portion 34 and shaped to have a truncated conical outer surface with the diameter thereof gradually increasing from the front end toward the rear end, a cutter assembly 48 fixedly attached to the front end portion of the rotor 44, an external gear 60 fixedly attached to the partition wall 20, and an internal gear 62 fixedly attached to the rotor 44 so as to be eccentric from the external gear 60 by a distance indicated by e and meshing with the external gear 60. The excavating machine 116 may be also provided with a discharge mechanism 68 as shown by a two-dotted line in FIG. 1.
Each of the members as noted above is similar in structure and arrangement to the corresponding one of the members as shown in FIGS. 1 through 5. Accordingly, the crankshaft 30 is so arranged that the eccentric portion 34 of the crankshaft is located inside the chamber 130. However, the crankshaft 30 in this embodiment is connected to the rotary shaft 124.
While boring is done, the excavating machine 116 pays out the rope 114 by a predetermined amount at a time, whereby the excavating machine 116 is made to descend by its own weight. When the excavating machine 116 is descended, the drive mechanism 120 is operated. By so doing, the crankshaft 30 is rotated about the axis of the body 128, so that both of the rotor 44 and the cutter assembly 48 are revolved about the axis of the body 128 while being rotated about the axis of the eccentric portion 34.
As a result, the bottom of a hole is excavated by the cutter assembly 48 and the excavated substances are received in the chamber 130. While the rotor 44 revolves around the axis of the body 128 and rotates around its own axis, large solid bodies contained in the excavated substances received in the chamber 130 are crushed by the rotor 44 in cooperation with the body 128. The excavated substances in the chamber 130 are forcibly thrust out of the periphery of the body 128 through each of the window holes 26 with the revolution of the rotor 44. The substances 134 thrust out of the shield body 128 are discharged between the body 128 and the existing earth and sand 136 by compressing the existing earth and sand 136 around the body 128, as shown in FIG. 7.
The substances 134 and earth and sand 136 around the body 128 are repeatedly compressed with the revolution of the rotor 44. Accordingly, the substances 134 and earth and sand 136 are gradually consolidated while the expansive force of the substances 134 and that of the earth and sand 136 are gradually reduced. As a result, a great quantity of earth and sand may be discharged to the periphery of the body 128 and there is no possibility of increasing the resistance between the body 128 and the earth and sand therearound when the excavating mechanism 126 is advanced.
When the boring is done to a predetermined depth, the excavating machine 116 is pulled out by winching up the rope 114 with the winch and then a pile is inserted into a spot produced after the excavation. The pile is stably maintained by the earth and sand around the pile with the lapse of time. | A system for boring a hole in the ground including an excavating machine provided with a tubular body; an excavating mechanism supported by the body; a mechanism for shifting the excavated substances to the periphery of the body; and a driving mechanism for operating the excavating mechanism. | 4 |
This application is a continuation-in-part application of Ser. No. 08/328,694, filed on Oct. 25, 1994, now U.S. Pat. No. 5,432,207.
FIELD OF THE INVENTION
The present invention relates to a composition for producing foamed shaped articles comprised of phenolformaldehyde resin, using carbon dioxide formed in situ as the blowing agent.
BACKGROUND OF THE INVENTION
"In place" foaming is a process in which two reactive components are brought together in a mixing head where they react. The resulting reaction mixture is then transferred to a mold where the mixture is foamed and cured into a solid resin. While this process is known for foams comprised of reactive systems such as polyurethane and polyisocyanurate resins, it has not hitherto been practical to apply it to foams comprised of phenol-formaldehyde resins.
A mixing head for use in carrying out "in place foaming" is described in Fiorentini, U.S. Pat. No. 4,332,335. The head comprises a mixing chamber which communicates with a discharge orifice and first and second ducts which dispense the reactive components into the mixing chamber. Means are provided for regulating the flow of the reactants to the reaction chamber.
Phenol-formaldehyde resins can be produced from partially-reacted phenol-formaldehyde resins known as "resols". Resols are resins which are made by reacting a phenol, normally phenol itself, with formaldehyde, using an excess of formaldehyde. The resulting low polymer or oligomer has reactive methylol groups which can react further to enlarge and cross-link the polymer into a cured, three-dimensional network. If the curing is carried out in the presence of a blowing agent, the product is a phenolformaldehyde foam. It is known to use, e.g., chlorofluorocarbons as blowing agents.
Typically, phenol and formaldehyde are reacted in the presence of a basic catalyst such as sodium hydroxide and triethyl amine, followed by neutralization and distilling off water. The initially produced resin is called an A-stage resin. It is known to add urea to this initial product. The A-stage resin can then be reacted further in the presence of an acid catalyst, during which time some formaldehyde and water are liberated. If urea is present, the formaldehyde, may react with the urea to form bis methylol urea, which can also polymerize.
Typical phenolic resin foams are rigid. To increase the flexibility of these foams, large quantities of elastomers are admixed therein. However, the foam then has the qualities of the elastomers, such as low temperature resistance and emission of toxic fumes when burned. There is a great need for a flexible phenolic resin foam which does not require the use of elastomers.
SUMMARY OF THE INVENTION
An object of the invention is to provide a composition for making a phenolic resin foam, a method of making the phenolic resin foam, and a phenolic resin foam.
Another object of the invention is to provide a flexible phenolic resin foam which does require the use of elastomers. A further object of the invention is to provide a composition and method for making the flexible phenolic resin foam. The above objects and other objects are accomplished by the following.
In accordance with the present invention, a reactive phenol-formaldehyde oligomer, that is to say a resol or A-stage resin, is combined with urea, a catalyst and a reactive isocyanate. The urea and resol react to, inter alia liberate water. The water in turn reacts with the reactive isocyanate, to generate carbon dioxide while the resol is curing. As a consequence, the concurrent polymerization and carbon dioxide-liberating reactions cause carbon dioxide to be entrapped as bubbles in the polymer, as it is cured, thereby producing a foam.
These reactions may be carried out by simply mixing the components, or in a mixing head. When a mixing head is used, preferably, one side of the mixing head is supplied with a liquid containing the resol, surfactants, urea, and the isocyanate component. The other side of the mixing head is supplied with a catalyst.
The foam producing composition can be present as a two, or more, part system. In such a system, the resin and isocyanate are separated from the catalyst. The foam is easily prepared by mixing together the ingredients. Preferably, the composition is present as a two part system in which the first part comprises the phenolic resin, urea, and the isocyanate, and the second part comprises the catalyst. If needed, the first part can further include an emulsifier to facilitate mixing of the phenolic resin and the isocyanate.
The two part systems can also include conventional additives for there known use, including, surfactants, viscosity modifiers, emulsifiers, etc.
A wide variety of reactive phenol aldehyde resins may be used for the present invention. In general, they are the reaction products of a phenol, such as phenol itself and substituted phenols, for example alkyl-substituted phenols, such as cresols and nonyl phenol, paraphenyl phenol and resorcinol, alone or in mixtures of such phenols. The phenol is reacted with an aldehyde, preferably formaldehyde, although other aldehydes may be used such as acetaldehyde and furfurylaldehyde. The phenol and aldehyde are reacted in proportions such that there is an stoichometric excess of aldehyde to phenol, for example 1.75 to 2.25 mols of aldehyde for each mol of phenol. This reaction is normally carried out in the presence of a basic catalyst, for example sodium hydroxide or potassium hydroxide, and triethyl amine may also be present in combination with the hydroxide. Ordinarily, the phenol and base are charged into a reactor initially, and then formaldehyde is added. The mixture is heated to for example 70°-75° C. The heating is continued until a desired molecular weight is achieved, for example measured by could point. Oxalic acid may be added as a scavenger for the sodium or potassium chloride which may be formed during the reaction. When the desired molecular weight is achieved, the mixture is cooled and neutralized, following which water is distilled off to increase solids, for example to 78-82%. Then, the mixture is cooled to, e.g., 50° C. Urea is then added, but not reacted.
The above-described reaction results in the formation of a resin containing aliphatic alcohol groups, methylol groups in the case of formaldehyde. Useful resins are, for example characterized by viscosities of 3,000 cps to 20,000 and a molecular weight of 300 to 600.
For example, the reactive resin can be present in the foam composition in an amount of about 60 to about 92% by weight, preferably, about 70 to about 85% by weight of the total composition.
The second constituent of the foam-forming reaction mixture is urea, which preferably is introduced into the resol in the manner described above. The amount used can vary from 4 to 20%, based on the weight of phenolic resin. As noted above, during further reaction, the urea reacts with formaldehyde. For example, the urea can be present in the foam composition in an amount of about 1 to about 20% by weight, preferably, about 5 to about 10% by weight of the total composition.
The isocyanate constituent can be for example an isocyanate which does not react with the other components until the reaction temperature is elevated, for example to 130° F. Thus, a blocked isocyanate may be used. Preferably, isocyanate is PAPI, i.e., a polyphenylenemethylenepolyisocyanate having the formula: ##STR1##
Several different products of this formula can be used, both TDI and polymer varying in average molecular weight from 200 to 500, viscosities from 200 to 4,000 cps, functionalities from 2-4 and isocyanate equivalent wt. range from 78.5-150.
For example, the isocyanate can be present in the foam composition in an amount of about 1 to about 15% by weight, preferably, about 1 to about 5% by weight of the total composition.
It is possible to slow down the reaction, for example, by using a blocked TDI or MDI isocyanate. However, as water is not liberated until the A-stage resin-described above starts to polymerize in the presence of an acid catalyst, PAPI can be used in unblocked form.
The density of the foam can be varied by adjusting the molecular weight of the phenolic resin. A higher molecular weight phenolic resin will result in a denser foam. The density of the foam is easily adjusted to within about 1 pcf using the molecular weight of the phenolic resin. However, if a more precise density of the foam is desired, the density of the foam can be fine tuned by varying the amount of isocyanate. By increasing the amount of isocyanate present, the amount of carbon dioxide produced will be increased, causing the density to be reduced. If amounts of isocyanate above 5% are used, preferably the foam is kept under pressure. For example, if about 15% of isocyanate is used, a pressure of 200 psi can be applied to the foam to prevent frothing.
An open cell foam can be made by adding compounds which lyse the cell walls, which include, for example, dodecylbenzene sulfonic acid, sodium ether lauryl sulfate, and sodium sulfosuccinate.
The flexibility of the foam can be increased by prolonging the curing time of the foam. The curing time is the time measured from the when the mixed foam composition is charged into the mold until when the produced foam is no longer tacky. For example, the rigid foams produced in the examples below cured in about 30 seconds to about 2 minutes, with the compositions containing lower molecular weight phenolic resins curing closer to 30 seconds and the compositions containing higher molecular weight phenolic resins curing closer to about 2 minutes. If the amount or type of catalyst, such as blocking the catalyst, is adjusted to provide a curing time of greater than 2 minutes the resulting foam will be more flexible. Another way of prolonging the curing time is to add triethanolamine. For example, the flexible foams produced below in examples 11 and 12 had a curing time of about 8 minutes.
The polymerization and foaming reaction may be carried out in the presence of a catalyst, for example an acid catalyst. Suitable catalysts include phenol sulfonic acid, toluene sulfonic acid (TSA), xylene sulfonic acid (XSA), sulfonic acid and phosphoric acid which may be used independently and in mixtures. The acid catalyst preferably is diluted with methanol. A particularly preferred catalyst is a mixture of toluene sulfonic acid and phenol sulfonic acid in a 30/70 blend. This mixture gives a better curing rate and the closed cell content of the foam was higher. In turn, this increased the flex modulus compression rating, and also shear resistance. This catalyst also gives a stronger, less friable foam, and this effect is believed to be caused by utilizing more of the water liberated in the reaction and converting it to carbon dioxide. Other catalysts were used in some cases because they reduced oxidation of metal molds. Another preferred catalyst is a 20/80 blend of XSA/TSA. The amount of catalyst added may be about 1 to about 20%, preferably, 5 to 20% based on the weight of the reaction mixture.
The ratio of the reactive phenoxy resin to the catalyst, for example, can be in the range of about 7:1 to about 14:1, and more preferably about 10:1.
In addition to the reactive constituents, it is desirable to include surface active agents which assist in the foaming action, i.e., in stabilizing the foam. There are many surfactants which can be used for this purpose, for example polysorbates which have an HLB greater than 11. Other fatty acids may be used such as those having the structure: ##STR2## Other surfactants which can be used are the sodium dialkyl sulfosuccinates having the structure: ##STR3## where R is an alkyl group.
Nonionic surfactants which can be used are N-alkyl phenyl polyoxyethylene ethers of the formula:
R--C.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.x H
where R is an alkyl group.
Another useful group of surfactants are the dimethyl(polysiloxane) copolymers. There are a wide range of these products which can be used. Examples include General Electric Co.'s SFl188, Union Carbide's L-5340 and Dow Corning's DC 193 and DC 201.
In accordance with a preferred embodiment of the invention, an anionic surfactant and a cationic surfactant are added. Surfactants which have been used successfully include polysorbate 40 polyoxyethylene 20 monopalmitate, acid no. 2.2, hydroxyl no. 89-105 and DC 193 dimethylpolysiloxane. A particularly useful mixture comprises DC 193 and SF 1188 in a 20/80 wt./wt. mixture.
The concentration of surfactant varies in accordance with the surfactant, but generally is in the range 0.3 to 4%. The evaluation of potential surfactants and the amount of surfactant is carried out in a manner similar to that in other foaming processes.
Fillers may also be added such as aluminum trihydrate which provides fire retardant properties, but it can be omitted if not needed for a particular application.
In addition, microspheres may be added, as is known for foamed products. Microspheres are added to provide higher insulation (R factor) properties.
A particularly important feature of the present invention is that the foaming reaction reduces the level of residual formaldehyde in the product. This, a sample of the foamed product was found to have a residual formaldehyde level of 0.9 parts per billion. This value was determined by sampling air as it was released from the foam using a calibrated pump. The gaseous products from the foam were flushed into an impinger to collect the formaldehyde released over an eight-hour period. The resulting solution was then analyzed for formaldehyde using the chemistry of NIOSH Method 3500. While the reason for the reduced formaldehyde levels is not known, it is believed to arise from reaction between formaldehyde and primary amine formed when the polyisocyanate reacts with water, according to the reaction:
RNCO+H.sub.2 O±RNH.sub.2 +CO.sub.2 ↑.
The following formulation has been found to be particularly useful for a closed cell foam:
A. Phenolic Resin: 100 parts
B. Anionic surfactant: 1-3 parts
C. Ionic surfactant: 1-3 parts
D. PMDI resin: 0.5 to 1.5 parts
E. Catalyst 5 to 9 parts
F. Aluminum trihydrate: 10 parts
G. Microspheres 2 to 7 parts, if used. pH is 5.5-6.0.
In a batch process, all of the components are added to a mixing vessel and combined. In a continuous process, the components are supplied to a mixing head, all of the components except the catalyst being supplied to one side of the head, and the catalyst being supplied to the other side. The foam emerging from the head is deposited on a continuous belt, moving at between 2 and 20 feet per minute.
The phenolic resin, A, is a phenol-formaldehyde A-stage resin which contains 10.3% urea, based on the weight of phenol. It is obtained in the manner described above, using 1.75 to 2.25 moles formaldehyde for each mole of phenol and a basic catalyst (NaOH or KOH). The mixture of phenol and formaldehyde is reacted until a molecular weight of 350 400 is achieved, following which the mixture is neutralized with oxalic acid, which also scavenges leachable sodium or potassium chloride. After distillation, 4 to 14% urea is added, based on the weight of the phenol. Since the urea is present in the form of beads, heat is applied to dissolve it. The reactivity of the resin mixture is adjusted in relation to the density desired for the final product.
The surfactant used is a mixture of polysorbate 40 polyoxyethylene 20 sorbitan monopalmitate, acid no. 2.2, hydroxyl no. 89-104, sophinocation no. 41-52, HLB 15.6, and DC-193 dimethylpolysiloxane, Union Carbide 1-5340 of Union Carbide or SF-1188 of General Electric.
The isocyanate which is used is PAPI having an NCO content of 30.8, average molecular weight of 375, functionality of 3, isocyanate equivalent weight of 136.5.
The catalyst is phenol sulfonic acid cut with methanol. Total acidity is 19.3, wt % phenol sulfonic acid is 66.8, specific gravity 1.3140, wt. % H 2 SO 4 0.58. Toluene sulfonic acid may also be used. Weight per cent of catalyst is 5-9%, based on the weight of the phenolic resin.
For an open cell foam, the phenolic resin should have a molecular weight of 300 to 600. The amount of urea is 4 to 14%, based on the phenolic resin. Surface active agents used include a first type to reduce surface tension between cells, such as dodecyl benzene sulfonic acid, sodium lauryl sulfate, acetyl trimethyl ammonium bromide and sodium sulfosuccinate. A mixture of these may be used. In addition, a surfactant is used for nucleation of the cell site, and to control cell size. Suitable materials are polyoxyethylene 20, sorbitan mono palmitate, dimethylpolysiloxanes L5340, S1 1188, and DC 193. Mixtures of these may be used. Isocyanates which can be used are PAPI from Union Carbide and Mobay's Lupranite M205. The catalyst may be phenol sulphonic acid cut with methanol, total acidity 19.3 wt %, PSA 66.0, specific gravity 1.3140, Wt % H 2 SO 4 , 0.58. 4 to 14% catalyst is used.
The specifications for particularly useful urea modified phenolic resins is illustrated in the following table:
______________________________________ Urea ContentResin Reactivity.sup.1 (%)______________________________________HRJ 11761 280-310° F. 8.3HRJ 12667 180-210° F. 10.3GP 541053 300-320° F. 8.3GP 200-220° F. 7.3HRJ 4173h 165-185° F.______________________________________ .sup.1 Peak exotherm temperature when resin and urea cured with catalyst but no isocyanate
The following table illustrates the performance of samples of foam made from these resins:
______________________________________ Foam PAPI Urea DensityResin Reactivity (Wt %) (Wt %) Pounds/ft.sup.3______________________________________HRJ 12667 180-220° F. 1.5 10.3 12HRJ 11761 280° F. 1.5 8.3 1.6GP 305° F. 1.5 8.3 1.4GP 305° F. 3 8.3 1HRJ 12667 180° F. 1 10.3 20______________________________________
The data gives an approximate range of the densities which can be achieved by the selection of the resin according to its reactivity. Fine tuning of density can be achieved by adjusting the proportion of PMDI. Examples of densities which have been achieved successfully are:
______________________________________Open Cell Closed Cell Density DensitySample pounds/ft.sup.3 Sample pounds/ft.sup.3______________________________________A 0.8 A 1.0B 1.0 B 2.0C 1.5 C 2-28______________________________________
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention is illustrated by the following non-limiting examples, in which all parts are by weight unless indicated otherwise.
EXAMPLE 1
Resin HRJ 12667-500 grams
PMDI 2 grams
Tween 8 grams
Silicone surfactant--3 grams
Glycerine--5 grams
Catalyst (PSA/TSA 1 )--50 grams
The first five components were mixed for 3 minutes, and then the catalyst was added, and mixed in for 1 minute. The reaction mixture was then dumped into a mold. A foam density of 20 pounds per cubic foot (hereinafter "pcf") was obtained.
EXAMPLE 2
An open cell foam was made from the following formulation:
Resin GP 541053 (Reactivity 305° F.)--275 grams
Resin HRJ 12667-- 25 grams
Tween 40--5 grams
SF 1188--1 gram
Dodecylbenzene sulfonic acid-- 5.5 grams
Sodium ether lauryl sulfate-- 5.5 grams
PMDI--5 grams
Phenol sulfonic acid-- 30 grams.
The foam was relatively dense, and a larger amount of PMDI was added to decrease the density, in the following formulation:
Resin GP 541053-- 275 grams
Resin HRJ 12667-- 25 grams
Tween 40-- 6 grams
SF 1188-- 1 gram
Dodecylbenzene sulfonic acid--5.5 grams
Sodium ether lauryl sulfate--5.5 grams
PMDI--7 gram
Phenol sulfonic acid--30 grams.
The last formulation was repeated, except that the amount of SF 1188 was increased to 3 grams.
EXAMPLE 3
An open cell foam was produced from the following formulation, the proportion of silicone being increased to reduce cell size:
Resin HRJ 11761-- 275 grams
Resin HRJ 12667-- 38.1 gram
Tween 40-- 6.4 grams
SF 1188/15340-- 4 grams/2 grams
Dodecylbenzene sulfonic acid--6 grams
Sodium ether lauryl sulfate--6 grams
Rhodaquat--6 grams
Sodium Sulfosuccinate--5.5 grams
PMDI--7 grams
Phenol sulfonic acid--36 grams
EXAMPLE 4
A foam was produced from the following formulation:
Resin HRJ 11761-- 400 grams
Resin HRJ 12667-- 200 grams
Tween 40-- 18 grams
DC 193-- 9 grams
SF 1188-- 6 grams
PMDI--22 grams
Phosphoric acid (85%)--75 grams
EXAMPLE 5
A foam was produced from the following formulation:
Resin HRJ 11761-- 400 grams
Resin HRJ 12667-- 200 grams
Tween 40-- 22 grams
DC 193-- 9 grams
SF 1188-- 6 grams
PMDI--22 grams
Phosphoric acid (85%)--75 grams
EXAMPLE 6
A foam was made from the following formulation:
Resin HRJ 11761-- 400 grams
Resin HRJ 12667-- 200 grams
Tween 40-- 18 grams
DC 193-- 9 grams
SF 1188-- 6 grams
PMDI--22 grams
Phosphoric acid (85%)--55 grams
EXAMPLE 7
A foam was made from the following formulation:
Resin HRJ 11761-- 400 grams
Resin HRJ 12667-- 200 grams
Tween 40-- 18 grams
DC 193-- 9 grams
SF 1188-- 6 grams
PMDI--22 grams
Phosphoric acid (85%)--85 grams
EXAMPLE 8
A foam was made from the following formulation:
Resin GP 541053-- 500 grams
Resin HRJ 12667-- 100 grams
Tween 40-- 12 grams
Silicone 407-2178-- 26 grams
Dodecylbenzene sulfonic acid--12 grams
Sodium ether lauryl sulfate--16 grams
Sodium sulfosuccinate--12 grams
PMDI--9 grams
Phenyl sulfonic acid--72 grams
EXAMPLE 9
A rigid phenolic foam was made from the following formulation:
(a) Resin GP 541053-- 100 parts
(b) PMDI--1.5 parts
(c) tween polysorbate--5 parts
(d) 20% wt. XSA/80% wt. TSA--10 parts
(e) DC 193-- 7 parts
(f) gamabutylactone--3 parts
Components a, b and c were combined as part I. Components d, e and f were combined as part II. Parts I and II were mixed together and charged into a mold. A rigid foam was produced.
The density of the foam can be varied by adjusting the molecular weight of the phenolic resin. A higher molecular weight phenolic resin will result in a denser foam. The density of the foam is easily adjusted to within about 1 pcf by the molecular weight of the phenolic resin. However, is a more precise density of the foam is desired, the density of the foam can be fine tuned by varying the amount of isocyanate. By increasing the amount of isocyanate present, the amount of carbon dioxide produced will be increased, causing the density to be reduced. If amounts of isocyanate above 5% are used, preferably the foam is kept under pressure. For example, if about 15% of isocyanate is used, a pressure of 200 psi can be applied to the foam to prevent frothing.
An open cell foam can be made by adding compounds which lyse the cell walls, which include, for example, dodecylbenzene sulfonic acid, sodium ether lauryl sulfate, and sodium sulfosuccinate.
The flexibility of the foam can be increased by prolonging the curing time of the foam. The curing time is the time measured from the when the mixed foam composition is charged into the mold until when the produced foam is no longer tacky. For example, the rigid foams produced above cured in about 30 seconds to about 2 minutes, with the compositions containing lower molecular weight phenolic resins curing closer to 30 seconds and the compositions containing higher molecular weight phenolic resins curing closer to about 2 minutes. If the amount or type of catalyst is adjusted to provide a curing time of greater than 2 minutes the resulting foam will be more flexible. Another way of prolonging the curing time is to add triethanolamine. The following Examples had curing times of about 8 minutes.
EXAMPLE 10
A flexible foam was made from the following formulation:
(a) Resin GP 541053-- 500 grams
(b) PMDI--9 grams
(c) triethanolamine--15 grams
(d) 20% wt. XSA/80% wt TSA--25 grams
(e) DC 193-- 35 grams
(f) polysorbate--5 grams
(g) butylactone--15 grams
Components (a), (b) and (f) were combined to form part I. Components (c), (d), (e) and (g) were combined to form part II. Parts I and II were mixed together for about 30 seconds and then charged into a mold. The foam rise time was 1 minute and 30 seconds. The foam density was 2 pcf. The flexibility of the foam was excellent.
EXAMPLE 11
A flexible foam was made from the following formulation:
(a) Resin GP 541053-- 500 grams
(b) PMDI--9 grams
(c) polysorbate--7 grams
(d) triethanolamine--10 grams
(e) 20% xylene sulfonic acid / 80% toluene sulfonic acid--50 grams
(f) DC 193-- 35 grams
(f) butylactone--15 grams
Components (a), (b) and (c) were combined to form part I. Components (d), (e), (f) and (g) were combined to form part II. Parts I and II were mixed together for about 1 minute and then charged into a mold. The foam rise time was about 40 seconds. The foam density was 2 pcf. The flexibility of the foam was excellent, but less than the foam of Example 10.
The foams made according to the present invention exhibit significantly greater resistance to pressure because of the thicker cell walls, than conventional phenolic resin foams.
The foams made according to the present invention exhibit a very high temperature resistance, for example, at least 90% integrity of a phenolic foam made according to Example 9 was maintained to a temperature above 450° F. Thus, the phenolic resin foams according to the present invention do not require a flame retardant. However, if desired, a flame retardant can be included, for example aluminum trihydrate.
In contrast, typical urethane foams, containing flame retardants and fillers to increase temperature resistance, lose integrity at temperatures of at most 250°.
Furthermore, when the phenolic foams made according to the present invention are burned, only carbon dioxide and water are given off, which are non-toxic. In contrast, typical urethane foams give off toxic fumes, such as hydrogen cyanide, when they are burned.
Phenolic foams of different density were made according to Example 9 above and sent to an independent lab, American Foam Technologies, for testing. Using the ASTM E-84 fire test method, the phenolic foams according to present invention exhibited a flame spread in the range of 10-15 and a smoke density of 5. This data indicates that the phenolic foams according to the invention are significantly greater resistance to flame than urethane foams which typically only have a flame spread of around 27 and a smoke density in the 60's.
The thermal expansion of the phenolic foams made according to Example 9 was also tested, and ranged from 38.4 ppm/°C. to 40.9 ppm/°C. This data demonstrates that the size of the phenolic foams according to the present invention are affected less by changes in temperature than conventional urethane foams.
The resistance of the phenolic foams made according to Example 9 to chlorinated solvents, acids, and bases was also tested. The phenolic foams did not swell or break down when exposed to chlorinated solvents, acids and bases. In contrast, conventional urethane foams readily swell when exposed to chlorinated solvents.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one of ordinary skill in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. | Provided is a composition for making a foam including a reactive phenolic resin, urea, and an isocyanate. Also provided is a method for making the foam and a foam made from the composition. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority from Japanese Patent Application No. 2009-159008 filed on Jul. 3, 2009, the entire contents of which are incorporated herein by reference.
BACKGROUND
[0002] 1. Field
[0003] The embodiments discussed herein relate to a receiving circuit.
[0004] 2. Description of Related Art
[0005] In an orthogonal frequency division multiplexing (OFDM) method used for transmitting a digital signal, data may be allocated to a plurality of mutually orthogonal carriers. At a transmitting side, data may be modulated by using inverse fast fourier transform (IFFT). Then, at a receiving side, data may be demodulated by using fast fourier transform (FFT). Since the OFDM method has high frequency usage efficiency, the OFDM method may be adopted for Integrated Services Digital Broadcasting-Terrestrial (ISDB-T), a standard for terrestrial digital broadcasting.
[0006] Related techniques are disclosed in Japanese Laid-open Patent Publication No. 2007-68038, Japanese Laid-open Patent Publication No. 2001-274696, Japanese Laid-open Patent Publication No. 2005-318374, Japanese Laid-open Patent Publication No. 2001-320345, Japanese Laid-open Patent Publication No. 2003-101505, and Japanese Laid-open Patent Publication No. 2007-318330.
SUMMARY
[0007] According to one aspect of the embodiments, a data receiving circuit is provided which includes a first de-interleave circuit configured to de-interleave first data which is demodulated and is soft-decision-processed; a second de-interleave circuit configured to de-interleave second data which is demodulated and is soft-decision-processed; a memory configured to be shared by the first de-interleave circuit and the second de-interleave circuit and store respective hard decision information and respective soft decision information of the first data and the second data; and a memory control circuit configured to vary first through fourth numbers of bits stored in the memory. The first number corresponds to the hard decision information of the first data. The second number corresponds to the soft decision information of the first data. The third number corresponds to the hard decision information of the second data. The fourth number corresponds to the soft decision information of the second data.
[0008] Additional advantages and novel features of the invention will be set forth in part in the description that follows, and in part will become more apparent to those skilled in the art upon examination of the following or upon learning by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 illustrates an exemplary receiver;
[0010] FIGS. 2A , 2 B, and 2 C illustrate exemplary diversity combinations;
[0011] FIG. 3 illustrates an exemplary error correction circuit;
[0012] FIGS. 4A and 4B illustrate an exemplary allocation of TMCC information;
[0013] FIG. 5 illustrates an exemplary hard decision process;
[0014] FIG. 6 illustrates an exemplary number of bits used for soft decision information;
[0015] FIG. 7 illustrates an exemplary memory control circuit;
[0016] FIG. 8 illustrates exemplary bit locations;
[0017] FIG. 9 illustrates an exemplary time de-interleave circuit;
[0018] FIG. 10 illustrates an exemplary switching process;
[0019] FIG. 11 illustrates an exemplary switching process;
[0020] FIG. 12 illustrates an exemplary switching process;
[0021] FIG. 13 illustrates an exemplary memory ratio switching process; and
[0022] FIG. 14 illustrates an exemplary receiving system.
DESCRIPTION OF EMBODIMENTS
[0023] A signal received by an antenna may be demodulated by using FFT. An error correction section may perform a demapping process on demodulated data. Maximum likelihood decision may be performed on data subjected to soft decision processing using Viterbi decoding. Then, data subjected to the maximum likelihood decision may be error-corrected using Reed-Solomon (RS) decoding. The error-corrected data may be output as a transport stream (TS). An MPEG decoder or the like, provided in a stage subsequent to an OFDM demodulating circuit, may decode the transport stream.
[0024] The error correction section may perform de-interleave process. Examples of the de-interleave process may include a frequency de-interleave process in which sorting in the frequency axis direction is performed, a time de-interleave process in which sorting in the time axis direction is performed, a bit de-interleave process in which sorting in units of bits is performed, and a byte de-interleave process in which sorting in units of bytes is performed. A memory for storing data temporarily may be provided.
[0025] In ISDB-T, a standard for terrestrial digital broadcasting, a bandwidth of six MHz, allocated to one channel, is divided into 13 segments. One segment among the 13 segments adopts a modulation method such as quadrature phase shift keying (QPSK) or the like, which has a low bit rate and high noise tolerance, and is used for broadcasting for a mobile receiver such as a mobile phone or the like. The other 12 segments adopt a modulation method such as 64 quadrature amplitude modulation (64 QAM) or the like, which has a high bit rate and low noise tolerance, and are used for broadcasting for a fixed terminal.
[0026] In an in-vehicle terminal, 12-segment broadcasting may be received using diversity combining. For example, four antennas may perform four-diversity reception. Two channels may be used contemporaneously. Alternatively, one channel may be used for viewing and the other channel may be used for recording. Therefore, two TS outputs may be provided.
[0027] FIG. 1 illustrates an exemplary receiver. The receiver illustrated in FIG. 1 may perform diversity combining. The receiver includes antennas 10 - 1 to 10 - 4 , tuners 11 - 1 to 11 - 4 , A/D conversion circuits 12 - 1 to 12 - 4 , orthogonal demodulation circuits 13 - 1 to 13 - 4 , FFT circuits 14 - 1 to 14 - 4 , and transmission channel equalization circuits 15 - 1 to 15 - 4 . The receiver includes a diversity combining circuit 16 and error correction circuits 17 - 1 and 17 - 2 . The receiver includes a four-diversity reception function and a two-TS output function. The number of diversity combinations and the number of outputs TS may be arbitrary. A plurality of error correction circuits may be provided. The diversity combining may not be performed.
[0028] Signals received by the antennas 10 - 1 to 10 - 4 are input to the tuners 11 - 1 to 11 - 4 . The tuners 11 - 1 to 11 - 4 extract signals, which exist in a frequency band corresponding to a designated reception channel, from reception signals. Then, the tuners 11 - 1 to 11 - 4 convert the extracted signals to intermediate frequency (IF) signals and output the signals. The A/D conversion circuits 12 - 1 to 12 - 4 convert the output signals of the tuners 11 - 1 to 11 - 4 from analog signals to digital signals. The orthogonal demodulation circuits 13 - 1 to 13 - 4 convert the digital signals to complex baseband signals. The FFT circuits 14 - 1 to 14 - 4 perform fast fourier transform (FFT) on the complex baseband signals and convert time domain signals to frequency domain signals. Signals subjected to orthogonal frequency division multiplexing are demodulated and signals corresponding to a plurality of carriers are obtained.
[0029] The outputs of the FFT circuits 14 - 1 to 14 - 4 include data signals and scattered pilots (SP) used for synchronous detection. The outputs of the FFT circuits 14 - 1 to 14 - 4 include additional information transmission carriers (AC: Auxiliary Channel) used for additional information transmission and control information transmission carriers (TMCC: Transmission and Multiplexing Configuration Control) used for transmitting transmission parameter information or the like. The SP signals are BSPK-modulated and data signals are modulated using one of QPSK, 16 QAM, and 64 QAM. AC signals on the AC carriers and TMCC signals on the TMCC carriers are subjected to differential BPSK (DBPSK) modulation. The transmission channel equalization circuits 15 - 1 to 15 - 4 perform equalization process on the data signals output from the FFT circuits 14 - 1 to 14 - 4 based on the SP signals output from the FFT circuits 14 - 1 to 14 - 4 . Transmission channel characteristics are equalized. The equalization-processed data signals are supplied to the diversity combining circuit 16 . The diversity combining circuit 16 , for example, may perform diversity combination on the equalized data signals received from four process lines of demodulation circuits. For example, reception data which has the largest reception intensity may be selected from among a plurality of process lines of reception data. The plurality of process lines of reception data may be combined by overlapping the phases of the reception data. The diversity combining circuit 16 supplies the reception data subjected to diversity combination to the error correction circuits 17 - 1 and 17 - 2 .
[0030] FIGS. 2A , 2 B, and 2 C illustrate an exemplary diversity combination. The diversity combination illustrated in FIGS. 2 A, 2 B, and 2 C may be performed by the diversity combining circuit 16 illustrated in FIG. 1 . As illustrated in FIG. 2A , for example, dual process lines of received data may be combined and supplied to the error correction circuit 17 - 1 and the other dual process lines of received data may be combined and supplied to the error correction circuit 17 - 2 . As illustrated in FIG. 2B , three process lines of received data may be combined and supplied to the error correction circuit 17 - 1 and received data corresponding to the other process line may be supplied to the error correction circuit 17 - 2 . Three process lines of received data may be combined and supplied to the error correction circuit 17 - 2 and received data corresponding to the other process line may be supplied to the error correction circuit 17 - 1 . As illustrated in FIG. 2B , four process lines of received data may be combined and supplied to the error correction circuit 17 - 1 and no received data may be supplied to the error correction circuit 17 - 2 . Four process lines of received data may be combined and supplied to the error correction circuit 17 - 2 and no received data may be supplied to the error correction circuit 17 - 1 .
[0031] FIG. 3 illustrates an exemplary error correction circuit. The error correction circuit illustrated in FIG. 3 may correspond to the error correction circuits 17 - 1 and 17 - 2 illustrated in FIG. 1 . Diversity combining circuits 16 - 1 and 16 - 2 illustrated in FIG. 3 may correspond to the diversity combining circuit 16 illustrated in FIG. 1 . The error correction circuit 17 - 1 may include a frequency de-interleave circuit 20 - 1 , a demapping circuit 21 - 1 , a time de-interleave circuit 22 - 1 , a bit de-interleave circuit 23 - 1 , a Viterbi decoding circuit 24 - 1 , a byte de-interleave circuit 25 - 1 , and an RS decoding circuit 26 - 1 . The error correction circuit 17 - 1 may include a TMCC error correction circuit 27 - 1 . Memories 28 - 1 , 29 - 1 , and 30 - 1 may be used by the frequency de-interleave circuit 20 - 1 , the bit de-interleave circuit 23 - 1 , and the byte de-interleave circuit 25 - 1 , respectively. An error correction path with the error correction circuit 17 - 1 may be referred to as a first process line.
[0032] The error correction circuit 17 - 2 may include a frequency de-interleave circuit 20 - 2 , a demapping circuit 21 - 2 , a time de-interleave circuit 22 - 2 , a bit de-interleave circuit 23 - 2 , a Viterbi decoding circuit 24 - 2 , a byte de-interleave circuit 25 - 2 , and an RS decoding circuit 26 - 2 . The error correction circuit 17 - 2 may include a TMCC error correction circuit 27 - 2 . Memories 28 - 2 , 29 - 2 , and 30 - 2 may be used by the frequency de-interleave circuit 20 - 2 , the bit de-interleave circuit 23 - 2 , and the byte de-interleave circuit 25 - 2 , respectively. An error correction path with the error correction circuit 17 - 2 may be referred to as a second processing line.
[0033] Under the control of a CPU 35 , a diversity combining specification circuit 34 specifies the type of diversity combination. For example, one of diversity combining methods illustrated in FIGS. 2A , 2 B, and 2 C is specified. Diversity combining specification is supplied from the diversity combining specification circuit 34 to the diversity combining circuits 16 - 1 and 16 - 2 . The diversity combining circuits 16 - 1 and 16 - 2 perform diversity combining based on the diversity combining specification. The diversity combining specification from the diversity combining specification circuit 34 is supplied to a memory control circuit 32 . The memory control circuit 32 controls a memory 31 in response to the diversity combining specification.
[0034] Under the control of the CPU 35 , a TS switching instruction circuit 33 instructs switching between TS output operations. For example, switching between a two-TS-output operation in which two TS outputs are output from the error correction circuits 17 - 1 and 17 - 2 respectively and a one-TS-output operation in which one TS output is output from either the error correction circuit 17 - 1 or 17 - 2 may be performed. A plurality of error correction circuits, more than three, may output a plurality of TS output, for example, more than three TS outputs which may be at a maximum. The TS switching instruction circuit 33 supplies TS switching information to the memory control circuit 32 . The memory control circuit 32 controls the memory 31 in response to the TS switching information. The TS switching instruction circuit 33 controls the number of soft decision bits used in the Viterbi decoding circuits 24 - 1 and 24 - 2 , according to TS switching.
[0035] The TMCC error correction circuit 27 - 1 performs error correction on a control information transmission carrier TMCC extracted from a reception signal in the first process line and obtains TMCC information, such as transmission parameter information or the like, based on the error correction result. The TMCC error correction circuit 27 - 2 performs error correction on a control information transmission carrier TMCC extracted from a received signal in the second process line and obtains TMCC information based on the error correction result. FIGS. 4A and 4B illustrate an exemplary allocation of the TMCC information. FIG. 4A illustrates TMCC carriers included in given locations of 204 symbols corresponding to symbol numbers 0 to 203. For example, three-bit data which includes TMCC signal values of three symbols corresponding to symbol numbers 28 to 30 indicates a current modulation method. FIG. 4B illustrates meanings assigned to data illustrated in FIG. 4A . For example, when three-bit data which indicates the current modulation method is “010”, a 16 QAM modulation method is used. The TMCC error correction circuits 27 - 1 and 27 - 2 supply extracted information, which relates to a data modulation method and a time interleave length, to the memory control circuit 32 . The memory control circuit 32 controls the memory 31 in response to the supplied information which relates to the data modulation method and the time interleave length.
[0036] The memory 31 is shared by the time de-interleave circuits 22 - 1 and 22 - 2 . The time de-interleave circuit 22 - 1 de-interleaves first received data subjected to demodulation process and soft decision process. The time de-interleave circuit 22 - 2 de-interleaves second received data subjected to demodulation process and soft decision process. Hard decision information and soft decision information of the first received data and the second received data are stored in the memory 31 . The memory control circuit 32 varies the number of bits stored in the memory for the hard decision information of the first data, the soft decision information of the first data, the hard decision information of the second data, and the soft decision information of the second data. The number of bits may be varied dynamically. With respect to the first reception data and the second reception data, the memory control circuit 32 varies the number of bits stored in the memory based on at least one of information indicating the validity or the invalidity of a TS output, a data modulation method, a time interleave length, and the number of diversity combinations. The information which indicates the validity or the invalidity of the TS output for example, information which relates to the TS output for the first received data and the second received data, is supplied from the TS switching instruction circuit 33 . Information which relates to the data modulation method and the time interleave length is supplied from the TMCC error correction circuits 27 - 1 and 27 - 2 . Information which relates to the number of diversity combinations is supplied from the diversity combining specification circuit 34 . In another de-interleave processing such as frequency de-interleave process or the like, a memory may be shared and the number of bits may be reduced.
[0037] The demapping circuits 21 - 1 and 21 - 2 illustrated in FIG. 3 perform demapping process. In the demapping process, the data transmission point of data transmitted from a transmitting side is hard-decided.
[0038] FIG. 5 illustrates an exemplary hard decision process. A modulation method illustrated in FIG. 5 may be 64 QAM. For example, in the received signals subjected to transmission path equalization by the transmission path equalization circuits 15 - 1 and 15 - 4 , a signal point which is at a short distance from the received signal is specified among 64 signal points of 64 QAM, which exist on a complex plane illustrated in FIG. 5 . The specified signal point is estimated to be a transmission point. In 64 QAM, three-bit hard decision information which indicates eight locations in an I axis direction and three-bit hard decision information which indicates eight locations in a Q axis direction, for example, six-bit hard decision information in all, are obtained. B 0 , b 1 , b 2 , b 3 , b 4 , and b 5 illustrated in FIG. 5 indicate the hard decision information. When the modulation method is 16 QAM, four-bit hard decision information is obtained by combining four bits from the I axis and the Q axis. When the modulation method is QPSK, two-bit hard decision information is obtained by combining two bits from the I axis and the Q axis. Error correction is performed by using Viterbi decoding based on the hard decision information, so that transmission data is obtained. A decoding error may occur. In addition to the hard decision information indicating “0” or “1”, soft decision information which indicates a decision result by using a value between “0” and “1” is obtained by finely dividing a distance between a current location for the hard decision and an adjacent location for the hard decision. The soft decision information may be used for the Viterbi decoding. A decoding error may be reduced.
[0039] A location of an asterisk “*” illustrated in FIG. 5 may be a candidate for a soft decision point. Between two adjacent signal points whose locations are different from each other on the I axis, a bit value, which corresponds to one of three bits, b 1 , b 3 , and b 5 , the three bits indicating a location on the I axis, may be different from each other. Between two adjacent signal points whose locations are different from each other on the Q axis, a bit value, which corresponds to one of three bits, b 0 , b 2 , and b 4 , the three bits indicating a location on the Q axis, may be different from each other. A value between “0” and “1” is determined by using 16 values ranging from “0000” to “1111” in order to indicate the accuracy of a signal point using, for example, four-bit soft decision information. How close the value is to either “0” or “1” is indicated. Since the most significant bit coincides with the hard decision, the number of bits used for the soft decision information may be six bits in all, by combining three bits from the I axis and three bits from the Q axis. The number of bits used for the soft decision information may include four-bit location information, which includes two-bit location information of the soft decision for one of three bits indicating a location on the I axis and two-bit location information of the sift decision for one of three bits indicating a location on the Q axis. The number of bits used for the four-bit soft decision process in 64 QAM may include six bits used for the hard decision information, six bits used for the accuracy information of the soft decision information, and four bits used for the location information of the soft decision information.
[0040] FIG. 6 illustrates an exemplary number of bits used for soft decision information. In FIG. 6 , the number of bits used for the soft decision information varies with the modulation method used. The number of bits used for the four-bit soft decision process in 64 QAM may be, for example, 16 bits as illustrated in FIG. 6 . The number of bits used for three-bit soft decision process in 16 QAM may be 10 bits. In time de-interleave process, data corresponding to the time duration specified in a standard is accumulated, each piece of the data having the number of bits illustrated in FIG. 6 . According to a standard for terrestrial digital broadcasting, when a time interleave length I is “4” in a reception mode 3 , the largest amount of data may be accumulated. In full-segment reception (13-segment reception), 948480 signal points (=72960*13 (segment)) may be accumulated. In the four-bit soft decision process in the modulation method 64 QAM, memory capacity corresponds to 15175680 bits (=948480*16) and is smaller than memory capacity which is used for two-processing-line time interleave process and corresponds to 2*15175680 bits. For example, when the time interleave length I is “4” in the reception mode 3 , the memory capacity of the memory 31 may correspond to the capacity of a memory in one process line used for the four-bit soft decision process in the modulation method 64 QAM, for example, 15175680 bits.
[0041] FIG. 7 illustrates an exemplary memory control circuit. The memory control circuit illustrated in FIG. 7 may be the memory control circuit illustrated in FIG. 3 . The memory control circuit 32 includes a soft-decision-bit-to-be-used number calculation circuit 41 and a bit-to-be-used location specification circuit 42 . The soft-decision-bit-to-be-used number calculation circuit 41 receives first-process-line TMCC information from the TMCC error correction circuit 27 - 1 and second-process-line TMCC information from the TMCC error correction circuit 27 - 2 . The TMCC information includes, for example, information relating to a data modulation method and a time interleave length. The soft-decision-bit-to-be-used number calculation circuit 41 receives information, which indicates the number of combination branches, from the diversity combining specification circuit 34 . The information, which indicates the number of combination branches, includes the number of first-process-line diversity combinations and the number of second-process-line diversity combinations. Examples of the diversity combinations include the case where dual-process-line combination is performed in the first process line and the second process line, the case where three-process-line combination and one-process-line combination are performed in the first process line and the second process line, respectively (or vice versa), and the case where four-process-line combination is performed in either the first process line or the second process line. The soft-decision-bit-to-be-used number calculation circuit 41 receives information, which indicates the number of outputs TS and the number of output lines, from the TS switching instruction circuit 33 . The information includes information which indicates whether or not TSs of the first process line and the second process line are output.
[0042] The soft-decision-bit-to-be-used number calculation circuit 41 determines the number of soft decision bits used for error correction processing based on the information. For example, when a data modulation method used for the first process line has higher noise tolerance than a data modulation method used for the second process line, the number of soft decision bits used for the first process line may be smaller than the number of soft decision bits used for the second process line. For example, when the number of first-process-line diversity combinations is larger than the number of second-process-line diversity combinations, for example, when noise is smaller, the number of soft decision bits used for the first process line may be smaller than the number of soft decision bits used for the second process line. With respect to the first received data and the second received data, the soft-decision-bit-to-be-used number calculation circuit 41 determines the number of soft decision bits respectively based on the validity or the invalidity of a TS output, a data modulation method, a time interleave length, and the number of diversity combinations or the like. The determination may be performed dynamically. The soft-decision-bit-to-be-used number calculation circuit 41 calculates a memory occupation ratio between the first process line and the second process line based on the information. For example, when the hard decision process is performed in 64 QAM, for example, when the number of soft decision bits is “1”, the number of bits assigned to one signal point may be six bits. When the three-bit soft decision process is performed in 16 QAM, the number of bits assigned to one signal point may be 10 bits. For example, in the first process line, six bits may be used for the hard decision process performed in 64 QAM, and, in the second process line, 10 bits may be used for the three-bit soft decision process performed in 16 QAM. The memory occupation ratio may turn out to be 6:10.
[0043] The bit-to-be-used location specification circuit 42 receives the number of soft decision bits in the first process line, the number of soft decision bits in the second process line, and the memory occupation ratio between the first process line and the second process line. The bit-to-be-used location specification circuit 42 outputs a signal which specifies a bit location used for the first process line and a signal which specifies a bit location used for the second process line based on the information.
[0044] FIG. 8 illustrates an exemplary bit location. FIG. 8 may illustrate the memory space of the memory 31 . A longitudinal direction in FIG. 8 corresponds to an interleave length which indicates an address of a memory storage location. A lateral direction in FIG. 8 corresponds to a bit location in one word. One word may correspond to 16 bits. The hard decision information in the first process line is stored in six bits ranging from bit 1 to bit 6 of each word in the memory 31 , the soft decision information in the first process line is stored in four bits ranging from bit 7 to bit 10 , and the hard decision information in the second process line is stored in six bits ranging from bit 11 to bit 16 . At the time of writing data into the memory 31 , bit masking is performed in response to the signal which specifies the bit location used for the first process line and the signal which specifies the bit location used for the second process line. All the data at one signal point used for the four-bit soft decision process in 64 QAM, for example, the hard decision information and the soft decision information may be stored in one word.
[0045] FIG. 9 illustrates an exemplary time de-interleave circuit. FIG. 9 may illustrate connections between the time de-interleave circuit and the memory, both shown in FIG. 3 . Time de-interleave circuits 22 - 1 and 22 - 2 supply address signals and read/write instruction signals to a memory 31 . The time de-interleave circuits 22 - 1 and 22 - 2 specify an address, assert a write instruction, and write one word, for example, 16-bit write data. When a write destination word is occupied by data in one process line, the number of bits at one signal point used for the four-bit soft decision process in 64 QAM may be written. When one write destination word is occupied by data in two process lines, data whose number of bits is smaller than 16 bits is written. The memory 31 is controlled, for example, by the memory control circuit 32 illustrated in FIG. 7 . Write data from the time de-interleave circuit 22 - 1 is bit-masked so that the write data is written at a storage bit location in the first process line. For example, as illustrated in FIG. 8 , the write data from the time de-interleave circuit 22 - 1 may be written into 10 bits ranging from bit 1 to bit 10 . Write data from the time de-interleave circuit 22 - 2 is bit-masked so that the write data is written at a storage bit location in the second process line. The write data from the time de-interleave circuit 22 - 2 may be written into six bits ranging from bit 11 to bit 16 .
[0046] When each of the time de-interleave circuits 22 - 1 and 22 - 2 specifies an address and asserts a read instruction, one word, for example, 16-bit read data, is read out. When one word is occupied by data in one process line, the number of bits at one signal point used for the four-bit soft decision process in 64 QAM is read out. When one word is occupied by data in two process lines, valid bit data is not stored in given bits from among the read-out 16-bit read data. Read data for the time de-interleave circuit 22 - 1 is stored at storage bit locations in the first process line. Bit masking is performed by inserting “0” at other bit locations. Read data for the time de-interleave circuit 22 - 2 is stored at storage bit locations in the second process line. Bit masking is performed by inserting “0” at other bit locations. Data at bit locations at which “0” is inserted may not be used in Viterbi decoding. The memory 31 may be a single-port memory. The time de-interleave circuit 22 - 1 and 22 - 2 may access the memory 31 at different times, respectively.
[0047] FIG. 10 illustrates an exemplary switching process. In FIG. 10 , switching between a two-TS-output configuration and a one-TS-output configuration is performed. FIG. 11 illustrates an exemplary switching process. In FIG. 11 , switching between a two-TS-output configuration and a one-TS-output configuration is performed in 64 QAM. In Operation S 1 illustrated in FIG. 10 , the first process line operates in the one-TS-output configuration. For example, as a bit configuration 50 illustrated in FIG. 11 , six bits from among 16 bits included in one word may be assigned to the hard decision information in the first process line and the remaining 10 bits may be assigned to the soft decision information in the first process line. During time de-interleave process, the time de-interleave circuit 22 - 1 in the first process line writes data into the memory 31 based on the bit configuration 50 illustrated in FIG. 11 . For example, when the four-bit soft decision process in 64 QAM illustrated in FIG. 6 is performed, 16-bit data may be written. The Viterbi decoding circuit 24 - 1 illustrated In FIG. 3 , subsequently coupled to the time de-interleave circuit 22 - 1 , decodes using the four bit-soft decision information.
[0048] In Operation S 2 , whether or not switching to two-TS reception is specified is determined. When switching to two-TS reception is specified, the hard decision information is input to Viterbi decoding in the first process line in Operation S 3 . The Viterbi decoding circuit 24 - 1 uses the hard decision information. When the first process line uses the hard decision information and the soft decision information after the switching, the hard decision information and the soft decision information may be used in Viterbi decoding. In Operation S 4 , the second process line starts an operation and a portion of a part used by the first process line in the memory 31 is yielded to the second process line. For example, as a bit configuration 51 illustrated in FIG. 11 , leading six bits from among 16 bits of one word are assigned to the hard decision information in the first process line, trailing six bits are assigned to the hard decision information in the second process line, and the remaining four bits are assigned to the soft decision information in the first process line. For example, when the three-bit soft decision process in 64 QAM is performed, the number of bits may be 14. When the three-bit soft decision process is performed either in the I axis or the Q axis, process is performed using 10 (=6+(14−6)/2) bits. In the first process line, the three-bit soft decision processing in 64 QAM may be performed either in the I axis or the Q axis using 10 bits, and, in the second process line, hard decision process in 64 QAM may be performed using six bits.
[0049] In Operation S 5 , an operation in the two-TS-output configuration is performed. At the time of time de-interleave process, the time de-interleave circuit 22 - 1 in the first process line writes 10 bits based on the bit configuration 51 illustrated in FIG. 11 . In Viterbi decoding of the Viterbi decoding circuit 24 - 1 , the three-bit soft decision information is used in one of the I axis and the Q axis, and the hard decision information is used in the other axis. At the time of time de-interleave process, the time de-interleave circuit 22 - 2 in the second process line writes six bits based on the bit configuration 51 illustrated in FIG. 11 . In Viterbi decoding of the Viterbi decoding circuit 24 - 2 , the soft decision information is used.
[0050] Storage bit locations of the hard decision information in the first process line and a portion 53 of storage bit locations of the soft decision information in the first process line, illustrated in the bit configuration 50 , are switched to storage bit locations of the hard decision information in the first process line and storage bit locations of the soft decision information in the first process line, illustrated in the bit configuration 51 . Since the hard decision information and the soft decision information, used after the switching, are stored at a certain memory-locations for storing the information used before the switching, the switching may performed seamlessly. The number of bits used in the Viterbi decoding before the switching is preliminarily set to the number of bits used in the Viterbi decoding after the switching, so that seamless switching may be performed.
[0051] In Operation S 6 , whether or not switching to one-TS reception is specified is determined. After switching to one-TS reception is specified, when, in Operation S 7 , whether or not switching to the first process line is performed is determined and the switching to the first process line is performed, the operation in the second process line is halted and a part occupied by the second processing line in the memory 31 is yielded to the first processing line, in Operation S 8 . For example, as the bit configuration 50 illustrated in FIG. 11 , six bits from among 16 bits of one word are assigned to the hard decision information in the first process line and the other 10 bits are assigned to the soft decision information in the first processing line. In Operation 9 , whether or not data in the first process line is accumulated in the memory 31 is determined. Whether or not data corresponding to a part 54 of the soft decision information in the bit configuration 50 illustrated in FIG. 11 is accumulated is determined. In the other part, the information may be accumulated before the switching. When, in Operation S 9 , when data in the first process line is accumulated in the memory 31 , the soft decision information is used in the Viterbi decoding in the first process line, in Operation S 10 . The Viterbi decoding circuit 24 - 1 performs maximum likelihood decision by using all the soft decision information.
[0052] Storage bit locations of the hard decision information in the first process line and a portion 53 of storage bit locations of the soft decision information in the first process line, illustrated in the bit configuration 51 , are switched to storage bit locations of the hard decision information in the first process line and storage bit locations of the soft decision information in the first process line, illustrated in the bit configuration 50 . Since the hard decision information and the soft decision information, used after the switching, are stored at certain memory-locations for storing the information used before the switching, the switching may be performed seamlessly. The number of bits used in the Viterbi decoding before the switching is preliminarily set to the number of bits used in the Viterbi decoding after the switching, so that seamless switching may be performed. After data 54 is accumulated in the memory after the switching, the number of bits is modified for the Viterbi decoding.
[0053] When, in Operation S 7 , when switching to the second process line is performed, the operation in the first process line is halted and a part occupied by the first process line in the memory 31 is yielded to the second process line, in Operation S 11 . For example, as a bit configuration 52 illustrated in FIG. 11 , six bits from among 16 bits of one word are assigned to the hard decision information in the second process line and the other 10 bits are assigned to the soft decision information in the second process line. In Operation 12 , whether or not data in the second process line has been accumulated in the memory 31 is determined. When data in the second process line is accumulated in the memory 31 , the soft decision information is used in the Viterbi decoding in the second process line, in Operation S 13 . The Viterbi decoding circuit 24 - 2 performs maximum likelihood decision using the soft decision information.
[0054] In Operation S 14 , an operation in the one-TS-output configuration is performed in the second process line. Operations S 16 and S 17 may be substantially the same as or similar to Operations S 3 and S 4 .
[0055] FIG. 12 illustrates an exemplary switching process. In FIG. 12 , switching between the two-TS-output configuration and the one-TS-output configuration is performed in 16 QAM. In the one-TS-output configuration, for example, as a bit configuration 60 illustrated in FIG. 12 , four bits from among 16 bits included in one word are assigned to the hard decision information in the first process line and eight bits from among the remaining 12 bits are assigned to the soft decision information in the first process line. For example, when the four-bit soft decision process in 16 QAM illustrated in FIG. 6 is performed, 12-bit data is written. When switching to the two-TS-output configuration is performed, leading four bits from among 16 bits of one word are assigned to the hard decision information in the first process line and trailing four bits are assigned to the hard decision information in the second process line, as a bit configuration 61 . Four bits, one half of the remaining eight bits, are assigned to the soft decision information in the first process line and four bits, the other half of the remaining eight bits, are assigned to the soft decision information in the second process line. For example, as illustrated in FIG. 6 , the number of bits used for two-bit soft decision process in 16 QAM may be eight, for example, four bits, one half of the eight bits, used for hard decision and the other four bits used for soft decision. In the first and second process lines, the two-bit soft decision process in 16 QAM may be performed and 16 bits may be used in units of eight bits. Switching from the two-TS-output configuration to, for example, the one-TS-output configuration in the second process line, illustrated in a bit configuration 62 , is performed. In the bit configuration 62 , for example, four bits from among 16 bits included in one word are assigned to the hard decision information in the second process line and eight bits from among the remaining 12 bits are assigned to the soft decision information in the second process line. For example, the four-bit soft decision process in 16 QAM, whose number of bits is 12 bits, may be performed. The switching illustrated in FIG. 12 may be performed seamlessly.
[0056] FIG. 13 illustrates an exemplary memory ratio switching process. In FIG. 13 , the two-TS-output configuration may be adopted. In Operation S 1 , a reception operation is performed using a current memory ratio. In Operation S 2 , whether or not the memory ratio is switched is determined. For example, when a modulation method is switched, when the number of diversity combinations is switched, or when a time interleave length is switched, the memory ratio may be switched. When the memory ratio is switched, the bit width of input data for Viterbi decoding in a process line in which the memory ratio is reduced is set to a bit width which corresponds to the memory ratio set after the switching in Operation S 3 . For example, in the bit configuration of the first process line corresponding to four-bit for soft decision process in 16 QAM, the number of bits used for soft decision processing in 16 QAM is switched to two bits.
[0057] In Operation S 4 , the memory ratio is switched. In the first and second process lines, bit configurations in the memory 31 are switched. Switching from a configuration in which data in the first process line is stored in 12-bit width and data in the second process line is stored in four-bit width to a configuration in which data in the first process line is stored in four-bit width and data in the second process line is stored in 12-bit width is performed. In Operation S 5 , whether or not data in a process line where the memory ratio is increased is accumulated in the memory is determined. For example, whether or not data increased owing to the switching is accumulated in the memory is determined. When the data is accumulated in the memory, the bit width of input data for Viterbi decoding in a process line where the memory ratio is increased is set to a bit width which corresponds to the memory ratio set after the switching, in Operation S 6 . For example, when the bit configuration in the second process line before the switching corresponds to one-bit for soft decision process in 16 QAM, the bit configuration is switched to the bit configuration corresponding to two-bit for soft decision process in 16 QAM. The number of bits used for soft decision used in the Viterbi decoding in the second process line increases from one bit to two bits.
[0058] De-interleave process in the first process line and de-interleave process in the second process line may be performed seamlessly at the time of the switching. During execution of de-interleave process in the first process line and de-interleave process in the second process line, the number of bits used for the Viterbi decoding is modified and the bit configuration of the memory is switched.
[0059] In terrestrial digital broadcasting, the time interleave length I corresponding to 12 segments may be “2”. In comparison with the time interleave length I which is “4” in the reception mode 3 , the amount of data accumulated may be a half.
[0060] The TMCC information includes information relating to a time interleave length and a data modulation method. When the TMCC information is switched, a transmission parameter switching index included in the TMCC information is sequentially counted down from “1111” one by one. After the transmission parameter switching index reaches “0000”, the TMCC information is switched at the time of returning to “1111”. FIGS. 4A and 4B illustrate a transmission location of the transmission parameter switching index and the content thereof. With respect to the modulation method and the time interleave length or the like, current information and next information are specified. When the transmission parameter switching index is counted down, a parameter to be used next is specified as the next information. For example, the number of bits used for the Viterbi decoding may be decreased based on the next information.
[0061] FIG. 14 illustrates an exemplary receiving system. The receiving system illustrated in FIG. 14 includes an OFDM demodulating circuit. In FIG. 14 , elements which are substantially the same as or similar to elements illustrated in FIG. 1 are assigned with the same numbers and descriptions of the components may be omitted and reduced.
[0062] The receiving system includes antennas 10 - 1 and 10 - 4 , tuners 11 - 1 and 11 - 4 , an OFDM demodulating circuit 112 , decoders 113 - 1 and 113 - 2 , a CPU 114 , displays 115 - 1 and 115 - 2 , and speakers 116 - 1 and 116 - 2 . The tuners 11 - 1 and 11 - 4 receive signals received by the antennas 10 - 1 and 10 - 4 and outputs IF signals. The OFDM demodulating circuit 112 may not include the antennas 10 - 1 and 10 - 4 and the tuners 11 - 1 and 11 - 4 , illustrated in FIG. 1 . The other configuration may be substantially the same as or similar to the configuration illustrated in FIG. 1 . The OFDM demodulating circuit 112 receives the IF signals and outputs OFDM-demodulated digital signals as transport streams TS. The decoders 113 - 1 and 113 - 2 decode the transport streams TS and generate output signals including video signals and audio signals. The CPU 114 controls the OFDM demodulating circuit 112 and the decoders 113 - 1 and 113 - 2 . The displays 115 - 1 and 115 - 2 output video based on the video signals. The speakers 116 - 1 and 116 - 2 output audio based on the audio signals. The receiving system adopts a two-TS output function. The decoders 113 - 1 and 113 - 2 , the displays 115 - 1 and 115 - 2 , and the speakers 116 - 1 and 116 - 2 may be provided.
[0063] The previous aspects of the embodiments may be adapted to a system where a plurality of interleave process sections in a plurality of reception signal process systems share a memory.
[0064] Example embodiments of the present invention have now been described in accordance with the above advantages. It will be appreciated that these examples are merely illustrative of the invention. Many variations and modifications will be apparent to those skilled in the art. | A data receiving circuit includes: a first de-interleave circuit configured to de-interleave first data which is demodulated and is soft-decision-processed; a second de-interleave circuit configured to de-interleave second data which is demodulated and is soft-decision-processed; a memory configured to be shared by the first de-interleave circuit and the second de-interleave circuit and store respective hard decision information and respective soft decision information of the first data and the second data; and a memory control circuit configured to vary a first through fourth number of bits stored in the memory, the first number corresponding to the hard decision information of the first data, the second number corresponding to the soft decision information of the first data, the third number corresponding to the hard decision information of the second data, the fourth number corresponding to the soft decision information of the second data. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for the selective alkylation of the unsubstituted ortho position or positions of phenolic compounds. More particularly, it relates to a process for carrying out the aforesaid alkylation with excellent results and long time stability in the presence of an improved catalyst containing manganese oxide as a main component.
2. Description of the Prior Art
The preparation of 2,6-dimethylphenol, among other ortho-alkylated phenols, has heretofore been the subject of many studies because it is a raw material for the manufacture of polyphenyleneether having a wide range of utility as a heat resisting resin.
Currently, a process for the ortho-alkylation of phenols is in industrial use which involves the vapor phase reaction of a phenol with an alcohol in the presence of an acidic solid catalyst such as alumina. However, in this process, the selectivity in the site of alkylation is insufficient. That is, not only the ortho-positions thereof are subject to alkylation, so that a complicated procedure for the separation and purification of ortho-alkylated reaction products is required.
Another industrial process for the ortho-alkylation of phenol is based on vapor phase reaction in the presence of a magnesium oxide catalyst. However, this catalyst has inherently low activity and requires high temperatures of 475° C. or higher, practically 500° C. or higher, to achieve sufficient reaction.
Moreover, the life of the catalyst is not long enough, so the regeneration procedure must be required in a relatively short period of time for practical use.
In order to solve these problems, there have been proposed many kinds of catalysts, especially those comprising mainly manganese oxide. For example, U.S. Pat. No. 3,971,832 discloses a catalyst comprising mainly trimanganese tetraoxide, Japanese Patent Publication No. 11100/1976 discloses a manganese oxide catalyst which has magnesium oxide or selenium oxide added to it, and Japanese Patent Laid-open No. 32425/1979 discloses the addition of silicon dioxide.
A catalyst comprising mainly manganese oxide has excellent selectivity of ortho-alkylation and high activity; however, the present inventors propose a catalyst disclosed in U.S. Pat. No. 4,227,023 which comprises a mixed oxide of manganese and silicon and one or more additives selected from alkaline earth metals for improving physical strength of the catalyst, and a catalyst disclosed in Japanese Patent Laid-Open No. 76830/1980 which comprises manganese oxide and is treated with alkali metal compound for preventing the depositing of oxygen containing hydrocarbon species onto the surface of the catalyst and for prolonging the service life of the catalyst.
The catalysts exhibit good characteristics as practical catalysts; however, they are still insufficient in effective utilization of alcohols.
The present inventors have undertaken extensive studies for the purpose of overcoming the above mentioned disadvantage in the aforesaid prior art process, and have discovered that mixed metal oxide catalysts with one or more additives included selected from group (A) consisting of germanium oxide, tin oxide and lead oxide are excellent for the improvement of effective utilization of alcohols.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved process for the selective ortho-alkylation of a phenolic compound having at least one ortho-positioned hydrogen atom by catalytically reacting the phenolic compound with an alcohol in the vapor phase.
It is another object of the present invention to provide a catalyst which is available in carrying out the aforesaid selective ortho-alkylation reaction, the catalyst exhibiting not only enhanced catalytic activity and excellent characteristics required for industrial catalysts, such as good shapability and high mechanical strength, but also are excellent for improving the effective utilization of alcohols.
These and other objects of the present invention will become more apparent from the following detailed description and examples.
According to the present invention, there is provided a process for the selective ortho-alkylation of a phenolic compound having at least one ortho-positioned hydrogen atom by catalytically reacting the phenolic compound with an alcohol in the vapor phase wherein the improvement comprises carrying out the reaction in the presence of a catalyst containing manganese oxide, silicon oxide and one or more additives selected from group (A) consisting of germanium oxide, tin oxide and lead oxide, or a catalyst containing manganese oxide, silicon oxide, one or more additives selected from group (A) consisting of germanium oxide, tin oxide and lead oxide, and one or more additives selected from group (B) consisting of alkali metal oxides and alkaline earth metal oxides.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The phenolic compound which is used in the practice of the invention is one having a hydrogen atom in at least one of the ortho positions and can be represented by the formula ##STR1## where R 1 , R 2 , R 3 and R 4 independently represent hydrogen atoms or aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl groups.
Specific examples of the phenolic compound include phenol; o-, m- and p-cresols; 2,3-, 2,4-, 2,5-, 3,4- and 3,5-xylenols; trimethylphenols; tetramethylphenols; n- and iso-propylphenols; n-, iso- and tert-butylphenols; and the like. In addition, phenolic compounds having at least two different alkyl substituent groups on the same aromatic ring are also usable.
The alcohol which is used in the practice of the invention is a saturated aliphatic alcohol having from 1 to 4 carbon atoms. Specific examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and the like.
The catalyst which is used in the process of the invention surely contains manganese oxide and silicon oxide and is suitably present in such proportion as to provide an atomic ratio of manganese to silicon ranging from 100:0.01 to 100:20 and preferably from 100:0.05 to 100:10.
The catalyst which is used in the process of the invention contains manganese oxide, silicon oxide and one or more additives selected from group (A) consisting of germanium oxide, tin oxide and lead oxide. Said additives selected from group (A) are suitably present in such proportion as to provide a metal atomic ratio of manganese oxide to said additives ranging from 100:1 to 100:50 and preferably from 100:0.3 to 100:30.
When the catalyst further contains one or more additives selected from group (B) consisting of alkali metal oxides and alkaline earth metal oxides, said additives are present in such proportion as to provide an atomic ratio of manganese to alkaline earth metals ranging from 100:0.01 to 100:30 and preferably 100:0.05 to 100:20, and an atomic ratio of manganese to alkali metals ranging from 100:10 -4 to 100:5 and preferably from 100:10 -3 to 100:1.
The role of an alkaline metal oxide in this invention is one of mainly providing moldability as a practical catalyst, in other words, the moldability of the catalyst is improved while maintaining the selectivity of obtaining ortho-alkylated phenols based on phenols and alcohols at high level.
On the other hand, the role of an alkali metal oxide is mainly one of suppressing the decomposition of alcohols, which is useless for objective reaction, and reducing the deposition of hydrocarbons produced by reaction of organic materials onto the surface of the catalyst and prolonging the service life of the catalyst.
As raw materials of various metal oxides which are used in this invention, derivatives of each metal, such as hydroxides, carbonates, salt of various mineral acids, salt of organic acids, in some cases sulfide, hydride and the like, may be used.
A number of methods are available for the preparation of the catalyst. For example, it may be prepared either by adding a small amount of water to a mixture of various compounds as described above and blending the mixture well in a kneader or mixer, or by adding a suitable basic component to an aqueous solution of various raw materials and obtaining the coprecipitated insoluble products. It is also possible to form a mixture of some component first and then the remaining components are added by dipping or mixing. Usually, the resulting catalyst is dried at a temperature below 150° C., and suitable additives or processing aids are added such as polyvinyl alcohol, microcrystallite cellulose, and the like, if desired, and formed into any desired shape by a suitable technique such as extrusion, compression molding, vibration, rolling, or the like, and then calcined to make it ready for use.
In carrying out the process of the invention, a phenolic compound and an alcohol are mixed in a molar ratio ranging from 1:1 to 1:15 and preferably from 1:1 to 1:6. Prior to being fed the reactants to the reaction zone, these starting materials may be diluted with a suitable inert gas such as nitrogen or carbon dioxide to make the reaction proceed smoothly. Furthermore, it is also effective to introduce a small amount of water with the reactants into the reaction zone. The presence of such water serves not only to prolong the service life of the catalyst but also to suppress any undesirable decomposition of the alcohol.
The process of the invention is carried out at a temperature of from 300° C. to 550° C. and preferably from 350° to 500° C. If the reaction temperature is higher, the selectivity for ortho-alkylation is reduced and the formation of various high-boiling products is increased. On the other hand, if the reaction temperature is lower, the conversion of the reactants is insufficient for the practical use, as a result, great amounts of unreacted starting materials or intermediate products must be recovered and recycled.
The reactants are preferably fed to the reaction zone at a liquid space velocity of from 0.1 to 12 per hour. Generally speaking, greater liquid space velocities are suitably used for the reactions of higher temperature, and vice versa. The reaction may be carried out under a pressure high or lower than atmospheric pressure. The reaction may be carried out according to any of the fixed bed, fluidized bed, and moving bed processes.
The present invention is further illustrated by the following examples.
EXAMPLE 1
One thousand g of manganese nitrate hexahydrate was heated to 40° C. On the other hand, 21 g of water glass No. 3 was diluted with 100 ml of water and then added drop by drop to the above manganese solution. The resulting manganese nitrate solution was diluted with 5,000 ml of water, and aqueous ammonia was added thereto, whereby a precipitate of manganese oxide containing silica was formed. Then 10 g of germanium dioxide was added thereto. After sufficient mixing, the mixture was washed with water, filtered and then dried at 180° C. for 8 hours. The dried filter cake was ground and molded by compression into cylindrical pellets having a diameter of 18 mm and a height of 3.2 mm. After the pellets were burnt at 500° C., 100 g of them were packed into a stainless steel tubular reactor having an internal diameter of 21 mm.
Alkylation of phenol with methanol was carried out according to the following procedure.
A mixture of phenol and methanol (in a molar ratio of 1:5) was gasified passing through the carburetor at a controlled temperature of 230° C., and then introduced into the reactor, the internal temperature of which was kept at 425° C., at a rate of 40 g per hour.
The reaction products were analyzed by gas chromatography. The results are summarized in Table 1. The rate of methanol effective utilization is calculated according to the following formula. ##EQU1##
EXAMPLE 2
A catalyst consisting of manganese oxide, silicon oxide and tin oxide was prepared in the same manner as described in Example 1 except that the germanium dioxide was replaced by tin oxalate. (with a Mn:Si:Sn atomic ratio of 100:2.9:5.0).
And the reaction was carried out in the same manner as described in Example 1. The results are shown in Table 1.
EXAMPLE 3
A catalyst consisting of manganese oxide, silicon oxide, tin oxide and calcium oxide was prepared as described in Example 2 except that calcium hydroxide was further added with tin oxalate. (with a Mn:Si:Sn:Ca atomic ratio of 100:2.9:5.0:1.0)
And the reaction was carried out in the same manner as described in Example 1. The results are shown in Table 1. After 400 hours continuation of reaction, the pelletized catalyst was taken out of the tubular reactor, and almost no pellets were damaged in shape.
EXAMPLE 4
One hundred g of the pelletized catalyst prepared in Example 1 was dipped into 0.01 N of potassium hydroxide aqueous solution, whereby a catalyst treated with potassium was prepared. (with a Mn:Si:Ge:Ca atomic ratio of 100:2.9:2.7:0.003)
And the reaction was carried out under the same conditions as described in Example 1. The results are shown in Table 1.
EXAMPLE 5
A catalyst treated with potassium was prepared as described in Example 4 using the pelletized catalyst prepared in Example 3. (with a Mn:Si:Sn:Ca:K atomic ratio of 100:2.9:4.8:1.1:0.003)
And the reaction was carried out under the same conditions as described in Example 1. The results are shown in Table 1.
EXAMPLE 6
A catalyst consisting of manganese oxide, silicon oxide and lead oxide was prepared in the same manner as described in Example 1 except that the germanium dioxide was replaced by lead dioxide. (with a Mn:Si:Pb atomic ratio of 100:2.9:1.4)
And the reaction was carried out under the same conditions as described in Example 1. The results are shown in Table 1.
TABLE 1__________________________________________________________________________ Hours afterComposition of Initiation Phenols in Products (mol %) Rate of MethanolExampleCatalyst of 2,4,6-Trimethyl- Effective UtilizationNo. (Atomic Ratio) Reaction Phenol o-Cresol 2,6-Xylenol phenol (%)__________________________________________________________________________1 Mn:Si:Ge = 10 0.2 5.0 92.1 2.5 60100:2.9:2.7 100 0.8 5.3 91.0 2.0 582 Mn:Si:Sn = 10 1.0 7.8 90.1 1.0 65100:2.9:5.0 100 3.0 9.0 87.0 0.5 633 Mn:Si:Sn:Ca = 100 0.5 4.0 93.0 2.3 63100:2.9:5.0:1.0 200 0.9 6.2 91.5 1.0 60 300 1.5 8.0 89.0 1.0 614 Mn:Si:Ge:Ca = 50 0.3 5.1 90.9 2.7 59100:2.9:2.7:0.003 200 0.8 6.0 90.1 2.4 58 400 1.0 6.9 88.9 2.0 585 Mn:Si:Sn:Ca:K = 50 0.1 2.0 95.7 2.1 64100:2.9:5.0:1.0: 200 0.5 3.1 93.2 2.3 620.001 400 1.0 4.2 91.9 2.0 626 Mn:Si:Pb = 10 1.1 9.3 86.9 2.5 69100:2.9:1.4 100 1.3 13.5 83.0 1.9 64__________________________________________________________________________
COMPARATIVE EXAMPLE
A catalyst consisting of manganese oxide and silicon oxide was prepared in the same manner as described in Example 1 except that the germanium oxide was not used. And the reaction was carried out in the same manner as described in Example 1 except that the reaction temperature was changed to 430° C. The results are shown in Table 2.
TABLE 2______________________________________ Rate ofPhenols in Products (mol %) Methanol 2,4,6,-Tri- EffectivePhe- o- 2,6- methyl- Utilizationnol Cresol Xylenol phenol (%) Note______________________________________0.5 3.0 94.3 1.5 53 10 hours after initiation of reaction1.0 5.1 91.5 1.4 50 100 hours after initiation of reaction2.5 11.0 85.0 1.1 49 200 hours after initiation of reaction The shape of about 10 to 20% of pelletized catalyst was damaged at 300 hours after initiation of reaction.______________________________________ | This invention relates to a process for the selective ortho-alkylation of a phenolic compound having at least one ortho-positioned hydrogen atom by catalytically reacting the phenolic compound with an alcohol in the vapor phase. In this process, the reaction of the phenolic compound with the alcohol is carried out at a temperature of from 300° to 550° C. in the presence of a catalyst containing manganese oxide, silicon oxide and one or more additives selected from group (A) consisting of germanium oxide, tin oxide and lead oxide, or a catalyst containing manganese oxide, silicon oxide, one or more additives selected from the aforesaid group (A), and one or more additives selected from group (B) consisting of alkali metal oxides and alkaline earth metal oxides. The catalyst used in this invention exhibits not only excellent catalytic activity in the selective ortho-alkylation of phenols, continuous stability of the activity, good shapability, and good mechanical strength but also effective utilization of alcohols. | 1 |
BRIEF DESCRIPTION OF THE FIGURES
[0001] FIG. 1 shows a partially schematic diagram of an environment(s) and/or an implementation(s) of technologies described herein.
DETAILED DESCRIPTION
[0002] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.
[0003] With reference now to the Figures and with reference now to FIG. 1 , FIG. 1 shows a partially schematic diagram of an environment(s) and/or an implementation(s) of technologies described herein. FIG. 1 depicts atypical person 100 resident within the confines of Room 101 of the Cato Institute. FIG. 1 illustrates that Room 101 of the Cato Institute is surveilled by camera 102 , where camera 102 has an associated identifier (e.g., name) of “Skynet Security Camera Alpha.”
[0004] FIG. 1 illustrates that Camera-to-Obscure Co. Circuitry 104 creates a pseudo-public-private key pair. FIG. 1 shows that Camera-to-Obscure Co. Circuitry 104 transmits Camera-to-Obscure Co. generated Pseudo-Public Key to
[0005] Skynet Name Obscuring Unit 106 . FIG. 1 depicts that the output of Skynet Name Obscuring Unit 106 is “Encrypted-Camera-ID” which is a string that results from encrypting “Skynet Security Camera Alpha” with the pseudo-public key delivered to Skynet Name Obscuring Unit 106 by Camera-to-Obscure Co. Circuitry 104 . FIG. 1 further depicts that Camera-to-Obscure Co. Circuitry 104 transmits Camera-to-Obscure Co. generated Pseudo-Private Key to FBI Name DE-Obscuring Circuitry 136 , which as show herein, in one implementation, will subsequently attempt to unlock various received encrypted names by trying to decrypt the received encrypted names via trying various pseudo-private keys on the FBI Name DE-Obscuring Circuitry 136 's private key chain until the encrypted name is unlocked; that is, in a fashion analogous to a human trying similar looking keys on his key chain to find the key that opens the front door to his house. In other implementations FBI Name DE-Obscuring Circuitry 136 uses a Unique Camera-to-Obscure Co. Key pair designator (not shown), analogous to the ways unique key pair designators are used as described elsewhere herein with respect to, for example, the pseudo-public-private key pairs respectively generated by Cyberdine Protective Services and Heuristic Algorithm Services such as described herein; such alternate implementations for the FBI Name DE-Obscuring Circuitry 136 that use a Unique Camera-to-Obscure Co. Key pair designator are not shown in the drawings for sake of clarity but can be understood in light of at least the reference examples herein.
[0006] FIG. 1 illustrates that Skynet Name Obscuring Unit 106 transmits output—“Encrypted-Camera-ID”—which is the string that is the result of encrypting “Skynet Security Camera Alpha” with the pseudo-public key of the pseudo-public-private key pair generated by Camera-to-Obscure Co. circuitry 104 —plus a date and time window for which “Encrypted-Camera ID” is good (e.g., Jun. 16, 2014 from 10:00 a.m. to 11:00 a.m.) to Skynet Level One Encryption Circuitry 110 . In some implementations, the date and time is optional, and Skynet Level One Encryption Circuitry 110 just appends the appropriate date and time during which CCD output 112 is received from camera 102 .
[0007] FIG. 1 shows that in one implementation CCD output 112 from camera 102 feeds—via a hardwired connection—directly into Skynet Level One Encryption Circuitry 110 as a stream—not a frame. Thus, in one implementation such as illustrated herein, at no point can camera 102 's output be intelligibly accessed until/unless several different legal entities—controlling very different encryption/decryption automation the keys to which encryption/decryption are at no time held by a single party who can decrypt and see the camera output—work in a transparent and coordinated fashion.
[0008] FIG. 1 shows atypical person 100 (e.g., one with an alternative lifestyle) who just wants to be left alone but is aware that camera 102 —“Skynet Security Camera Alpha”—is surveilling Room 101 of the Cato Institute where atypical person 100 is resident. Accordingly, atypical person 100 is depicted as saying “respect my privacy, and keep your intrusive cameras off my body!”
[0009] In one implementation, the public safety is served by constant camera surveillance of Room 101 of the Cato Institute, but atypical person 100 has legitimate concerns as to how such surveillance data might be used. To allay atypical person 100 ′s concerns, illustrated is that CCD output 112 of camera 102 is clocked directly into Skynet Level One Encryption Circuitry 110 as a stream (e.g., such that it can't typically be viewed as video data), which in one implementation immediately encrypts the stream of CCD output 112 using a pseudo-public key generated by Cyberdine-Protective-Services Key-Pair Generation Automation 114 .
[0010] Continuing to refer to FIG. 1 , illustrated is that Cyberdine-Protective-Services Key-Pair Generation Automation 114 creates pseudo-public-private key pairs. Shown is that Cyberdine-Protective-Services Key-Pair Generation Automation 114 delivers the pseudo-public key along with a Unique Cyberdine-Protective-Services Key Pair Designator to Skynet Level One Encryption Circuitry 110 (as show herein Unique Cyberdine-Protective-Services Key Pair Designator will ultimately be utilized to coordinate the pseudo-public and pseudo-private keys by two different and unique legal entities; that is, the unique designator will allow different entities, which are “blind” to the pairing of the pseudo-public and pseudo-private keys, to subsequently use the correct pseudo-private key to decrypt that which was encoded with the corresponding pseudo-public key). Skynet Level One Encryption Circuitry 110 is depicted as under the legal control and administration of Skynet Security Company.
[0011] FIG. 1 shows that Cyberdine-Protective-Services Key-Pair Generation Automation 114 delivers the pseudo-private key along with a unique Cyberdine-Protective-Services Key Pair Designator which serves to identify the pseudo-public-private key pair of which the pseudo-private key forms a part to Federal Bureau of Investigation (“FBI”) Level One DEcryption Circuitry 130 .
[0012] FIG. 1 illustrates that while Cyberdine Protective Services has legal control and administration of both keys of the pair, as well as the Cyberdine-Generated Unique Key Pair Designator which serves to identify/coordinate the key pair, Cyberdine Protective Services does not have access to CCD output 112 of camera 102 . FIG. 1 shows that when Skynet Level One Encryption Circuitry 110 encrypts CCD output 112 of camera 102 with the Cyberdine-Security-Services generated pseudo-public key, Skynet has no legal control, administration, or possession of the corresponding Cyberdine-Security-Services generated pseudo-private key which could be used to unlock the encryption of CCD output 112 of camera 102 that was/is instantiated by Skynet Level One Encryption Circuitry 110 . Cyberdine-Protective-Services Key-Pair Generation Automation 114 is depicted as under the legal control and administration of Cyberdine Protective Services Company which is separate and apart from Skynet Security Company.
[0013] FIG. 1 illustrates that the system ensures that Skynet Security Company cannot see any image because it only holds the pseudo-public key of a pseudo-public-private key pair that has been generated by another legal entity, Cyberdine Protective Services Company.
[0014] FIG. 1 shows that, in one implementation, Skynet Level One Encryption Circuitry 110 , after receipt of “Encrypted-Camera-ID” which is the string that is result of encrypting “Skynet Security Camera Alpha” plus a date and time window for which “Encrypted-Camera ID” is good (e.g., Jun. 16, 2014 from 10:00 a.m. to 11:00 a.m.) from Skynet Name Obscuring Unit 106 , encrypts CCD output 112 of camera 102 that occurred on Jun. 16, 2014 from 10:00 a.m. to 11:00 a.m. via the pseudo-public key of the pseudo-public-private key pair generated by Cyberdine Protective Services Company. Thereafter, illustrated is that Skynet Level One Encryption Circuitry 110 associates the Level One encryption of CCD output 112 of camera 102 with meta-data composed of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator.”’ In the instance shown, the “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ meta-data is kept outside the Level One encryption applied by Skynet Level One Encryption Circuitry 110 , but those skilled in the art will appreciate that in other implementations all or part of such meta-data may be emplaced inside the Level One encryption.
[0015] FIG. 1 shows that, subsequently, Skynet Level One Encryption Circuitry 110 sends Level One encrypted CCD output 118 , and its associated meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ to Skynet Level Two Encryption Circuitry 120 . FIG. 1 depicts that upon receipt of Level One Encrypted CCD output 118 , Skynet Level Two Encryption Circuitry 120 encrypts the received Level One Encrypted CCD output 118 as well as its associated meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ using a pseudo-public key of a pseudo-public-private key pair that has been generated by another legal entity, Heuristic-Algorithm Services, thus creating a Level Two encryption of Level One Encrypted CCD output 118 . With reference now back to CCD output 112 of camera 102 at this point FIG. 1 shows that the Level Two encryption of Level One Encrypted CCD output 118 is a doubly-encrypted version of CCD output 112 of camera 102 .
[0016] FIG. 1 illustrates that the system ensures that Skynet Level Two Encryption Circuitry 120 can only encrypt because it holds only the pseudo-public key of a pseudo-public-private key pair that has been generated by yet another legal entity, Heuristic-Algorithm Services. FIG. 1 shows that Heuristic-Algorithm Services also generates a “Unique Heuristic-Algorithm-Services Key Pair Designator” that will subsequently be used to “pair” the correct pseudo-private key with the correct pseudo-public key by separate legal entities that are effectively “blind” to the pairing done by Heuristic-Algorithm Services. As shown herein, the pseudo-public-private key pairs and the Unique Heuristic-Algorithm-Services Key Pair Designator are generated by Heuristic-Algorithm-Services Key Pair Generation Automation 127 , which is under the legal control and administration of Heuristic-Algorithm Services Company.
[0017] Illustrated is that Skynet Security Level Two Encryption Circuitry 120 thereafter associates the meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Heuristic-Algorithm-Services Key Pair Designator”’ with the Level Two Encrypted CCD output 121 .
[0018] Thereafter, illustrated is that Skynet Security Level Two Encryption Circuitry 120 sends the Level Two encrypted CCD output 121 , having associated meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10 a.m.-11:00 a.m.” +“Unique Heuristic-Algorithm-Services Key Pair Designator”’ to PreCrime Repository 122 .
[0019] Shown is that PreCrime Repository Double-Locked Box Storage Engine 124 receives the Level Two Encrypted CCD Output 121 , having associated meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10 a.m.-11:00 a.m.”+“Unique Heuristic-Algorithm-Services Key Pair Designator”’ which is then stored as a doubly-encrypted CCD output lockbox indexed by some or all of its meta-data (e.g., indexed by some or all of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10 a.m.-11:00 a.m.”+“Unique Heuristic-Algorithm-Services Key Pair Designator”’). In alternate implementations Level Two Encrypted CCD Output 121 is indexed by “Encrypted-Camera-ID” alone, while in other alternate implementations the Level Two encrypted data is indexed by “Unique Heuristic-Algorithm-Services Key Pair Designator” alone, but FIG. 1 shows meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Heuristic-Algorithm-Services Key Pair Designator”’ being used to index for sake of clarity.
[0020] It is expected that, in a free society in most instances the doubly-encrypted version of CCD output 112 of camera 102 (e.g., Level Two Encryted CCD Output 121 ) will never be retrieved and decrypted. That said, it is expected that in some instances public safety might demand that the doubly-encrypted version of CCD output 112 of camera 102 be retrieved and decrypted. For sake of illustration, such an example will now be discussed.
[0021] Referring now to the lower left corner of FIG. 1 , FIG. 1 depicts, for sake of example, Judge Judy acting subsequent to the event of a crime (e.g., a terrorist attack) committed in the vicinity of Room 101 of the Cato Institute at some time between 10:00 a.m. and 10:45 a.m. on Jun. 16, 2014. FIG. 1 illustrates the Department of Justice asking 160 Judge Judy to issue an order for the unlocking of the camera output from 10:00 a.m. and 10:45 a.m. on Jun. 16, 2014 that is associated with a view of Room 101 of the Cato Institute at the time in question. At this point, neither the Department of Justice nor Judge Judy has a name identifying the camera in question. In response, FIG. 1 shows Judge Judy's machine 166 asking 162 the Department of Treasury Encrypted Camera ID+Camera Location Repository Circuitry 163 (Camera-to-Obscure Co and/or Skynet Security Company is shown as having delivered such information to Treasury at or around the time of such output's creation) for the “Encrypted-Camera-ID” that is associated with the camera that was viewing Room 101 of the Cato Institute on the date of Jun. 16, 2014, between the times of 10:00 a.m. and 10:45 a.m.
[0022] In response, FIG. 1 shows the Department of Treasury Encrypted Camera ID+Camera Location Repository Circuitry 163 transmitting 164 to Judge Judy's machine 166 the “Encrypted-Camera-ID” that is associated with the camera at Room 101 of the Cato Institute for the date of Jun. 16, 2014, between the times of 10:00 a.m. and 10:45 a.m. (e.g. the output of camera 102 from 10:00 a.m. to 11:00 a.m. that the system stored). FIG. 1 depicts that Skynet Name Obscuring Unit 106 is shown as having transmitted to Department of Treasury Encrypted Camera ID+Camera Location Repository Circuitry 163 the “Encrypted-Camera-ID” that is associated with the camera having geographic location of Room 101 of the Cato Institute for the date of Jun. 16, 2014, and between the times of 10:00 a.m. and 11:00 a.m. at or around the time “Encrypted Camera ID” was created. That is, at some point prior to Judge Judy's machine 166 making the request.
[0023] FIG. 1 depicts that, subsequent to receiving “Encrypted-Camera-ID” that is associated with the camera that was surveilling Room 101 of the Cato Institute on the date of Jun. 16, 2014, and between the times of 10:00 a.m. and 11:00 a.m. (the encrypted envelope that holds the time of interest of 10:00 a.m. to 10:45 a.m.), Judge Judy's machine 166 transmits to Department of Justice Machine 168 an order directing that the output of “Encrypted-Camera-ID” associated with the camera at Room 101 of the Cato Institute for the date of Jun. 16, 2014, between the times of 10:00 a.m. and 11:00 a.m. be unlocked. FIG. 1 illustrates that Department of Justice Machine 168 transmits messages to Homeland Security Doubly-Encrypted Lockbox Retrieval Circuitry 180 , Homeland Security Level Two DEcryption Circuitry 128 , and FBI Level One DEcryption Circuitry 130 directing the retrieval and/or unlocking of the doubly-encrypted lockbox associated with “Encrypted-Camera-ID” for the date of Jun. 16, 2014, between the times of 10:00 a.m. and 11:00 a.m.
[0024] Referring now to the approximate middle-right portion of FIG. 1 , FIG. 1 illustrates that, in response to Judge Judy's order the content of which was relayed through the message of Department of Justice Machine 168 , Homeland Security Doubly-Encrypted Lockbox Retrieval Circuitry 180 asks PreCrime Repository Circuitry 122 for the files indexed by “‘Encrypted-Camera-ID”; “Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”’ More specifically, FIG. 1 shows that Homeland Security Doubly-Encrypted Lockbox Retrieval Circuitry 180 transmits a request for the double-encrypted lockbox files having index of “Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10 a.m.-11:00 a.m.”' to PreCrime Repository Doubly-Encrypted CCD Output Retriever Engine 126 .
[0025] FIG. 1 depicts PreCrime Repository Doubly-Encrypted CCD Output Retriever Engine 126 pulling the doubly-encrypted files indexed by ‘“Encrypted-Camera-ID”+Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.+“Unique Heuristic-Algorithm Services Key Pair Designator”’ from within PreCrime Repository 122 . FIG. 1 illustrates that thereafter PreCrime Repository Doubly-Encrypted CCD Output Retriever Engine 126 sends Level Two Encrypted CCD output 121 along with the associated meta-data of “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Heuristic-Algorithm Services Key Pair Designator”’ to Homeland Security Level Two DEcryption Circuitry 128 , which, in view of Judge Judy's order, upon receipt decrypts the received Level Two Encrypted CCD output 121 with the correct pseudo-private key generated by Heuristic Algorithm Services. In one implementation, Homeland Security Level Two DEcryption Circuitry 128 is able to retrieve the correct pseudo-private key to do the decryption via use of Unique Heuristic-Algorithm-Services Key Pair Designator which was previously delivered—by Heuristic-Algorithm Services Key-Pair Generation Automation 127 —to Homeland Security Level Two DEcryption
[0026] Circuitry 128 in association with the pseudo-private key that unlocks the corresponding pseudo-public key that was previously used by Skynet Level Two Encryption Circuitry 120 to encrypt as described herein. Thus, in one implementation Unique Heuristic-Algorithm-Services Key Pair Designator is used to retrieve the correct decryption key, even though the decryptor never had possession/control of the Heuristic-Algorithm pseudo-public key that was used to encrypt.
[0027] FIG. 1 shows that Homeland Security Level Two DEcryption Circuitry 128 uses the pseudo-private encryption key of Heuristic-Algorithm Services that is identified by Unique Heuristic-Algorithm-Services Key Pair Designator—which accompanies the doubly encrypted lockbox as meta-data—to undo the Level Two encryption that was previously instantiated by Skynet Level Two Encryption Circuitry 120 . Depicted is that in one implementation the decryption yields the Level-Two Decrypted-Level One Encrypted CCD output data 129 (e.g., the Level Two Decryption applied by Skynet Level Two Encryption Circuitry 120 has been unlocked but the data is still encrypted via the Level One encryption previously applied by Skynet Level One Encryption Circuitry 110 ) and further depicted is that the decryption done by Homeland Security Level Two Decryption Circuitry 128 —accomplished via retrieval of the correct key identified by the Unique Heuristic-Algorithm Services Key Pair Identifier—also provides as output the successful decryption of the Unique Cyberdine-Protective-Services Key Pair Designator (which as shown herein had previously been encrypted by Skynet Level Two Encryption Circuitry 120 ). FIG. 1 depicts that thereafter Homeland Security Level Two DEcryption Circuitry 128 associates as meta-data ‘“Encrypted-Camera-ID?+Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ with the Level-Two Decrypted-Level One Encrypted CCD output data 129 (which is still encrypted via the level one encryption previously applied by Skynet Level One Encryption Circuitry 110 ). FIG. 1 illustrates that Homeland Security Level Two DEcryption Circuitry 128 thereafter sends the meta-data “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time: 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ in association with the with the Level Two Decrypted-Level One Encrypted CCD output data 129 (which is still encrypted via the level one encryption previously applied by Skynet Level One Encryption Circuitry 110 ) to FBI Level One Decryption Circuitry 130 .
[0028] FIG. 1 shows that, FBI Level One DEcryption Circuitry 130 receives the meta-data “‘Encrypted-Camera-ID”+“Date: Jun. 16, 2014; Time 10:00 a.m.-11:00 a.m.”+“Unique Cyberdine-Protective-Services Key Pair Designator”’ in association with the Level-Two Decrypted-Level One Encrypted CCD output data 129 (which is still encrypted via the level one encryption previously applied by Skynet Level One Encryption Circuitry 110 ). FIG. 1 depicts that FBI Level One DEcryption Circuitry 130 determines that Judge Judy's order, as related through the message of Department of Justice Machine 168 , indicates that the data associated with “Encrypted-Camera-ID” is to be unlocked. Accordingly, FIG. 1 illustrates that FBI Level One DEcryption Circuitry 130 uses the received Unique Cyberdine-Protective-Services Key Pair Designator to retrieve the correct Cyberdine-Protective-Services pseudo-private key that corresponds to the Cyberdine-Protective-Services pseudo-public key that Skynet Level One Encryption Circuitry 110 used to encrypt CCD Output 112 . FIG. 1 shows that FBI Level One DEcryption Circuitry 130 uses the retrieved Cyberdine-Protective-Services pseudo-private key to unlock the Level One encryption. Thus, FIG. 1 shows FBI Level One DEcryption Circuitry 130 outputting doubly-decrypted CCD output 132 (e.g., the in-the-clear stream of CCD output 112 of camera 102 ).
[0029] FIG. 1 depicts that Stream-to Viewable-CCD Output Conversion Circuitry 134 converts the stream to viewable CCD output (e.g., still or motion image frames) which is securely displayed in Judge Judy's chambers. Depicted is that for an additional level of citizen's right's protection, “Encrypted-Camera-ID” is sent by FBI Level One DEcryption Circuitry 130 to FBI Name DE-Obscuring Circuitry 136 which then, using a pseudo-private key of a pseudo-public-private key pair generated by software created by Camera-to-Obscure Co., decrypts “Encrypted-Camera-ID” to “Skynet Security Camera Alpha” which is then used by Stream-to Viewable-CCD Output Conversion Circuitry 134 to associate the name of the camera with the viewable CCD output.
[0030] FIG. 1 illustrates Judge Judy in her Chambers viewing the output of “Skynet Security Camera Alpha” Video of 10:00 a.m. to 10:45 a.m. that was captured on Jun. 16, 2014. Depicted is that Judge Judy determines that atypical person 100 has done nothing wrong, and concludes that the Department of Justice need not see the output. Thus, FIG. 1 shows Judge Judy denying the Department of Justice's request to see the output of the camera viewing Room 101 of the Cato Institute for the date of Jun. 16, 2014 and time from 10:00 a.m. to 10:45 a.m.
[0031] Thus as shown herein, atypical citizen 100 's rights to privacy, as well as the public's right to safety, are thus protected and/or balanced by the disclosed technologies.
[0032] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims. | A method substantially as shown and described the detailed description and/or drawings and/or elsewhere herein. A device substantially as shown and described the detailed description and/or drawings and/or elsewhere herein. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 60/337,305, filed on Nov. 5, 2001, which is expressly incorporated by reference as though fully set forth herein.
FIELD OF THE INVENTION
[0002] The present invention relates to roofing systems, and in particular to a composite shingle, a method of manufacture, a method of packaging, and a method of installation thereof.
BACKGROUND OF THE INVENTION
[0003] Conventional roof coverings for sloped roofs include composite shingles, cedar shingles, wooden shakes, sheet metal, slate, clay and concrete tile. Sheet metal, clay and slate are advantageous because of their high weatherability. One of the problems with clay tile and slate roofs is that the clay and slate tiles require significant labor to apply. The composite or wood shingles are nailable and are simply nailed to a roof deck in courses, usually from the bottom or eave to the top or ridge of the roof. Clay, concrete and slate tiles are heavier than composite shingles, and require more support to hold up the roof. The installed cost of clay and slate tiles exceeds that of composite shingles. Clay and slate tiles are inherently fragile, and suffer much breakage during shipping and installation. These materials are fragile even after installation on the roof, and can be damaged by foot traffic on the roof.
[0004] Wooden shingles and shakes are generally flat boards, usually of cedar or other coniferous trees. A cedar shingle is generally ⅜″ thick and a wooden shake is generally ⅝″ thick. The wooden shingles or shakes are nailed in courses on the roof deck, with the exposed or tab portions of the shingles of a subsequent course being laid over the headlap portions of the previous course of shingles. The shingles are cut so that the wood grain runs up the slope of the roof for an aesthetically pleasing appearance. The cutting of the wood, and the subsequent weathering of the shingles after installation on the roof create grooves and ridges running in the direction of the wood grain.
[0005] One of the desirable attributes of any roofing material is to be able to resist fires. This is particularly true in regions having a hot and dry climate, although fire resistance is desirable everywhere. A particularly important aspect of fire resistance is the ability of the roofing material to prevent a fire from burning through the roofing material to thereby expose the roof deck or interior of the building to the fire. Metal roofs and clay and tile roofs have inherent advantages in fire resistance over wood shingle roofs. Composite shingles are sufficiently fire resistant to obtain a Class A fire rating when measured by appropriate tests. Wooden shingles, even when treated with a fire retardant material, are not generally fire resistant and cannot achieve a Class A fire rating. From a fire resistance perspective, a disadvantage of wooden shingles is that they must be applied in a spaced-apart arrangement to allow room for expansion. Because of the propensity of wooden shingles to absorb water, they also tend to curl and not remain flat on the roof. Wood shingles are particularly prone to failing the fire tests because of the gaps between adjacent shingles Because of fire safety concerns, in some jurisdictions it is now illegal to install any roof with less than a Class A rating, including all currently available wooden shingle roof materials.
[0006] For historical reasons, composite shingles are also often referred to as asphalt shingles even if modem composite shingles do not contain asphalt. Manufacturers of composite shingles have, for many years, endeavored to produce shingles that resemble natural materials in appearance. Typical materials that manufacturers have sought to have composite shingles resemble are natural slate tiles and cedar shingles. Techniques that manufacturers have employed have included applying an overlay to the shingle, or making a multiple-layered or laminated shingle. Such shingles are typically manufactured in a variety of weights and colors.
[0007] Improvements in shingle manufacturing have been subtle, often being devoted to the simulation of wood or other natural appearing shingles, having natural appearing textures. Some approaches have been toward applying granules of various color configurations. Other developments have applied shadow bands to give the appearance of depth at various locations along the shingles. Still other techniques have involved irregular cuts in the buttlap portion of the shingles, in an attempt to give a scalloped or random appearance.
[0008] Attempts have been made to produce more irregular surface contours, which would give the shingle a bulkier appearance. Examples of such composite shingles are shown in U.S. Pat. No. 2,099,131 to Miller; U.S. Pat. No. 5,094,058 to Slocum; and D369,421 to Kiik, et al. The complete disclosures of these patents are herein incorporated by reference.
[0009] Various composite shingles have been developed in an attempt to provide an appearance of thickness comparable to wood shingles. Examples of such composite shingles are shown in U.S. Pat. No. 3,921,358 to Bettoli; U.S. Pat. No. 4,717,614 to Bondoc, et al.; U.S. Pat. No. 5,232,530 to Malmquist, et al.; and U.S. Pat. Des. No. 309,027 to Noone, et al. The complete disclosures of these patents are herein incorporated by reference.
[0010] In U.S. Pat. No. 4,352,837 to Kopenhaver, an overlay is taught, whereby, a first single layer of shingle is made, comprised of a mat, asphalt, and granules on an upper surface. The first single layer thus made receives an overlay in the form of an additional partial coating of asphalt, which in turn, receives additional granules thereon, creating localized areas of additional thickness on the shingle, with such areas of additional thickness having an ornamentation appearance. The complete disclosure of this patent is herein incorporated by reference.
[0011] U.S. Pat. No. 5,052,162, to Bush et al, teaches a process of continually making a composite laminated shingle. The complete disclosure of this patent is herein incorporated by reference.
[0012] U.S. Pat. No. 5,181,361, to Hannah, et al, teaches a laminated shingle in which the shingle is comprised of a base layer and a secondary layer, and with a partial top layer. Each of the layers is comprised of an asphaltic web with granules applied to the top of the web. The final shingle has some portions being of two-layer thickness and other portions being of three-layer thickness. The complete disclosure of this patent is herein incorporated by reference.
[0013] U.S. Pat. No. 5,611,186, to Weaver, teaches a laminated composite shingle with an illusion of depth created by a value gradation from a light color to a dark color in a portion of the buttlap section. The complete disclosure of this patent is herein incorporated by reference.
[0014] U.S. Pat. No. 5,860,263, to Sieling , et al., teaches a rectangular roofing shingle having dissimilarly shaped, space-separated, snaggle-toothed sections in the buttlap portion of the shingle. The complete disclosure of this patent is herein incorporated by reference.
[0015] U.S. Pat. No. 6,212,843, to Kalkanoglu et al., describes a shingle and method for making multi-tab composite shingles having a thicker appearance for the tabs than the actual thickness of the shingle. The complete disclosure of this patent is herein incorporated by reference.
[0016] U.S. Pat. No. 6,220,329, to King, et al., describes a method and apparatus of making a laminated roofing shingle. The complete disclosure of this patent is herein incorporated by reference.
[0017] U.S. Pat. No. 6,253,512, to Thompson et al., describes a method of applying tiles to a roof in a random appearing manner so as to try to create an aesthetically pleasing appearance. The complete disclosure of this patent is herein incorporated by reference.
[0018] U.S. Pat. No. 6,289,648, to Freshwater, et al., describes a laminated composite shingle, the shingle having color striations across at least some parts of the buttlap portion in an attempt to improve the aesthetic appearance of the shingle. The complete disclosure of this patent is herein incorporated by reference.
[0019] Unfortunately, current manufacturing and installation methods of composite shingle roofing material result in roof with a less aesthetically pleasing appearance than a wood shingle or slate tile roof.
[0020] It is an object of the present invention to provide a composite shingle that will give the appearance of a wood shingles or a slate tile after installation.
[0021] Another object of the present invention is to provide a method of installing a plurality composite shingles to give the appearance of a wood shingle or a slate tile roof.
[0022] Another object of the present invention is to provide a method of manufacturing shingles that can be readily installed on a building surface to give the appearance of a wood shingle or slate tile roof.
[0023] Another object of the present invention is to provide a method of packaging composite shingles of various widths.
[0024] Other objects and advantages of the present invention will be readily apparent to those skilled in the art from a reading of the following summary of the invention, brief description of the drawing figures, detailed description of the invention and the appended claims.
SUMMARY OF PREFERRED EMBODIMENTS
[0025] In accordance to the present invention, there has now been developed a composite shingle and a method of installation that has the aesthetically pleasing appearance of a wooden shingle or slate tile roof. The prior art has taught that it is a disadvantage that wooden shingles or slate tiles must be installed in a spaced-apart arrangement to allow for expansion. However, this spaced-apart arrangement is in part what creates an aesthetically pleasing appearance. Likewise, the propensity of wooden shingles to curl and not remain flat on the roof creates random shadow lines that are also part of the aesthetically pleasing appearance. Additionally, because of the subsequent weathering of the wooden shingles after installation, variations between shingles in the grooves and ridges in the wood grain and variations in the color creates part of the aesthetically pleasing appearance. Even slight differences in color between neighboring shingles will add to an aesthetically pleasing appearance. Further still, after installation the width of each wood shingle or slate tile on the roof usually varies in width from the neighboring wood shingles or slate tiles. This random width also adds to the aesthetically pleasing appearance. Also, upon installation the butt edge portion of a wooden shingle or slate tile will often vary slightly from neighboring shingles or tiles. The slight random positioning of the shingles or tiles upon installation adds to the aesthetically pleasing appearance. Another random aspect of natural roofing material that adds to the aesthetically pleasing appearance is a slight variation in thickness between neighboring shingles or tiles. Past attempts to make and install composite shingles having the aesthetically pleasing appearance of wooden shingles or slate tiles have failed to duplicate one or more of the aesthetical characteristics of a wood shingle roof or a slate tile roof.
[0026] Currently available shingles attempt to create the illusion of the dimensions a wood shingles or slate tiles instead of actually approximating the same dimensions. An advantage of having composite shingles that are wider than wood shingles is a decrease in installation cost. However, wider composite shingles have up until now suffered from a decreased aesthetic appearance and a decrease in perceived value compared to natural roofing material. Perhaps because of concerns of having the nails from the underlying course show through the buttlap portion, currently available composite shingles almost always have a solid buttlap layer. Tab shingles are available, but these do not have random widths because of the problem with nails showing from the underlying course. A “tab shingle” is defined as a shingle with a cut completely through all layers of the buttlap portion of the shingle.
[0027] Historically, craftsman attempted to make perfect wood shingles or slate tiles. However, these craftsmen were limited by nature. In the past 100 years, the quality of manufacturing techniques has improved to the point where it is possible to create an almost perfect shingle. From an aesthetic point of view, composite roofing material is made too perfectly. Nature is not perfectly uniform, and as part of nature, people are inherently uncomfortable in a perfectly uniform setting. A perfectly uniform roof does not create the same aesthetically pleasing appearance as a roof with slight random variations.
[0028] The present invention is directed to using composite shingles in a novel manner to create the aesthetically pleasing appearance of a wood shingle roof or a slate tile roof. None of the prior art approaches of manufacturing or installing composite shingles focused on making the thickness of the shingle, the width of the shingle, the spacing between shingles, the butt end alignment of the shingles, and the color of the shingle match a wood shingle roof or slate tile roof. To more accurately approximate the appearance of a wood shingle roof, random appearing dimensions and colors need to be incorporated into the roofing material and/or installation. For the most aesthetically pleasing appearance, after installation each tab of a composite shingle needs to appear to be an independent shingle.
[0029] In one embodiment, a pseudo-wood shingle is created with the same dimensions as a cedar shingle. Each pseudo-wood shingle is an independent shingle, and thus the slight randomness in spacing and alignment inherent in hand installation will add to the aesthetically pleasing appearance of the roof.
[0030] In another embodiment of the present invention, a random tab composite shingle is provided with random tab widths, random cut widths between tabs, random tab colors, and/or random butt edge alignment. The tabs may also be of slightly random thickness.
[0031] In another embodiment of the present invention, when a plurality of the random tab composite shingles described herein are installed to a surface, the composite shingles give the appearance of independent wood shingles.
[0032] In another embodiment of the present invention, composite shingles are provided with a thickness and width approximating a wood shingle. Individual shingles vary in widths less than 18 inches, preferably from between 2 inches and 13 inches, more preferable between 4 inches and 8 inches. These shingles are called “pseudo-wood” shingles.
[0033] In another embodiment of the present invention, when a plurality of the composite shingles described herein are installed on a roof, the roof will have a Class A fire barrier rating.
[0034] In another aspect of the present invention, composite shingles are sorted and packaged by color groups and/or dimensional groups for delivery to construction sites.
[0035] In another embodiment of the present invention, composite shingles are provided with a width and thickness approximating a slate tile. Individual shingles vary in widths less than 24 inches, preferably from between 12 inches and 16 inches.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] [0036]FIG. 1 is a perspective view of a random tab shingle of the present invention.
[0037] [0037]FIG. 2A is a top plan view of a laminated composite shingle.
[0038] [0038]FIG. 2B is a front plan view of a laminated composite shingle.
[0039] [0039]FIG. 3 is a perspective view of a partial roofing section after installation in a thatch style of the pseudo-wood tab shingles by the method of the present invention.
[0040] [0040]FIG. 4 is a perspective view of a partial roofing section after a typical installation of the pseudo-wood tab shingles by the method of the present invention.
[0041] [0041]FIG. 5 is an enlarged perspective view of a partial roofing section after a typical installation of the pseudo-wood tab shingles by the method of the present invention.
[0042] [0042]FIG. 6 is an enlarged perspective view of a partial roofing section after a typical installation of the random tab shingles of the present invention.
[0043] [0043]FIG. 7 is an enlarged top plan view of the butt edge alignment of either pseudo-wood shingles, a random tab shingle, or pseudo-slate tiles.
[0044] [0044]FIG. 8 is an exploded isometric view showing the sectioned shingle components of the present invention.
[0045] [0045]FIG. 9 is a front plan view of the sectioned shingles of the present invention.
[0046] [0046]FIG. 10 is a perspective view of the sectioned shingles of the present invention and a pseudo-wood shingle of the present invention.
[0047] [0047]FIG. 11 is an illustration showing possible variations in colors and dimensions of the random tab composite shingles or the pseudo-wood composite shingles of the present invention after a typical installation.
[0048] [0048]FIG. 12 is a perspective view of a diamond pattern installation and of a scallops or “fish scales” installation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0049] First Embodiment—Random Tab Composite Shingle
[0050] In FIGS. 1 and 6, the reference number 10 generally designates the random tab shingle of the present invention. Shingle 10 has a body portion of a generally flat or planar, polygonal configuration. Preferably, shingle 10 is of rectangular configuration. Shingle 10 has a headlap portion 112 and a buttlap portion 113 . Cuts 101 are made through all layers of the butlap portion 113 , creating tabs 105 - 109 . Cuts 101 are preferably random appearing in width, approximately {fraction (1/4)}″ with variations preferably of plus or minus {fraction (1/16)}″. Thus, cuts 101 will give a spaced-apart appearance of approximately {fraction (1/4)}″ between tab 105 and 106 , as well as between tabs 106 and 107 , etc. Cuts 101 are made along the buttlap portion such that they create random appearing widths 115 - 119 in tabs 105 - 109 . Tab width 115 - 119 are less than 18″, preferably between 2″ and 13″, more preferably between 4″ and 8″. For illustration purposes only, in FIG. 1 tab width 105 is 5″, tab width 106 is 8″, tab width 107 is 4″, tab width 108 is 3″, etc. Nail targets 102 are marked on the top portion of shingle 10 in headlap portion 112 . On the topside of shingle 10 is glue strip 103 . The alignment of lower tab edge 104 is optionally random appearing. Lower tab edge 104 is preferably within ⅛″ of the neighboring lower tab edges, more preferably within {fraction (1/16)}″ of neighboring lower tab edges. Perforations 110 run up from cuts 101 through the headlap portion 112 . This allows easy of separation between any of tabs 105 - 109 . Preferably, the colors of each of tabs 105 - 109 appear to be random. The thickness 111 is preferred the same as a cedar shingle, that is ⅜″. Thickness 111 can also be that of a wood shake or other natural roofing material. Further, thickness 111 can vary slightly between tabs neighboring. Thus, in one embodiment, the random tab composite shingle may include random appearing tab widths 115 - 119 , random appearing tab thickness 111 , random appearing widths of cuts 101 , random appearing colors of tabs 105 - 109 , and random appearing lower edge alignment 104 of tabs 105 - 109 .
[0051] [0051]FIG. 6 shows a partial installation of random tab composite shingles. First course 601 is installed in the standard manner for composite shingles. The starter course 602 is completely covered by the first course 601 , except at cuts 101 . In the example shown, shingle 10 is secured to the roof by attaching shingle 10 to the roof at nail targets 102 . The second course 603 covers the headlap portion of first course 601 , third course 604 covers the headlap portion of second course 603 , and fourth course 605 covers the headlap portion of third course 604 .
[0052] After installation, each tab of the random tab composite shingle will appear to be independent from the neighboring tabs.
[0053] Second Embodiment—Pseudo-wood Shingle and Installation Thereof
[0054] In FIGS. 2 and 8, the reference number 20 generally designates a currently available composite shingle. FIGS. 2A and 2B show a bi-laminated composite shingle. The Owens Corning® thirty year composite shingle is one example of a composite shingle as shown in FIG. 2. Other shingles can be substituted for the Owens Corning® composite shingle and still practice the invention described herein. Shingle 20 is cut vertically along cut line 208 . Cut line 208 is preferably along the edge of tab lines 209 , through buttlap portion 22 , and extends vertically through headlap portion 21 . This creates sectioned shingles 202 , 204 and 206 of single thickness, and sectioned shingles 201 , 203 and 205 of double thickness, as shown in FIG. 8. The cutting of the shingles can easily be done with a razor, shear, knife, or other cutting means.
[0055] Sectioned shingles 201 - 206 are sorted according to width and thickness, as shown in FIG. 9. Single thickness shingles are matched with double thickness shingles of similar widths. In the example shown in FIG. 9, sectioned shingle 202 is matched with sectioned shingle 203 , and sectioned shingle 204 is matched with sectioned shingle 205 .
[0056] Sectioned shingles of similar widths are stacked on top of each other until the desired thickness is achieved. A cedar shingle is approximately {fraction (3/8)}″ thick. The Owens Corning® thirty year composite shingles achieves this thickness by stacking one single layer shingle with one double layer shingle, or three single layer shingles. This process can be used to “build-up” any desired thickness. Shake shingles are typically ⅝″ thickness, so if this thickness is desired a total of five layers need to be stacked on top of each other. Lamination is achieved in part by the glue strips 207 on the backside of the shingle. Heat from the sun melts glue strips 207 and causes the shingles to adhere to each other and act as one shingle. For example, in FIG. 10, sectioned shingle 202 adheres to shingle 203 and creates pseudo-wood shingle 1001 .
[0057] By laminating sectioned shingles in the fashion described, pseudo-wood shingle 1001 looks and installs in a the same fashion as a traditional wood shingle. However, the greater ease of cutting and nailing that comes from composition shingles is also achieved in the pseudo-wood shingle.
[0058] On a typical roof installation, the roof is prepared in a manner typical to that for a standard composition roof, preferably as required by the Uniform Building Code.
[0059] An example of a “thatched roof” style of installation of the pseudo-wood shingles is shown in FIG. 3. Starter course 301 is installed, in a manner as required by the installation. This usually includes roofing paper 302 under the starter course 301 . The pseudo-wood shingles of first course 303 are then installed in the same fashion as a traditional wood shingle roof. Subsequent courses 304 are also installed in the traditional fashion.
[0060] An example of a standard wood shingle installation method is shown in FIGS. 4 and 5. In FIG. 4, the buttlap portion 401 of the pseudo-wood shingles covers nailing 402 of the previous course. Roofing paper 302 is completely covered by the pseudo-wood shingles.
[0061] In FIG. 5, spacing 504 between each pseudo-wood shingle is the same as spacing between traditional wood shingles on a roof, or approximately {fraction (1/4)}″ to ⅜″. Nails 503 are covered by the buttlap portion of the subsequent courses. For illustration purposes, the color of pseudo-wood shingle 501 is different than pseudo-wood shingle 502 .
[0062] [0062]FIG. 7 illustrates how the lower edge portion of a shingle can vary. Reference numbers 71 - 74 designate separate pseudo-wood shingles or individual tabs of s random tab shingle. For illustration purposes, in this example lower edge alignment 701 varies slightly with lower edge alignment 702 . Lower edge alignment 703 is not exactly perpendicular to the roof edge (not shown). Lower edge alignment 704 is almost identical to lower edge alignment 701 . An unlimited number of variations are possible while still maintaining a slight random appearance to the lower edge alignment.
[0063] A finished roof is shown in FIG. 11. Either random tab shingles 10 or pseudo-wood shingles 20 may be used to create the appearance of a wood roof. Reference numbers 1101 - 1106 designate separate pseudo-wood shingles or individual tabs of random tab shingles. Shingles 1101 - 1106 may appear to be of random width, spacing, thickness, alignment, and color.
[0064] Third Embodiment—Off-site Manufacture of Shingles
[0065] In another embodiment of the present invention, a single layer of a composite shingle is manufactured to be approximately the thickness of a wood shingle. This single layer is then cut to approximate the dimensions of wood shingles, creating a plurality of pseudo-wood shingles. The pseudo-wood shingles may then be sorted by width and/or color. The pseudo-wood shingles may also be packaged with a plurality of widths and/or colors being provided in each unit.
[0066] Fourth Embodiment—Fancy Butts and Other Applications
[0067] A fancy butt is an exposed end of a shingle that is cut to create a decorative effect. Examples are shown in FIG. 12. FIG. 12A shows a diamond pattern. The buttlap portion of the shingle is cut as is well known in the art. FIG. 12B shows a scallop or “fish scale” style.
[0068] Fifth Embodiment—Standard Size Composite Shingle with Perforations or Grooves
[0069] In another embodiment of the present invention, shingle 20 is made as is known in the art, as shown in FIG. 2. During or after manufacture, perforations or grooves are made in shingle 20 at cut lines 208 . Sectioned shingles 201 - 206 are easily separated from each other, and pseudo-wood shingles are created. Each of sectioned shingles 201 - 206 may be a different random appearing color from the neighboring sectioned shingle.
[0070] Sixth Embodiment—Thick Composite Shingle with Perforations or Grooves
[0071] In another embodiment of the present invention, a composite shingle of approximately {fraction (3/8)}″ thickness or more is made, as is known in the art. (Not shown.) During or after manufacture, perforations or grooves are made in the thick shingle at random appearing widths. Pseudo-wood shingles are created by separating the thick shingle at the perforations or grooves. The buttlap portion of the thick shingle between the perforations or grooves may be of random appearing colors.
[0072] Seventh Embodiment—Pseudo-slate Tile and Random Tab Slate Shingle
[0073] The principles described in the first through seventh embodiments will also apply to slate tiles. Specifically, this includes random appearance in shingle width, spaced-apart installation, shingle butt end alignment, shingle thickness, and shingle color. Composite shingles can be manufactured following an analogous format for both the pseudo-wood shingle and the random tab shingle of the first embodiment. Installation methods of the pseudo-slate shingle | A composite shingle, comprising a headlap portion, a buttlap portion, the thickness of the buttlap portion is approximately between ¼ inch and ¾ inch, tab cuts that extend completely through the buttlap portion to create separate tabs, the tab cuts disposed along the lower buttlap portion edge such that the width of the separate tab have random appearance; wherein after installation of a plurality of the composite shingles, each tab appears to be a separate shingle. A method of covering a surface with composite shingles comprising providing a plurality of composite shingles having a thickness approximating the thickness of a wood shingle, wherein the plurality of composite shingles each have a width of between approximately 2 inches and approximately 10 inches; and attaching the plurality of composite shingles to the surface in a fashion similar to and/or identical to attachment of a wood shingle to a surface. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] This is a continuation of U.S. patent application Ser. No. 10/349,917, filed Jan. 24, 2003, which is a divisional of U.S. patent application Ser. No. 09/901,569, filed Jul. 11, 2001, and now U.S. Pat. No. 6,537,727. A claim of priority is made to both said applications, and the entire contents of both said applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to a chemically amplified resist composition, and more particularly, the present invention relates to a resist composition comprising a photosensitive polymer having lactone in its backbone.
[0004] 2. Description of the Related Art
[0005] As the integration density and complexity of semiconductor devices continue to increase, the ability to form ultra-fine patterns becomes more and more critical. For example, in 1-Gigabit or higher semiconductor devices, a pattern size having a design rule of 0.2 μm or less is needed. For this reason, in lithography processes, the lower wavelength ArF eximer laser (193 nm) has emerged as a preferred exposure light source to the more conventional and higher wavelength KrF eximer laser (248 nm).
[0006] However, compared with conventional (KrF) resist materials, resist materials which are suitable for use with the ArF eximer laser suffer from a variety drawbacks. The most serious problems relate transmittance and resistance to dry etching.
[0007] Almost all well-known ArF resist compositions contain (meth)acryl-based polymers. Among these polymers, a methacrylate copolymer having an alicyclic protecting group, which is expressed by the formula below, has been suggested ( J. Photopolym. Sci. Technol., 9(3), pp. 509 (1996))
[0008] This polymer has an adamantyl group, which contributes to enhancing resistance to dry etching, and a lactone group, which improves adhesiveness, in its methacrylate backbone. As a result, the resolution of the resist and the depth of focus are improved. However, resistance to dry etching is still weak, and serious line edge roughness is observed after line patterns are formed from the resist layer.
[0009] Another drawback of the aforementioned polymer is that the raw material used to synthesize the polymer is expensive. In particular, the manufacturing cost of a polymer having a lactone group, which is introduced to improve adhesiveness, is so high that its practical use as a resist is difficult.
[0010] As another conventional resist composition, a cycloolefin-maleic anhydride (COMA) alternating polymer having the following formula has been suggested ( J. Photopolym. Sci. Technol ., Vol. 12(4), pp. 553 (1999), and U.S. Pat. No. 5,843,624)
[0011] In the production of a copolymer, such as a COMA alternating polymer having the formula above, the production cost of raw material is relatively inexpensive, but the yield of the polymer sharply decreases. In addition, the transmittance of the polymer is very low at a short wavelength region, for example at 193 nm. The synthetic polymers have in their backbone the alicyclic group, which exhibits prominent hydrophobicity, and thus the adhesiveness to neighboring material layers is very poor.
[0012] The copolymer has a glass transition temperature of 200° C. or more due to the structural characteristic of the backbone. As a result, it is difficult to carry out an annealing process for eliminating free volume from the resist layer formed of the polymer, and accordingly the resist layer is influenced by ambient conditions which can cause, for example, a T-top profile of corresponding resist patterns. In addition, the resist layer itself becomes less resistant to ambient conditions during post-exposure delay, so that many problems can occur during subsequent processes with respect to the photoresist layer.
[0013] To improve the resolution of the resist layer, the polymer system must be charged with a polar group. In recent years, a technique of introducing a lactone group into a methacrylate monomer having an alicyclic protecting group, using the following alicyclic compounds with a lactone group, has been suggested so as to enhance the resistance to dry etching ( J. Photopolym. Sci. Technol ., Vol. 13(4), pp. 601 (2000), and Japanese Patent Laid-open No. hei 12-26446):
[0014] Unfortunately, the yield of the monomer having the above formula is so low as to substantially increase manufacturing costs.
SUMMARY OF THE INVENTION
[0015] It is an objective of the present invention to provide a resist composition that can be produced at relatively low costs while exhibiting improved dry etching resistance, improved adhesiveness to underlying material layers, improved line edge roughness of line patterns, and improved contrast characteristics.
[0016] To achieve the objective of the present invention, there is provided a resist composition comprising a photosensitive polymer polymerized with (a) at least one of the monomers having the respective formulae:
where R 1 and R 2 are independently a hydrogen atom, alkyl, hydroxyalkyl, alkyloxy, carbonyl or ester, and x and y are independently integers from 1 to 6, and (b) at least one comonomer selected from the group consisting of (meth)acrylate monomer, maleic anhydride monomer, and norbornene monomer; and a photoacid generator (PAG).
[0018] In one embodiment of the resist composition, the comonomer may be (meth)acrylate monomer, and the formula of the photosensitive polymer may be one selected from the formulae:
where R3 is a hydrogen atom or methyl, R4 is an acid-liable group, m/(m+p) is in the range of 0.01-0.5,
where R3 is a hydrogen atom or methyl, R4 is an acid-liable group, n/(n+p) is in the range of 0.01-0.5, and
where R3 is a hydrogen atom or methyl, R4 is an acid-liable group, (m+n)/(m+n+p) is in the range of 0.01-0.5.
[0022] In one embodiment of the resist composition, the comonomer may be norbornene monomer, and the formula of the photosensitive polymer may be one selected from the formulae:
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; m/(m+r) is in the range of 0.01-0.5,
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; n/(n+r) is in the range of 0.01-0.5, and
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; (m+n)/(m+n+r) is in the range of 0.01-0.5.
[0026] In one embodiment of the resist composition, the comonomers may be (meth)acrylate and norbornene monomer, and the formula of the photosensitive polymer may be one selected from the formulae:
where R3 is a hydrogen atom or methyl; R4 is an acid-liable group; R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; m/(m+p+r) is in the range of 0.01-0.5; p/(m+p+r) is in the range of 0.1-0.6; and r(m+p+r) is in the range of 0.1-0.6,
where R3 is a hydrogen atom or methyl; R4 is an acid-liable group; R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; n/(n+p+r) is in the range of 0.01-0.5; p/(n+p+r) is in the range of 0.1-0.6; and r(n+p+r) is in the range of 0.1-0.6, and
where R3 is a hydrogen atom or methyl; R4 is an acid-liable group; R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; p/(m+n+p+r) is in the range of 0.1-06; and q(m+n+p+r) is in the range of 0.1-0.6.
[0030] In one embodiment of the resist composition, the comonomers may be maleic anhydride monomor and norbornene monomer, and the formula of the photosensitive polymer may be one selected from the formulae:
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; m/(m+q+r) is in the range of 0.01-0.5, q/(m+q+r) is in the range of 0.1-0.6, and r(m+q+r) is in the range of 0.1-0.6,
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; n/(n+q+r) is in the range of 0.01-0.5, q/(n+q+r) is in the range of 0.1-0.6, and r(n+q+r) is in the range of 0.1-0.6, and
where R5 and R6 are independently a hydrogen atom, hydroxyl, hydroxymethyl, 2-hydroxyethyloxycarbonyl, carboxyl, t-butoxycarbonyl, methoxycarbonyl, or substituted or unsubstituted alicyclic hydrocarbon having from 6 to 20 carbon atoms; (m+n)/(m+n+q+r) is in the range of 0.01-0.5, q/(m+n+q+r) is in the range of 0.1-06, and r(m+n+q+r) is in the range of 0.1-0.6.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
SYNTHESIS EXAMPLE 1
Synthesis of Terpolymer
[0034]
Synthesis Example 1-1
[heading-0035] (R 3 =methyl, R 4 =2-methyl-adamantyl)
[0036] 12.0 g 2-methyladamantylmethacrylate (MAdMA), 3.4 g maleic anhydride (MA), and 1.66 g α-angelicalactone (AGL) were dissolved in 17 g tetrahydrofuran (THF). 1.38 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0037] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the terpolymer having the formula above was obtained with a yield of 72%.
[0038] The obtained terpolymer had a weight average molecular weight (Mw) of 11,400, and a polydispersity (Mw/Mn) of 2.4.
[0039] In the synthesis of the terpolymer, the mixing ratio of the monomers can be varied to adjust the solubility of the polymer. The various mixing ratios of the monomers and the characteristics of the resultant five terpolymers are listed below in Table 1.
TABLE 1 Mixing Ratio Concentration Solvent-to-Monomer Polymerization of Monomers of Initiator ratio (by Time (MAdMa:MA:AGL) (mol %) weight) (hr) Yield (%) Mw Mw/Mn 3:4:1 AIBN 0.05 0.5 24 68 32,100 3.3 3:3:1 AIBN 0.05 0.5 24 87 21,000 2.2 3:2:1 AIBN 0.05 0.5 24 80 17,300 2.7 3:1:2 V601 0.05 1 20 56 7,200 1.7 3:2:1 V601 0.05 1 20 73 9,800 2.8
Synthesis Example 1-2
[heading-0040] (R 3 =methyl, R 4 =8-ethyl-8-tricyclo[5.2.1.0 2,6 ]decanyl])
[0041] 14.8 g 8-ethyl-8-tricyclo[5.2.1.0 2,6 ]decanylmethacrylate (ETCDMA), 3.4 g maleic anhydride (MA), and 1.66 g α-angelicalactone (AGL) were dissolved in 20 g tetrahydrofuran (THF). 1.38 g dimethyl 2,2′-azobisisobutyrate (V601) was added into the solution, degassed and polymerized at 70° C. for 20 hours.
[0042] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the terpolymer having the formula above was obtained with a yield of 65%.
[0043] The obtained terpolymer had a weight average molecular weight (Mw) of 12,100, and a polydispersity (Mw/Mn) of 2.6.
Synthesis Example 1-3
[heading-0044] (R 3 =methyl, R 4 =1-methylcyclohexyl)
[0045] 5.5 g 1-methylcyclohexylmethacrylate (MChMA), 1.7 g maleic anhydride (MA), and 0.83 g α-angelicalactone (AGL) were dissolved in 8 g tetrahydrofuran (THF). 0.69 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0046] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the terpolymer having the formula above was obtained with a yield of 71%.
[0047] The obtained terpolymer had a weight average molecular weight (Mw) of 11,000, and a polydispersity (Mw/Mn) of 2.6.
SYNTHESIS EXAMPLE 2
Synthesis of Tetrapolymer
[0048]
[0049] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0050] 6 g 2-methyladamantylmethacrylate (MAdMA), 1.9 g maleic anhydride (MA), 1.0 g 5,6-dihydro-2H-pyrane-2-one (DHPone) and 0.63 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0051] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 71%.
[0052] The obtained tetrapolymer had a weight average molecular weight (Mw) of 12,000, and a polydispersity (Mw/Mn) of 2.1.
SYNTHESIS EXAMPLE 3
Synthesis of Tetrapolymer
[0053]
[0054] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0055] 6 g 2-methyladamantylmethacrylate (MAdMA), 1.9 g maleic anhydride (MA), 1.2 g α-angelicalactone (AGL) and 0.63 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0056] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 72%.
[0057] The obtained tetrapolymer had a weight average molecular weight (Mw) of 12,600, and a polydispersity (Mw/Mn) of 1.9.
[0058] In the synthesis of the tetrapolymer, the mixing ratio of the monomers can be varied to adjust the solubility of the polymer. The various mixing ratios of the monomers, and the characteristics of the resultant six tetrapolymers are listed below in Table 2.
TABLE 2 Mixing Ratio Concentration Solvent-to-Monomer Polymerization of Monomers of Initiator ratio (by Time (MAdMA:MA:Nb:AGL) (mol %) weight) (hr) Yield (%) Mw Mw/Mn 4:3:2:1 V601 0.05 1 24 74 8,300 2.6 4:3:1:2 V601 0.05 1 24 62 7,700 2.1 4:3:2:2 V601 0.05 1 24 65 6,700 2.2 4:2:2:2 V601 0.05 1 20 59 6,700 2.0 4::1:1:2 V601 0.05 1 20 31 6,800 1.7 4:1:1:3 V601 0.05 1 20 62 5,600 1.6
SYNTHESIS EXAMPLE 4
Synthesis of Terpolymer
[0059]
[0060] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0061] 12.0 g 2-methyladamantylmethacrylate (MAdMA), 3.4 g maleic anhydride (MA), and 1.66 g α-methylenebutyrolactone (α-MBL) were dissolved in 17 g tetrahydrofuran (THF). 1.38 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0062] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the terpolymer having the formula above was obtained with a yield of 73%.
[0063] The obtained terpolymer had a weight average molecular weight (Mw) of 15,400, and a polydispersity (Mw/Mn) of 2.9.
SYNTHESIS EXAMPLE 5
Synthesis of Tetrapolymer
[0064]
Synthesis Example 5-1
[heading-0065] (R 3 =methyl, R 4 =2-methyl--adamantyl)
[0066] 6 g 2-methyladamantylmethacrylate (MAdMA), 1.88 g maleic anhydride (MA), 0.63 g α-methylenebutyrolactone (α-MBL), and 1.21 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0067] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 88%.
[0068] The obtained tetrapolymer had a weight average molecular weight (Mw) of 15,800, and a polydispersity (Mw/Mn) of 3.3.
[0069] In the synthesis of the tetrapolymer, the mixing ratio of the monomers can be varied to adjust the solubility of the polymer. The various mixing ratios of the monomers, and the characteristics of the resultant three tetrapolymers are listed below in Table 3.
TABLE 3 Mixing Ratio Concentration Solvent-to-Monomer Polymerization of Monomers of Initiator ratio (by Time (MAdMA:MA:α-MBL:Nb) (mol %) weight) (hr) Yield (%) Mw Mw/Mn 3:3:1:2 V601 0.05 1 20 87 13,300 3.6 4:3:1:2 V601 0.05 1 20 88 15,800 3.4 5:3:1:2 V601 0.05 1 20 86 18,600 3.7
Synthesis Example 5-2
[heading-0070] (R 3 =methyl, R 4 =2-methyl-adamantyl)
[0071] 6.4 g 2-ethyladamantylmethacrylate (EAdMA), 1.88 g maleic anhydride (MA), 0.63 g α-methylenebutyrolactone (α-MLB), and 1.21 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0072] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 78%.
[0073] The obtained tetrapolymer had a weight average molecular weight (Mw) of 11,600, and a polydispersity (Mw/Mn) of 3.0.
Synthesis Example 5-3
[heading-0074] (R 3 =hydrogen, R 4 =2-methyl-adamantyl)
[0075] 6.2 g 2-methyladamantylacrylate (MAdA), 2.06 g maleic anhydride (MA), 0.69 g α-methylenebutyrolactone (α-MBL), and 1.32 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,21-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0076] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 76%.
[0077] The obtained tetrapolymer had a weight average molecular weight (Mw) of 7,010, and a polydispersity (Mw/Mn) of 1.96.
SYNTHESIS EXAMPLE 6
Synthesis of Tetrapolymer
[0078]
[0079] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0080] 6.4 g 2-methyladamantylmethacrylate (MAdMA), 1.88 g maleic anhydride (MA), 0.63 g γ-methylenebutyrolactone (γ-MBL), and 1.21 g norbornene (Nb) were dissolved in 9.7 g tetrahydrofuran (THF). 0.74 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0081] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 82%.
[0082] The obtained tetrapolymer had a weight average molecular weight (Mw) of 14,300, and a polydispersity (Mw/Mn) of 2.8.
SYNTHESIS EXAMPLE 7
Synthesis of Monomer
[0083]
[0084] A solution of 30 g 2-bromomethylacrylic acid ethyl ester in 100 ml anhydrous THF was added dropwise with vigorous stirring under nitrogen to a mixture of 10.6 g zinc and 15.5 g adamantanone in 50 ml anhydrous THF. The reaction mixture was reacted at 60° C. for 10 hours. The reaction product was cooled down to room temperature, poured into 500 ml diluted hydrochloric acid solution, and extracted with 700 ml ether twice. The extracted solution was washed with 400 ml aqueous sodium hydrogencarbonate (NaHCO 3 ) and with 400 ml water, and then dried over anhydrous sodium sulfate (Na 2 SO 4 ). The dried product was evaporated with ether under reduced pressure. The residue was recrystallized from methylene dichloride and hexane, so that white solid monomer A was obtained with a yield of 62%.
SYNTHESIS EXAMPLE 8
Synthesis of Terpolymer
[0085]
[0086] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0087] 7.03 g 2-methyladamantylmethacrylate (MAdMA), 1.96 g maleic anhydride (MA), and 2.18 g Monomer A synthesized in Synthesis Example 7 were dissolved in 11.2 g tetrahydrofuran (THF). 0.69 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 4 hours.
[0088] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 86%.
[0089] The obtained terpolymer had a weight average molecular weight (Mw) of 8,200, and a polydispersity (Mw/Mn) of 2.0.
[0090] In the synthesis of the terpolymer, the mixing ratio of the monomers can be varied. The various mixing ratios of the monomers, and the characteristics of the resultant three terpolymers are listed below in Table 4.
TABLE 4 Mixing Ratio Concentration Solvent-to- Polymerization of Monomers of Initiator Monomer ratio Time (MAdMA:MA:Monomer A) (mol %) (by weight) (hr) Yield (%) Mw Mw/Mn 3:6:1 V601 0.05 1 4 62 5,700 2.1 3:4:1 V601 0.05 1 4 72 7,000 2.0 3:2:1 V601 0.05 1 4 86 8,200 2.0
SYNTHESIS EXAMPLE 9
Synthesis of Tetrapolymer
[0091]
[0092] In the above formula, R 3 is methyl and R 4 is 2-methyl-adamantyl.
[0093] 9.7 g 2-methyladamantylmethacrylate (MAdMA), 4.06 g maleic anhydride (MA), 3 g Monomer A synthesized in Synthesis Example 7, and 2.6 g norbornene (Nb) were dissolved in 19.6 g tetrahydrofuran (THF). 1.6 g dimethyl 2,2′-azobisisobutyrate (V601) was added to the solution, degassed and polymerized at 70° C. for 20 hours.
[0094] After the reaction was completed, the obtained reaction product was precipitated with excess isopropyl alcohol twice, filtered, and dried in a vacuum oven for 24 hours, so that the tetrapolymer having the formula above was obtained with a yield of 86%.
[0095] The obtained tetrapolymer had a weight average molecular weight (Mw) of 5,500, and a polydispersity (Mw/Mn) of 2.4.
EXAMPLE 1
Preparation of Resist Composition
[0096] 1.0 g each of the polymers obtained in Synthesis Examples 1-1 through 1-3, Synthesis Example 2, and Synthesis Example 3, 0.01 g triphenylsulfonium trifluoromethanesulfonate (triflate) as a photoacid generator (PAG), and 3.2 mg triisodecylamine as an organic base, were completely dissolved in a mixed solution of 4.0 g propylene glycol monomethyl ether acetate (PGMEA) and 4.0 g cyclohexanone, and filtered through a membrane filter of 0.2 μm, so that resist compositions were obtained. Each of the resist compositions was coated on a silicon (Si) wafer treated with organic anti-reflective coating (ARC) to a thickness of about 0.35 μm.
[0097] The wafers coated with the respective resist compositions were soft baked at 130° C. for 90 seconds, exposed using an ArF eximer laser stepper (NA=0.6), and subjected to a post-exposure bake (PEB) at 120° C. for 60 seconds.
[0098] The resultant wafers were developed using 2.38% by weight tetramethylammonium hydroxide solution for about 60 seconds. As a result, 0.17-0.23 μm line and space patterns of photoresist were formed with an exposure dosage of 10 to 30 mJ/cm 2 .
EXAMPLE 2
Preparation of Resist Composition
[0099] 1.0 g each of the polymers obtained in Synthesis Example 4, Synthesis Examples 5-1 through 5-3, and Synthesis Example 6, 0.01 g triflate as a PAG, and 3.2 mg triisodecylamine as an organic base, were completely dissolved in a mixed solution of 4.0 g PGMEA and 4.0 g cyclohexanone, and filtered through a membrane filter of 0.2 μm, so that resist compositions were obtained. Each of the resist compositions was coated on a silicon (Si) wafer treated with organic anti-reflective coating (ARC) to a thickness of about 0.35 μm.
[0100] The wafers coated with the respective resist compositions were soft baked at 130° C. for 90 seconds, exposed using an ArF eximer laser stepper (NA=0.6), and subjected to a post-exposure bake (PEB) at 120° C. for 60 seconds.
[0101] The resultant wafers were developed using 2.38% by weight tetramethylammonium hydroxide solution for about 60 seconds. As a result, 0.17-0.23μ line and space pattern of photoresist were formed with an exposure dosage of 10 to 30 mJ/cm 2 .
[0102] The photosensitive polymer, which constitutes the photoresist composition according to the present invention, includes a cyclic lactone in its backbone. Thus, the manufacturing cost is very low, and the problems of the conventional polymers used in the production of ArF resists can be largely overcome. The resist composition prepared from the photosensitive polymer exhibits excellent resistance to dry etching, superior adhesiveness to underlying material layers, and improved transmittance. The cyclic lactone included in the polymer backbone is highly hydrophilic. When forming space and line patterns from the resist layer deposited with the resist composition according to the present invention, line edge roughness characteristic is improved. The dissolution contrast characteristic, which appears after developing, sharply increases, thereby enlarging the depth of focus (DOF) margin.
[0103] The photosensitive polymer of the resist composition according to the present invention has a desirable glass transition temperature of 140 to 180° C. As for the resist layer which contains the photosensitive polymer according to the present invention, the free volume of the resist layer can be decreased due to a sufficient annealing effect during a baking process. As a result, the resist layer becomes more resistant to the ambient environment during post-exposure delay (PED). Thus, use of the resist composition according to the present invention in a photolithography process exhibits superior lithography characteristics, and is therefore useful in the manufacture of future generation semiconductor devices.
[0104] While this invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made thereto without departing from the spirit and scope of the invention as defined by the appended claims.
[0105] It is noted that priority has been claimed to Korean Patent Application No. 00-39562, filed 11 Jul. 2000, and Korean Patent Application No. 00-75485, filed 12 Dec. 2000. Both of these Korean applications are incorporated herein in their entirety. | A resist composition includes a photoacid generator (PAG) and a photosensitive polymer. The photosensitive polymer is polymerized with (a) at least one of the monomers having the respective formulae:
where R1 and R2 are independently a hydrogen atom, alkyl, hydroxyalkyl, alkyloxy, carbonyl or ester, and x and y are independently integers from 1 to 6, and (b) at least one of a (meth)acrylate monomer, a maleic anhydride monomer, and a norbornene monomer. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to a fuse for insertion in the primary circuit of a high voltage transformer or other device and having a rupturable element wire which melts at a predetermined current level. The fuse includes an arc intercepting element and a resistor in circuit with the intercepting element to reduce fault currents momentarily to an arc extinguishing level to clear the circuit.
2. Background Art
In the art of protective fuses for electrical circuits and the like, and in particular for high voltage transformer circuits, it is known to provide so-called protective links to remove an internally faulted transformer from the primary line thereby preventing outages to other circuits on the line not served by the faulted transformer. The conventional approach to providing circuit clearing fuses for faulted transformers and other high voltage circuits has included the provision of a fuse having a component which melts or decomposes to produce an arc extinguishing gas to eliminate continued arcing. However, the conventional silver/sand current limiting fuses are expensive and it has been impractical to equip distribution transformers with this type of fuse. At the same time, there has been an increasing number of systems wherein potential fault currents are much higher than previous fuse designs are capable of interrupting without some danger to equipment and to the environment surrounding the transformer itself.
It has been determined that conventional weak link type current limiting fuses which, for example, operate by utilizing gas pressure to propel one end of the fuse structure away from the other end in an oil filled transformer to provide circuit interruption, have been found to be suitable for fault currents in the range of 1500 amps or less. For higher fault currents it has become necessary to strengthen the mechanical structure of the fuse, as well as the support bushing for the fuse. This has become increasingly expensive and a not entirely satisfactory solution to failures wherein fault currents in the range of 3,000 to 35,000 amps may occur.
Accordingly, since the conventional rupturable element type fuse, provided with a material such as a vulcanized fiber tube surrounding the fuse element to provide the arc extinguishing gas, has been relatively successful for current levels in the range of 100 to 1500 amps, it has been determined that it is desirable to provide for a fuse structure which will insert a resistor in the circuit on failure of either the transformer or any other circuit which might occur within the transformer enclosure. The object of the present invention is to provide for directing the arc established upon melting of the fuse element in such a way that it passes through a resistor to at least momentarily reduce the current level to a value which will result in extinguishment of the arc in the presence of a deionizing gas. This functional advantage is provided by structure which has heretofore not been provided in the art of protective link fuses for transformers and the like. Moreover, the particular arrangement of a protective fuse in accordance with the present invention also provides, in one compact structural unit, the capability of protecting the circuit against short circuit conditions when the current is at a relatively low level and upon heating of the resistor whereby sufficient mechanical separation of the fuse conductor elements may be obtained to prevent arc establishment or restrike.
SUMMARY OF THE INVENTION
The present invention provides an improved protective link or circuit interrupting fuse for relatively high voltage applications, particularly in the environment of protecting the primary circuit of a distribution transformer or the like, wherein an improved arrangement of a resistor element is provided to momentarily reduce the fault current to a level which will provide arc extinguishment by deionizing gases generated by failure of the fuse.
In accordance with one aspect of the present invention, there is provided a fuse element for a transformer or the like which includes a fusible link, which upon melting as a result of an overload current, establishes an arc or sufficient energy to decompose a gas generating substance. The fuse is also provided with an arc intercepting element which is in circuit with a resistor which momentarily reduces the fault current to a level which will enable the deionizing gas to extinguish the arc and to prevent restrike.
In accordance with another aspect of the present invention, there is provided an improved fuse structure including a fusible element, an arc intercepting element, and a resistor arranged in such a manner that heating of the resistor will cause mechanical separation of one terminal of the fuse with sufficient force to separate the fuse conductor elements to interrupt or extinguish an arc. The fuse is preferably disposed in an arc suppressing environment such as by being at least partially immersed in transformer insulating fluid.
In accordance with yet another important aspect of the present invention, there is provided a fuse of a type which is adapted to be inserted in an insulating bushing which includes a main current carrying member made of a suitable magnetic material which produces a magnetic field of sufficient strength to control the location of an electrical arc. The magnetic field produced by the current carrying member forces the arc into the vicinity of a gas generating fiber tube to produce a greater amount of arc extinguishing gas more rapidly than with prior art protective link type fuses.
The present invention still further provides an improved fuse construction for use in connection with transformers and other high voltage devices wherein the fuse is adapted to be immersed in oil and includes an orifice which allows the interior of the fuse structure to fill with oil when immersed but is also sized to control the generation of gas pressure upon failure of the fuse so that a pressure force will cause certain elements of the fuse to forcibly separate from the remainder of the fuse structure for greater separation of the conductor elements to provide arc extinguishment.
The overall construction of the protective link type fuse of the present invention is compact, economical to manufacture and superior to fuses heretofore known in the art. Those skilled in the art will appreciate the advantages discussed herein, as well as other superior features of the present invention which will become apparent upon reading the detailed description which follows in conjunction with the drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a partial elevation in section of a typical electrical distribution transformer showing the fuse of the present invention mounted in an insulating bushing; and
FIG. 2 is a longitudinal central section view of the fuse of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention comprises an expulsion type fuse of the type to be used in electrical distribution transformers and the like and which is adapted to be placed in series with the high voltage winding of the transformer to clear the circuit by generating an arc extinguishing gas to interrupt the fault current as the current approaches a zero point on its wave form. In particular, the fuse of the present invention is adapted to provide arc interruption and circuit clearing without the necessity of increasing the mechanical strength of associated structure such as, for example, the transformer bushing and tank.
Referring to FIG. 1 of the drawings, there is shown a portion of a typical electric utility distribution transformer generally designated by the numeral 10. The transformer 10 includes a tank 12 in which the transformer windings are disposed and covered with an insulating and cooling oil 13 with which the tank interior is filled. A high voltage conductor 15 is connected to the transformer at a porcelain bushing of a conventional type, designated by the numeral 14, which is mounted on a top wall or cover portion 17 of the tank and extends into the interior of the tank, as illustrated. The bushing 14 is provided with an internal bore 19 in which is mounted a fuse or protective link in accordance with the present invention and generally designated by the numeral 16. A lower portion of the fuse 16 extends from the bottom end of the bushing and the fuse is substantially immersed in the transformer oil contained within the tank. Although the fuse 16 is illustrated as being mounted within the high voltage bushing 14, it will be understood that the fuse may be mounted on a terminal block within the transformer tank or on other suitable structure within or even outside the tank. Moreover, the fuse 16 will also operate satisfactorily in the presence of air or other gaseous insulating fluids as well as liquid insulating fluids including the oil 13.
Referring further to FIG. 1, the fuse 16 includes an elongated conductor element or rod 20 which extends through the top of the bushing 14 and is suitably connected to a connector element 22 which in turn is connected to the high voltage conductor 15.
Referring now to FIG. 2, in particular, the fuse 16, including the conductor rod 20, is shown in longitudinal elevation with a major portion of the fuse shown in longitudinal central section. The lower end of the conductor rod 20 is fastened to an elongated tubular element 24 comprising a vulcanized fiber tube of a type which is adapted to generate a deionizing gas when exposed to a high voltage electrical arc or other heat generating phenomena which would tend to decompose the tube. The tube 24 is of a type commercially available for use in transformer fuses and the like. The tube 24 is snuggly fitted over the end of the rod 20 and is secured to the rod by a transverse pin 26 which extends through the rod and through a suitable diametral hole drilled through opposed portions of the sidewall of the tube 24. Directly below the rod 20 is a vent hole 28 which is drilled through the sidewall of the tube 24 to provide for controlled venting of gases from the interior of the tube and to permit the interior of the fuse to fill with insulating fluid such as transformer oil.
The lower end of the tube 24 is provided with a circumferential groove 25 which is engaged by a copper or steel tubular sleeve 30 suitably crimped into the groove as illustrated. Alternatively, the tube 24 could be provided with tapered threads engageable with cooperating threads formed on the sleeve member 30. The sleeve 30 is disposed around and contiguous with an arc intercepting member characterized by a cylindrical plate 33 having a cylindrical opening formed in the center thereof and which is delimited by a convex curved wall portion 35. The rounded surface or wall portion 35 is provided to reduce the effects of dielectric stress exerted on the member 33 when the member acts to intercept an electrical arc, as will be discussed in further detail hereinbelow. The member 33 may be formed of a suitable metal conductor material such as brass. Alternatively, the members 30 and 33 could be fabricated as a single piece.
The fuse 16 is still further characterized by a cylindrical tubular resistor element generally designated by the numeral 40 which is fitted within the interior of a depending portion 32 of the sleeve member 30 and is connected at its opposite end to a cap 42. The resistor element 40 may be of varied construction such as, for example, a resistive material with wound wire or, preferably, a high temperature material such as silicon carbide. In a preferred embodiment of the present invention, the resistor element 40 is of a type commercially available from the Carborundum Company, Niagara Falls, N.Y. as their type SP high power non-inductive resistors. The resistor element 40, for a particular fuse element having the capability of interrupting fault currents in the range of 100 amps to 3500 amps or more, has a nominal resistance of 7.5 ohms and is a type 885 SP 7R5L, the designation being that of the abovementioned source of this element. The resistor element 40 is secured to the member 30 at an interface 37 within the portion 32 by a relatively high temperature solder such as a conventional lead-tin solder having a 40/60 or 50/50 composition of lead with respect to tin of which the eutectic point is in the range of 456° F. The element 40 and member 30 could be provided with other means such as cooperating threads for securing these parts to each other. The fuse 16 is also preferably provided with a sleeve member 41 comprising a heat shrinkable fluorocarbon plastic tube disposed over the sleeve member 30 and extending longitudinally beyond each end of the sleeve member 30. The sleeve 41 forms a substantially gas tight seal and supports the assembled components of the fuse 16.
The lower end of the resistor element 40 is soldered to the cap 42 which also may be made of brass, for example. The resistor element 40 is secured to the cap 42 by a solder layer 45 having a lower melting point than the solder used to secure the upper end of the resistor element to the member 30. For example, a solder comprising 43% tin, 14% bismuth and 43% lead with a melting point in the range of 289° to 325° F. is preferably used. The use of the lower melting point solder layer 45 to form the connection between the cap 42 and the resistor element 40 provides for forcible separation of the cap from the remainder of the fuse due to melting of the solder upon heating of the resistor and generation of gas pressure within the interior of the fuse upon failure of the fuse element itself. In this way, a conductor 44 connected to the cap 42 and leading to the primary windings of the transformer, not shown, may be blown clear of the fuse into the interior of the tank to reduce the possibility of arc strike or restrike in the event of relatively slow failure of the fuse.
The fuse 16 is yet further characterized by an elongated fuse element 46 comprised of fuse element wire commonly used in distribution transformer fuses and properly sized to provide for rupture such as by melting of the wire on experiencing a fault current greater than a nominal 5 to 10 times the normal full load current in order to remove the transformer from the system circuit. The fuse element wire itself forms no part of the present invention and may be made of conventional fusible element materials used in distribution transformer fuses. The element 46 may be formed of silicon bronze and be a no. 25 to a no. 12 round AWG size wire, for example. The fuse element 46 is inserted in a hole formed in the lower end of the conductor rod 20 and a fixed thereto by brazing, for example. The opposite end of the fuse element 46 is secured to the stranded conductor 44 within the central bore 49 formed in the cap 42 by crimping the sleeve portion 43 of the cap to retain the conductor and fuse element 46 in assembly with the cap. The fuse 16 can also be provided with an elongated thin walled plastic tube or sheath, not shown, disposed around the fuse element 46 and spaced somewhat therefrom but within the bore formed by the tube 24 and the resistor element 40. Such a tube is adapted to surround the fuse element to confine low current arcing within the tube upon rupture of the fuse element 46 but which would burst on relatively high fault currents.
By providing the arc intercepting member 33 and also the resistor element 40 as part of the fuse structure, the improved fuse 16 of the present invention is operable to direct the electrical arc generated upon melting of the fuse element 46 in such a way that the fault current passes through the resistor element 40 and is momentarily reduced sufficiently to allow the gases generated within a chamber 47 formed by the bores of the resistor 40 and the tube 24 to extinguish the arc and prevent arc restrike after the current passes through the zero point on its wave form. The combination of the system grounding impedance and the resistive impedance of the resistor element 40 is sufficient to reduce fault currents in the 3,000 to 35,000 amp range and higher to values which have been successfully interrupted using the technique of arc extinguishment by the generation of a deionizing gas in the vicinity of the arc. The resistor element 40 is not a primary conductor element of the circuit except on separation of the fuse element 46 and establishment of an arc which is intercepted by the member 33. However, the resistor element 40 is inserted in the circuit as rapidly as the creation of the arc.
In accordance with another important aspect of the present invention, by providing the elongated conductor rod 20 of a soft annealed steel such as, for example, SAE 1019 low carbon steel, the rod is capable of generating a magnetic field 56 having a flux sufficient to direct an arc generated upon rupture or melting of the fuse element 46 in such a way that the arc remains in proximity to the interior of the fiber tube 24. By forcing the arc against the interior of the fiber tube, greater amounts of deionizing gas are quickly generated than would occur if the arc location were not controlled. At the same time, the arc is also, of course, directed into contact with the intercepting member 33 whereby the fault current passes through the resistor element 40 to momentarily reduce the current value as described above.
Another important aspect of the structure and function of the present invention pertains to the arrangement whereby the interior chamber 47 formed by the bores of the tube 24 and the resistor element 40 is substantially sealed except for the vent hole 28. The fit between the conductor rod 20 and the fiber tube 24 is substantially fluid tight as is the fit between the tube 41 and the members 24 and 40. The conductor 44, which is preferably of stranded wire, presents substantial resistance to rapid fluid flow through the bore 49 but has sufficient porosity to allow oil to enter the interior of the fuse. Accordingly, gas generated within the chamber 47 upon failure of the fuse element 46, is substantially confined to the interior of the fuse with some controlled venting through the vent hole 28. The vent hole 28 also allows the interior of the fuse to fill with oil or other fluid from the transformer tank when immersed therein, as illustrated.
Under certain operating conditions, upon failure of the fuse element 46 and shunting of the fault current through the resistor element 40, the resistor element will be heated sufficiently to melt the solder 45 joining the cap 42 to the resistor element. Accordingly, the pressure generated by the formation of the deionizing gas within the interior of the resistor would forcibly eject the cap 42 from the end of the resistor element into the transformer tank a sufficient distance to prevent sustainment of an arc.
Accordingly, the fuse 16 provides multiple arc extinguishment features comprising the shunt resistor 40 and the provision of an expulsion cap 42 which operates to physically separate the conductor 44 from proximity to the conductor rod 20 a sufficient distance to prevent sustainment of the fault current arc. Moreover, the fuse 16 is arranged within the support bushing 14 such that the resistor element 40 extends from the lower end of the bushing. Accordingly, in situations where a fault current arc may be occurring within the interior of the transformer tank enclosure as caused by either over voltage, lightning strike or insulation degradation, the arc can then move into contact with the resistor element whereby the circuit is established through the resistor element 40 to reduce the arc current sufficiently to effect extinguishment of the arc.
As indicated hereinabove, the materials of construction of the fuse 16 are of some importance, including the material used for the conductor rod 20. The rod 20 is preferably formed of cold rolled soft steel which has been annealed and plated with a suitable corrosion resistant plating or coating. The tube 24 is of a type which is known for use in connection with fuses for distribution transformers and the like and is formed of an organic fiber which generates a substantial amount of deionizing gas to counteract the generation of ionized gas produced by the arc in the presence of the transformer oil or other insulating fluid. The provision of the arc intercepting member 33 of soft steel or copper alloy with the curved surface 35 reduces the dielectric stress concentration in this element. The resistor element 40 may take various forms although the type of element described herein is preferable in that it provides a compact and suitable structural arrangement for the fuse itself. The particular commercial element described herein is provided with metallized ends to facilitate fixing the resistor element to the sleeve member 30 and to the cap 42 by soldering, as described.
Those skilled in the art of high voltage protective devices will appreciate from the foregoing that a superior protective link has been provided by the present invention which is economical to manufacture, and is reliable in operation. The fuse 16 includes a number of superior features which function in combination to provide for circuit clearing in high voltage and high amperage short circuit conditions such as are experienced in a number of electrical devices and, in particular, in electrical distribution system transformers. Those skilled in the art will also appreciate that various substitutions and modifications may be made to the present invention without departing from the scope of the appended claims. | A protective fuse comprising a fusible element disposed within an enclosure formed by a gas generating fiber tube connected at one end to a conductor rod and at the other end to an arc intercepting member. The arc intercepting member is connected to an elongated tubular resistor element which in turn is connected at its opposite end to a cap comprising a conductor connected to the fusible element. Upon parting of the fusible element an arc established by the fault current comes into contact with the arc intercepting member so that a circuit is established through the resistor element thereby momentarily reducing the fault current to a level which can be extinguished by the deionizing gases generated within the interior of the fuse. The conductor rod is formed of a magnetic material which is capable of generating a substantial magnetic flux which functions to bias the arc against the interior wall of the fiber tube to enhance the generation of deionizing gases. The resistor element is soldered to the arc intercepting member and the conductor cap with solders having different melting points whereby the cap may be blown off the resistor to lengthen the distance between conductor elements. | 7 |
FIELD OF THE INVENTION
The invention relates generally to control and payload systems for small underwater vehicles, and more particularly to an improved system for controlling position of a small underwater vehicle and for a modular payload system for a small underwater vehicle.
BACKGROUND OF THE INVENTION
A-size underwater vehicles (i.e., those having a size of about 4⅞″ diameter×36″ long) are often used as simulators for testing a variety of Navy shipboard systems. For example, such vehicles can be outfitted with systems that simulate the noise of a submarine or other water-borne vehicle or device, and are used to teach other systems to detect and recognize such noises as being associated with that specific device.
Currently there are no A-size underwater vehicles that employ stable, energy efficient, linear controls. At present, these small underwater vehicles have directional controls that are either binary (i.e., on-off) controls or which use linear motors that must be constantly electronically actuated to hold the vehicle on a desired position or course. Binary controls, which apply either full left rudder or full right rudder, cause the vehicle to swim erratically, while linear motors use too much power, since they employ a solenoid that must be constantly “on” in order to hold the rudder/elevator at a particular position. Thus, there is a need for an improved control system for an underwater vehicle that is stable, and that requires less power than existing systems.
Furthermore, current A-size underwater vehicles employ fixed payload sections which, as previously noted, may contain devices such as noisemakers for simulating the noise signature of a particular water-borne vehicle or device. Having a fixed payload section, however, limits use of the vehicle to specific applications and thus a larger number of such vehicles must be kept on hand to address a typical array of testing requirements. Thus, there is a need for an improved underwater vehicle having a simple modular payload arrangement that allows a variety of payloads to be simply and efficiently interchangeable with a single vehicle body.
SUMMARY OF THE INVENTION
A system is disclosed for controlling an underwater vehicle. The system may comprise a linear control assembly having a motor and a threaded rod. The motor may be engaged with an internally threaded member that is threadably engaged with the threaded rod. A control rod is connected to the threaded rod and a fin assembly is connected to the control rod. Thus arranged, actuation of the motor rotates the internally threaded member, thereby causing a linear movement of the threaded rod, the control rod, and the fin assembly.
A modular payload system is also disclosed for an underwater vehicle having a payload section and a central body section. The system includes a payload section having a bulkhead section, and a central body section. The central body section may have a circumferential lip portion and a plurality of fasteners circumferentially disposed on the lip portion. The bulkhead section may further include a plurality of L-shaped recesses positioned to receive the plurality of fasteners, each of the L-shaped recesses having an axially-disposed opening and a transversely disposed locking section. The central body section is engageable with the bulkhead section by aligning the plurality of fasteners with the axially-disposed openings of the recesses, pressing the bulkhead section toward the central body portion, and twisting the bulkhead portion with respect to the central body portion to engage the plurality of fasteners with the transversely disposed locking sections of the plurality of recesses.
DESCRIPTION OF THE DRAWINGS
The details of the invention, both as to its structure and operation, may be obtained by a review of the accompanying drawings, in which like reference numerals refer to like parts, and in which:
FIG. 1 is a side view of an A-size underwater vehicle;
FIG. 2 is a schematic of the interrelation of the components of the vehicle of FIG. 1 , taken along line 2 - 2 ;
FIG. 3 is an isometric view of the vehicle of FIG. 1 , showing the positioning of a communications antenna; and
FIG. 4 is an isometric view of the disclosed control system for use in the vehicle of FIG. 1 ;
FIG. 4A is a side view of an exemplary linear actuator for use in the vehicle of FIG. 1 ;
FIG. 5 is an isometric view of the control system of FIG. 4 fitted in the tail section of the vehicle of FIG. 1 ;
FIG. 6 is a side view of the control system and tail section of FIG. 5 ;
FIG. 7 is a top view of the control system and tail section of FIG. 5 ; and
FIGS. 8-11 are isometric views of the connection arrangement between the body section and the payload section of the vehicle of FIG. 1 .
DETAILED DESCRIPTION
In the accompanying drawings, like items are indicated by like reference numerals. This description of the preferred embodiments is intended to be read in connection with the accompanying drawings, which are to be considered part of the entire written description of this invention. In the description, relative terms such as “lower,” “upper,” “horizontal,” “vertical,”, “above,” “below,” “up,” “down,” “top” and “bottom” as well as derivative thereof (e.g., “horizontally,” “downwardly,” “upwardly,” etc.) should be construed to refer to the orientation as then described or as shown in the drawing under discussion. These relative terms are for convenience of description and do not require that the apparatus be constructed or operated in a particular orientation. Terms concerning attachments, coupling and the like, such as “connected” and “interconnected,” refer to a relationship wherein structures are secured or attached to one another either directly or indirectly through intervening structures, as well as both movable or rigid attachments or relationships, unless expressly described otherwise.
The disclosed system comprises an underwater vehicle having directional controls including screw-type linear actuators and position feedback controls. The screw-type linear actuators hold fin position using a fine pitched thread, which requires no continuous external electric power to maintain position. The disclosed system provides increased accuracy and control of the underwater vehicle as compared to current systems. The screw-type linear actuator also minimizes noise and power consumption, since the incline of the screw holds its position under load, without the need for external electrical power.
The disclosed system also includes a modular payload arrangement in which a quick connect bulkhead section enables quick connection/disconnection of the payload section from the rest of the vehicle via a single faster and a plurality of retaining pins. With this arrangement the user can simply loosen one fastener and twists the payload section to detach the section from the vehicle. A single user can manipulate and deploy the vehicle in minutes on the deck of a ship or rubber inflatable boat (RIB). The disclosed design is self contained and makes swapping out payloads a clean and simple transition.
Referring to FIGS. 1 and 2 , an underwater vehicle 1 is shown having a forward payload section 2 , a central body section 4 , and an aft propulsion section 6 . The payload section 2 may comprise a tapered nose 8 for reducing drag, while the central body section 4 may have a generally cylindrical shape and may contain the vehicle's battery assembly 10 , guidance, navigation and communications components. The propulsion section 6 may include a tapered aft portion 14 ending in a propulsion and steering assembly 16 .
The payload section 2 houses the vehicle's payload, which may include any of a variety of communications, sensing or ordnance devices, including, without limitation, sound simulation equipment, a camera, a Doppler velocity log, up-looking sonar, a conductivity-temperature-density measuring device, and the like. The payload section 2 may also include a standalone payload processor 18 for communicating with and/or controlling the payload. Where the payload is a sensor 19 , the payload processor 18 may receive and process data from the sensor. A signal conditioner 21 may be provided in communication with the sensor 19 to condition signals from sensor prior to their transmission to the payload processor 18 . The payload processor 18 may be in communication with a main processor 20 for the vehicle 1 , and may function to reduce the processing load on the main processor. This is an advantage over prior designs in which the main vehicle processor 20 runs all controls and sensors in the vehicle. In one embodiment, the payload processor communicates with the main processor 20 and tells it what the sensor is sensing. For example, if the payload sensor senses a mine near the vehicle, the payload processor 18 may send a signal to the main processor 20 to instruct it to control the vehicle to perform a desired action (e.g., stay, go). In one embodiment, the payload processor 18 is disposed on the forward side of a quick disconnect bulkhead 68 (see FIG. 8 ) inside the payload section 2 . It can communicate via a network cable to the main processor 20 via a single connection.
The main processor 20 may be connected to a data logger 23 to enable continuous storage of sensor and/or mission data received by and/or processed by the main processor 20 . The main processor 20 may also be in communication with a plurality of vehicle sensors 27 such as depth sensors or the like. A signal conditioner 31 may be provided to condition signals from the vehicle sensors 27 sensor prior to their transmission to the main processor 20 .
The payload section 2 may be connected to the central body section 4 using a quick connect/disconnect arrangement, which will be described in greater detail later. As previously noted, the central body section 4 may house the vehicle's battery 10 , which may be a rechargeable or replaceable battery. In one embodiment, the battery 10 is fixed within the central body section 4 and is provided with a power interface to allow recharging by plugging the battery into a power source on board a host vessel. In another embodiment, the battery 10 is removable from the central body section 4 so that, when depleted, the battery can be unplugged and replaced with a fully charged battery to enable quick redeployment of the vehicle 1 .
As noted, the central body section 4 may also include guidance, navigation and communications components. In one embodiment, these components include a series of printed wire boards (PWBs) in communication with the battery 10 . These PWBs may control the navigation, guidance and control functions of the vehicle 1 . The main processor 20 may be included on one of the PWB's, or it may be part of a separate board or card. Regardless of the physical arrangement, the main processor 20 communicates with, and controls the operation of, the PWBs. One of the PWB's may be a navigation board 24 , which can include, or connect to, a compass or Inertial Measuring Unit (IMU) and a global positioning system (GPS) 25 . Another of the PWB's may be a guidance board 26 , which may include a control loop that accepts, for example, depth sensing information and vehicle heading information and controls the vehicle to turn, dive or surface. Another of the PWB's may be a communications board 28 , which may include a WiFi connection 29 , a satellite modem, and/or a control and mission algorithm to enable a ship-based or land-based user to communicate with the vehicle's main processor 20 or payload processor 18 while the vehicle is in the water or on the deck of a host ship. In one embodiment, the communications board 28 enables a user to locally program the main processor 20 and/or the payload processor 18 using a laptop computer or handheld device. The user may program a mission or run-plan for the vehicle 1 via the vehicle's wireless link. Alternatively, the wireless link may enable user to download data collected by the vehicle during its run. As shown in FIG. 3 , the vehicle may be provided with an antenna 30 to facilitate modem operations. The antenna 30 may be embedded in the vehicle fin, mounted flush on the hull, or it may be retractable and/or optional depending on the vehicle's particular mission application.
The modem may also enable the payload processor 18 and/or the main processor 20 to communicate with other unmanned vehicles or with a local buoy, which can then transmit data collected by the vehicle (or vehicles) to a satellite transmission system and/or a nearby vessel. In one embodiment, the vehicle may collect data, surface, and call a host ship. The host ship may then retrieve the vehicle and download the vehicle's collected data to a shipboard computer.
The battery 10 may be connected to a DC/DC converter 11 for powering the PWB's 24 , 26 , 28 . In addition, battery power may be used, either directly, or via the DC/DC converter 11 , to power some payloads.
The propulsion section 6 is positioned immediately aft of the central body section 4 and may be attached thereto by a permanent or removable connection. As shown in FIG. 2 , the propulsion section 6 may include a linear actuator control 32 , a propulsion motor 34 , linear actuators 36 a, b and a steering assembly 16 . The steering assembly 16 may include a pair of rudders 38 , and a pair of elevators 40 . The linear actuator control 32 is in communication with one or more of the PWB's 24 , 26 , 28 for receiving control commands from the main processor 20 and to instruct the linear actuators to start and stop.
Referring to FIGS. 4-7 , the linear actuators 36 a, b are shown, along with connections to the associated rudders 38 and elevators 40 . Each of the linear actuators 36 a, b includes a linkage rod 42 a, b that connects to a central linkage 44 a, b of the associated rudders 38 and elevators 40 to move the rudders/elevators via corresponding movement of the actuators. As can be seen, the individual rudders 38 are connected together via central linkage 44 a , while the individual elevators 40 are connected together via central linkage 44 b . The rudders 38 and elevators 40 further each include an extension rod 46 , 48 that rotatably connects the rudder/elevator to an inner surface of the propeller shroud 50 ( FIGS. 2 , 5 ) so that when linear actuator 36 a moves the central linkage 44 a , the rudders 38 rotate together about the extension rod 46 to change their angle of inclination with respect to the vehicle. Likewise, when linear actuator 36 b moves the central linkage 44 b , the elevators 40 rotate together about the extension rod 48 to change their angle of inclination with respect to the vehicle.
FIG. 5 shows the linear actuators 36 a, b positioned within the aft structure of the propulsion assembly 6 . In this embodiment, the actuators are mounted on an intermediate bulkhead 52 so that they straddle the opening 54 that houses the vehicle's propulsion shaft bearing and seal (not shown).
Referring to FIG. 4A , each of the linear actuators 36 a, b may comprise an actuator element 56 , a threaded rod 58 , a position sensor 60 and a spring compensator 62 . A coupling 64 is provided at an aft end of the actuator 36 a, b for engaging an associated extension rod 42 a, b . The actuator element 56 may comprise a motor that spins a threaded nut 57 , which in turn, engages the threaded rod 58 to more forward. Actuation of the motor in a second direction causes the threaded rod 58 to move aft. When coupled to an extension rod 42 a, b , rotation of the motor controls the angular position of the rudders 38 and elevators 40 .
In one embodiment, the position sensor 60 comprises a slide rheostat which changes resistance with a change in rod position. As the threaded rod 58 moves, the rheostat provides feedback to a control loop to inform the linear actuator control 32 that the elevators (or rudders) are positioned at, for example 10-degrees. The control system, in turn, can order a change in position by controlling the motor to spin the nut 57 , thereby moving the threaded rod, and actuating the associated elevators/rudders to achieve the desired movement of the vehicle.
Self locking of the threaded rod 58 is obtained whenever the coefficient of friction is equal to or greater than the tangent of the thread angle. This is a function of pitch and friction. Thus, a fine thread per inch will produce this self-locking condition due to small thread angle and increased coefficient of friction.
The spring compensator 62 may be a coil spring calibrated to compensate for the forces of seawater pressure on the linear actuator 36 a, b . As will be understood, sea pressures at increased depths can counteract the force of the linear actuators 36 a, b , hindering or preventing them from moving the linkage rods 42 a, b . This is because the linkage rods are subject to full sea pressure, while the linear actuators 36 a, b are subject only to the pressures associated with the interior of the vehicle (the dividing line is shown in the figures as the intermediate bulkhead 52 ). To counteract the forces of sea pressure on the linkage rods, the spring compensator 62 provides a pre-load on the threaded rod 58 that acts in direction opposite to the load applied by the sea.
Thus arranged, the rudders 38 and elevators 40 can be adjusted simply by rotating the threaded nut and translating the associated threaded rod by a desired amount. Once a desired position of the elevators and/or rudders has been achieved, the actuator element 56 is turned off and the position of the rod (and the elevators or rudders) is held constant without the need for further operation of the actuators 36 a, b . As previously noted, this fixed positioning feature results from the use of a fine thread pitch on the nut and threaded rod. Fine thread pitches are exceptionally resistant to rotation when subjected to large axial forces, such as the force of sea pressure and the forces applied to the rudders and elevators as the vehicle moves through the water.
Referring now to FIGS. 8-11 , the disclosed modular connection arrangement between the payload section 2 and the central body section 4 will be described in greater detail. As previously noted, providing a quick connect/disconnect arrangement facilitates quick change-out of vehicle payloads and batteries, resulting in a highly versatile vehicle.
FIG. 8 shows the payload section 2 and central body section 4 connected via a quick disconnect bulkhead 68 . The quick disconnect bulkhead 68 may be a cylindrical ring that approximates the outer diameter of the payload section 2 and the central body section 4 to provide a smooth and uninterrupted exterior surface between the sections. As shown in FIG. 11 , the quick disconnect bulkhead 68 is sized so that its inner surface 70 fits over, and engages, a circumferential lip portion 72 of the central body section 4 . An opposite side of the quick disconnect bulkhead 68 may be fixed to the payload section 2 by fasteners, welding or other appropriate connection arrangement. The quick disconnect bulkhead 68 may be sealed to the circumferential lip portion 72 of the central body section 4 via an o-ring seal.
The circumferential lip portion 72 of the central body section 4 may carry first and second fasteners 74 , 76 configured to mate with corresponding first and second recesses 78 , 80 in the quick disconnect bulkhead 68 . In the illustrated embodiment, the first fastener 74 may be a screw-type fastener having an increased diameter head 82 and a threaded body 84 ( FIG. 11 ). The first fastener 74 may be sized to engage the first recess 78 in the bulkhead 68 . In the illustrated embodiment, the first recess 78 is an L-shaped recess having an axially-oriented open mouth section 78 a and a transversely-oriented locking section 78 b . The locking section 78 b may have a bevel that matches a corresponding bevel of the head 82 of the first fastener 74 such that when the first fastener is engaged with the locking section 78 b of the first recess 78 and the fastener is tightened, the head 82 of the fastener engages the locking section 78 b to lock the bulkhead 68 to the central body section 4 .
A plurality of second fasteners 76 may be provided at spaced intervals around the circumference of the circumferential lip portion 72 . Likewise, a plurality second recesses 80 may be correspondingly spaced around the circumference of the quick disconnect bulkhead 68 . In the illustrated embodiment, the second fasteners 76 are cylindrical pins, and the second recesses 80 are L-shaped recesses having an axially-oriented open mouth section 80 a and a transversely oriented locking section 80 b . In contrast to the first fasteners, the second fasteners do not have an increased diameter head portion, and thus they do not lock down onto quick disconnect bulkhead. Rather, they serve as retention pins, preventing axial movement of the payload section (and bulkhead section) with respect to the central body section when received within the locking section 80 b of the associated recess.
It will be appreciated that, although the second fasteners 76 have been described as being pins, they (as well as the second recesses 80 ) could instead be of the same design as that of the first fasteners 74 and the first recesses 78 . Further, although the illustrated embodiment contemplates a total of four fasteners and four recesses, fewer or greater numbers of fasteners and recesses could be provided as desired. It will also be appreciated that it is not critical to provide a separate bulkhead element, and thus the locking features described in relation to the bulkhead could instead be implemented directly in the payload section 2 , or the bulkhead could be an integral part of the payload section or the central body section. Moreover, although the bulkhead is described as fitting over a portion of the central body section, an opposite arrangement could be provided, with fasteners provided on the bulkhead and corresponding recesses provided in the central body section.
Referring again to FIG. 8 , the quick connect bulkhead 68 is shown locked in place, with the first and second fasteners 74 , 76 residing in the transversely oriented locking sections 78 b , 80 b of their respective recesses 78 , 80 . To disconnect the payload section 2 from the central body section 4 , the first fastener 74 is loosened as shown in FIG. 9 , so that the fastener head 82 disengages from the locking section 78 b of the first recess 78 . As shown in FIG. 10 , the payload section 2 (and bulkhead 68 ) are then twisted in the direction of arrow “A” so that the first and second fasteners 74 , 76 align with the axially oriented open mouth sections 78 a , 80 a of the associated recesses 78 , 80 . Since the second fasteners 76 do not tighten down onto the surface of the bulkhead 68 , there is no need to loosen these fasteners in order to twist the bulkhead. The payload section 2 and bulkhead 68 are then moved axially in the direction of arrow “B” to disconnect them from the central body section 4 . One connector may be provided that carries all wires (e.g., power, digital, analog, network) that provide communications between the payload section 2 and the central body section 4 .
In this manner the payload section 2 can be quickly disassembled from the central body section 4 simply by loosening a single fastener, and twisting the two apart. The user can then quickly install another payload section with the central body section 4 and send the vehicle back out on another run. Alternatively, the user can reattach the payload section 2 to another central body section 4 having a fully charged battery 10 . In another case, the user can simply remove a depleted battery 10 from the central body section, install a fully charged battery, reinstall the payload section 2 and send the recharged vehicle back out on another run.
Although the system has been described in relation to A-sized vehicles it will be appreciated that the arrangements disclosed herein could find application in any of a variety of vehicles of different sizes and configurations.
Further, although the invention has been described in terms of exemplary embodiments, it is not limited thereto. Rather, the appended claims should be construed broadly, to include other variants and embodiments of the invention, which may be made by those skilled in the art without departing from the scope and range of equivalents of the invention. | A system for enhancing control of an underwater vehicle, and providing a quick change modular payload section includes a motor configured to rotate an internally threaded member threadingly engaged with a threaded rod. Rotating the member creates linear motion of the threaded rod. A control rod connected to the threaded rod provides movement of a rudder or fin. The threaded rod and member are configured with threads having a fine pitch which maintains a stable position of the fins without needing to supply power to the motor for adjustments. The modular payload arrangement includes a bulkhead ring having L-shaped recesses that receive fasteners disposed on a central body section. The payload section may be fastened to the vehicle by pressing the payload section onto the central body such that the fasteners align with the recesses and turning the payload section to secure the payload section. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to automatic method and apparatus for pick-up sewing of curved edges of a fabric piece on clothing, and more particularly relates to computerized automation of a process for pick-up sewing of curved edges of a fabric piece such as an outer pocket to clothing such as a jacket.
Automation has increasingly been introduced into the field of sewing of clothing but pick-up sewing of outer pockets on jackets or the like is still performed by manual operation without allowing introduction of automation. This is due to the fact sewing of curved edges of fabric pieces such as outer pockets on jackets or the like necessitates very complicated movement of a sewing needle. Thus handling of the sewing needle requires highly skilled technique and causes significantly low process efficiency.
SUMMARY OF THE INVENTION
It is the object of the present invention to fully automatize under computer control pick-up sewing of curved edges of a fabric piece on clothing.
In accordance with the basic aspect of the present invention, clothing kept in a horizontal state and pressed against a sewing needle is displaced two dimensionally as programmed by combined operations of X- and Y- directional shifter units having respective servo motors on receipt of operation signals issued by a center control circuit under computer control while the sewing needle on a sewing unit is driven for concurrent horizontal rotation by operation of a servo motor also connected to the above-described center control circuit, whereby the point of the sewing needle should always be directed in tangential directions of a sewing line on the fabric piece.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of one embodiment of the automatic apparatus in accordance with the present invention,
FIG. 2 is a side view partly in section, of the pressor unit used for the automatic apparatus shown in FIG. 1,
FIG. 3 is a fragmentary perspective view of clothing on which a fabric piece is pick-up sewn along a curved sewing line, and
FIG. 4 is a fragmentary perspective view of another embodiment of the automatic apparatus in accordance with the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
One embodiment of the automatic apparatus in accordance with the present invention is shown in FIG. 1, in which the apparatus includes a flat and horizontal base plate 1 and a flat and horizontal operation table 2 which can be properly secured to the base plate 1. The operation table 2 is adapted for placing clothing to be sewn thereon and provided with a circular opening 2a. A circular rotary disc 3 is concentrically received in the circular opening in an arrangement flush with the top face of the operation table 2. The rotary disc 3 is provided with a center opening 3a.
The apparatus further includes, as major elements, a sewing unit 20 for pick-up sewing, a pressor unit 40 for pressing the fabric piece of the clothing to be sewn, a clothing controller 90 for moving the clothing two dimensionally on the operation table 2 as programmed, a X-directional shifter unit 60 for shifting the pressor unit 40 in the X direction and a Y-directional shifter unit 80 for shifting the pressor unit 40 in the Y direction.
Sewing unit of any conventional types are usable for the present invention. In the case of the illustrated embodiment, the sewing unit 20 includes a holder bracket 21 which is made up of a pair of spaced, parallel and vertical walls 21a, 21b and a bottom section 21c connecting the vertical walls 21a and 21b. One vertical wall 21a securedly carries a needle drive motor 22 whose output shaft 22a extends rotatably through the vertical walls 21a and 21b and, outside the holder bracket 21, securedly carries a cam disc 23. Another vertical section 21b has an upper extension 21d located somewhat below the rotary disc 3 and a needle holder 24 is pivoted at its lower end to the upper extension 21d of the holder bracket 21. The needle holder 24 carries a sewing needle N facing the center opening 3a of the rotary disc 3. The upper extension 21d of the holder bracket 21 further carries a bobbin case 25 which contains a thread to be used for sewing. The bobbin case 25 is located just below the center opening 3a of the rotary disc 3 at a position to be operated by the needle N. The holder bracket 21 is secured, via a part of the upper extension 21d, to the bottom face of the rotary disc 3. A pin 26 secured to the needle holder 24 above its lower pivot is linked, via a connecting rod 27, to a pin 28 secured near the periphery of the cam disc 23. A servo motor 29 is located below the holder bracket 21 and its output shaft is coupled to a rotary shaft 30 via a connector 31. The top end of the rotary shaft 30 is secured to the bottom face of the holder bracket 21. The servo motor 29 is connected to a center control circuit which issues operation signals under computer control.
As the needle drive motor 22 operates, the cam disc 23 rotates and the needle holder 24 swings about its lower pivot so that the need N should deliver a thread from the bobbin disc 25 for pick-up sewing. As the servo motor 29 is driven for operation on receipt of an operation signal from the center control circuit, the holder bracket 21 with the needle N and the rotary disc 3 rotates in the horizontal direction about the center of the rotary disc 3.
The pressor unit 40 includes a solenoid 41 secured vertically on the operation table 2 and the plunger 41a of the solenoid holds a horizontal arm 42. The horizontal holder arm 42 carries at its free end a pressor bar 43 which extends downwards and directed to the center of the rotary disc 3.
On operation of the solenoid 41, the pressor rod 43 moves downwards in order to press the section of the clothing to be sewn into the center opening 3a of the rotary disc 3 as shown in FIG. 2.
The X-directional shifter unit 60 includes a pair of spaced parallel guide rails 61 secured on the base plate 1 and a horizontal mobile block 62 slidably mounted to the guide rails 61. The guide rails 61 extend in the X direction. A threaded drive shaft 63 extends on the base plate 1 in parallel to the guide rails 61 while being rotatably carried by bearings 64. The drive shaft 63 is in screw engagement with a thread piece 65 secured to the bottom face of the mobile block 62. One end of the drive shaft 63 is coupled via a connector 66 to a servo motor 67 arranged on the base plate 1. This servo motor 67 is also connected to the above-described center control circuit. As the servo motor 67 is driven for operation on receipt of an operation signal from the center control circuit, the drive shaft 63 rotates so that the mobile block 62 should move in the X-direction along the guide rails 61.
The Y- directional shifter unit 80 includes a guide rail 81 secured on the mobile block 62 of the X-directional shifter block 60 and a horizontal mobile block 82 slidably mounted to the guide rail 81. The guide rail 81 extends in the Y direction. A threaded drive shaft 83 extends on the mobile block 62 in parallel to the guide rail 81 while being rotatably carried by bearings 84. The drive shaft 83 is in screw engagement with a thread piece 85 secured to the bottom face of the mobile block 82. One end of the drive shaft 83 is coupled via a connector 86 to a servo motor 87 arranged on the mobile block 62 of the X-directional shifter unit 60. This servo motor 87 is also connected to the above-described center control circuit. As the servo motor 87 is driven for operation on receipt of an operation signal from the center control circuit, the drive shaft 83 rotates so that the mobile block 82 should move in the Y direction along the guide rail 81.
The clothing controller 90 takes the form of an elongated flat plate fixed at one end to the mobile block 82 of the Y-directional shifter unit 80. The other end of the clothing controller 90 terminates near the rotary disc 3 in the operation table 2. The level of the clothing controller 90 should preferably be adjustable so that the clothing to be sewn should be clamped firm between the top face of the operation table 2 and the bottom face of the clothing controller 90 as best seen in FIG. 2.
Thus, as the servo motors 67 and 87 are driven for operation on receipt of the operation signals from the center control circuit, the clothing controller 90 and the clothing clamped thereby move on the operation table 2 in X and Y directions as programmed under computer control and, concurrently, operation of the servo motor 29 caused by receipt of the operation signal from the center control circuit makes the needle N rotate in the horizontal direction as programmed under computer control so that the point of the needle should always be directed in tangential directions of the sewing line L on the clothing C (see FIG. 3). Sewing operation of the needle N itself is driven by the needle drive motor 22 on the holder bracket 21.
As shown in FIG. 3, the present invention is most typically applied to pick-up sewing of an outer pocket P to the clothing C. However, by properly changing the programme to be loaded on the computer, the apparatus in accordance with the present invention is usable for pick-up sewing of any fabric pieces to clothing which have curved sewing lines.
In the case of the embodiment shown in FIG. 1, the section of the clothing to be sewn is pressed to the needle N by operation of a pressor rod 43 carried by the holder arm 42. The pressor rod 43 is axially displaceable but blocked against axial rotation. When pick-up sewing is carried out along a curved section of a sewing line, absence of the axial rotation of the pressor rod 43 tends to cause unstable follow of the fabric piece of the clothing to be sewn to the horizontal rotation of the sewing unit 20 generated by the operation of the servo motor 29. Such unstable follow connects to disorder in the sewing line whilst impairing the appearance of the clothing processed. Such unstable follow further increases loads on the servo motors 67 and 87 for the shifter units 60 and 80 and, as a consequence, degrades smoothness in movement of the clothing controller 90.
These troubles may be avoided if the pressor rod 43 is rotated axially in synchronism with the horizontal rotation of the sewing unit 20. This requirement is satisfied by use of another embodiment of the apparatus in accordance with the present invention shown in FIG. 4, in which elements substantially same in construction and operation as those used for the embodiment shown in FIG. 1 are indicated with same reference numerals.
In the case of this embodiment, the holder bracket 21 of the sewing unit 120 is secured to the top of a hollow rotary shaft 130 and a spar gear 31 is secured to the lower end of the rotary shaft 130 in meshing engagement with a spar gear 132 secured to the output shaft of a servo motor 29. Like the first embodiment, this servo motor 29 is also connected to the central control circuit which issues operation signals under computer control.
A rod 133 of a smaller diameter extends freely through the rotary shaft 130 and freely through the bottom section 21c of the holder bracket 21. The top end of the rod 133 is coupled to a pin 134 secured near the periphery of a cam disc 135. The cam disc 135 is secured to the output shaft 22a of the needle drive motor 22. The lower end of the rod 133 is coupled via a pivotal joint 136 to one end of a swing lever 137 which is pivoted to a fixed stand 138. The other end of the swing lever 137 is pivoted to the lower end of a connecting link 139.
The pressor rod 43 is coupled via a connector 141 to a rod 140 which extends through a rotary shaft 142. The rod 140 and the rotary shaft 142 are in spline engagement with each other. That is, the rod 140 is axially displaceable in the rotary shaft 142 but follows rotation of the rotary shaft 142. The top end of the rod 140 is coupled via a pivotal joint 143 to one end of a swing lever 144 which is pivoted to a fixed stand 145. The other end of the swing lever 144 is pivoted to the top end of the connecting link 139.
In the case of this embodiment, the holder arm 42 is secured at its one end to an upright post 146 mounted to the operation table 2. The holder arm 42 rotatably carries the rotary shaft 142 which securedly carries a spar gear 147. The holder arm 42 further carries at its another end a servo motor 148 whose output shaft carries a spar gear 149 in meshing engagement with the spar gear 147 on the rotary shaft 142. The servo motor 148 is connected to the center control circuit so that it should operates in synchronism with the operation of the servo motor 29 for the sewing unit 20.
On operation of the needle drive motor 22, the rod 133 moves up and down and this movement is transmitted to the pressor rod 43 via the elements 137, 139, 144 and 140. In this way, the vertical movement of the pressor rod 43 is generated in synchronism with the swing motion of the needle N which, as in the first embodiment, is also caused by the needle drive motor 22. As the servo motor 29 operates to rotate the sewing unit 120 with the needle N, the pressor rod 43 follows this rotation being driven by the servo motor 148 synchronized in operation with the servo motor 29.
Use of this embodiment assures smooth control on movement of the clothing in the operation table 2, thereby avoiding undesirable disorder in the sewing line on the clothing. Further, when compared with the first embodiment, loads on the servo motors 67 and 87 for the shifter units 60 and 80 are greatly reduced and, as a consequence, movement of the clothing controller 90 is significantly smoothed. | In an automatic pick-up sewing system for curved edges of a fabric piece such as an outer pocket on clothing such as a jacket, the clothing kept in a horizontal state with the fabric piece pressed against a sewing needle is displaced two dimensionally during pick-up sewing as programmed under computer control while the sewing needle is driven for concurrent horizontal rotation so that the point of the sewing needle should always be directed in tangential directions of a sewing line on the fabric piece. Beautiful pick-up sewing is achieved quite at high efficiency without any need for highly skilled manual operation. | 3 |
BACKGROUND OF THE INVENTION
This application is a continuation in part application of U.S. Patent Application Ser. No. 08/192,599 filed Feb. 7, 1994 by Edward Sucato and John A. Powers III and entitled STUD ASSEMBLY.
This invention relates to channels or studs for walls of buildings and more particularly to a stud assembly comprising a pair of channels held together by a stiffener at one or more points or places along their length to form a new and improved stud assembly.
DESCRIPTION OF THE PRIOR ART
Todate, the studs of buildings comprise U-shaped configurations the legs of which are bent over at a ninety degree angle to face each other. These studs forming channels were usually formed of metal thick enough to form a rigid structure and because of the metal content are costly to manufacture and the solid configuration allows a higher degree of heat transfer. Thus, a need exists for a plastic or metal stud or channel structure which will serve its function, contain a reduced amount of plastic or metal content, reduces heat transfer and noise transmission and retain the rigidity or stiffness of the prior art structures.
The following U.S. patents disclose studs and ceiling joists employing a cross member for stiffening the structure.
______________________________________ 1,011,583 1,849,811 1,242,892 2,089,023 1,360,720 2,141,642 1,696,039 2,157,233 1,762,112 2,668,606 1,839,178______________________________________
U.S. Pat. No. 2,998,108 discloses a structural post assembly for walls employing an interlocking bite.
U.S. Pat. No. 3,995,403 discloses a structural building module employing sections joined together by cross members.
U.S. Pat. No. 4,291,515 discloses a structural element employing a webbing in the form of a zig-zag strip.
U.S. Pat. No. 5,095,678 discloses a structural stud having an open faced end flange that can be snap fitted into the end of a similar stud.
The British patent application GB 2205875A discloses a composite beam having parts to fill both sides of a wall.
U.S. Pat. No. 768,594 to Finlay discloses a hollow tube c2 connected to a bite of channels b2.
U.S. Pat. No. 2,082,792 to Dean shows a trough at 15 or 16 with a connection at 7 to U-shaped channel members 1, 2.
U.S. Pat. No. 2,284,898 to Hartman shows interchangeable structural units for building construction.
U.S. Pat. No. 3,656,270 to Phillips discloses a structural member having male and female parts utilizing an adhesive disposed between these parts to bond them together.
French patent 1,162,523 shows a mesh connected to parallel side rails. The diamond shaped mesh is oriented perpendicular to the long axes of the side rails to preclude expansion or adjustment of the spacing between the side rails.
None of these patents disclose the claimed structure set forth within.
SUMMARY OF THE INVENTION
In accordance with the invention claimed, a new and improved stud is provided for wall, ceiling joist and floor use in building construction. This stud comprises an assembly of parts which attach into a solid, rigid stud assembly which greatly reduces the amount of material needed to form the assembly over the prior art structures.
The claimed assembly comprises a pair of U-shaped channels the legs of which are arranged to face each other in a parallel spaced arrangement and are interconnected by a rigid stiffener. This stiffener extends between the U-shaped channels and into the legs of each of the channels to attach them in a rigid configuration to form the novel stud assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily described by reference to the accompanying drawings in which:
FIG. 1 is a perspective view of the prior art stud for mounting in or forming a part of a wall, ceiling joist or floor assembly of a building.
FIG. 2 is a perspective view of an improved stud serving the same functions as the prior art stud shown in FIG. 1 and embodying the invention.
FIG. 3 is a cross sectional view of FIG. 2 taken along the line 3--3;
FIG. 4 is a perspective view of the stiffener shown in FIGS. 2 and 3;
FIG. 5 is a cross sectional view of FIG. 4 taken along the line 5--5;
FIG. 6 is a top view of FIG. 4;
FIG. 7 is a perspective view of a plastic or metal strap that can be suspended from the cross member of the stiffener shown in FIGS. 2, 3 and 4 for supporting conduits, pipes and the like extending between studs in a wall, ceiling joist or floor assembly;
FIG. 8 is a side view of the strap shown in FIG. 7 illustrating it in series with another like strap and showing pipes or conduits being supported by one of the straps;
FIG. 9 is a perspective view of the stud a modification of the stiffener shown in FIG. 2;
FIG. 10 is a cross sectional view of the stiffener shown in FIG. 9;
FIG. 11 is a side view of the stiffener shown in FIG. 9;
FIG. 12 is a top view of FIG. 9;
FIG. 13 is a perspective view of a further modification of the stiffener shown in FIGS. 2 and 9;
FIG. 14 is a cross sectional view of FIG. 13 taken along the line 14--14;
FIG. 15 is an end view of the stiffener shown in FIG. 14;
FIGS. 16-18 are perspective views of modifications of the stiffeners shown in FIGS. 2-15;
FIG. 19 is a further perspective view of a stud showing an inverted U-shaped stiffener;
FIG. 19A is a view showing the stiffener before insertion between the studs;
FIG. 20 is a front elevational view of a expandable metal purlin joist or truss embodying the invention before expansion;
FIG. 21 is a front elevational view of the joist shown in FIG. 20 in its expanded condition; and
FIG. 22 is a cross sectional view of FIG. 21 taken along the line 22--22.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to the drawings by characters of reference, FIG. 1 discloses the prior art which comprises a stud 20 formed of plastic or metal which is bent or formed into a U-shaped channel like configuration. Legs 21 and 22 of stud 20 are laterally bent at their ends to form ninety degree like portions 23 and 24 which face each other in common planes.
FIG. 2 illustrates a modification of the prior art structure shown in FIG. 1 wherein channel or stud assembly 25 comprises two members 26 and 27. These members may be formed of suitable materials such as plastic or metal each bent into a U-shaped configuration as shown. The U-shaped configurations 26 and 27 comprises legs 26A, 26B and 27A, 27B, respectively interconnected by bites 26C and 27C.
As shown in FIGS. 2-6, an elongated stiffening member 28 is provided for extending between and interlocking with members 26 and 27 of stud 25 to hold members 26 and 27 in a stiff rigid condition.
Member 28 is formed of a rigid wire or rod that is bent laterally of its length at each of its ends to provide feet 30 and 31 of identical configuration that rest against and interlock and/or attach with the inside surface of members 26 and 27. As noted from FIG. 2, each of the inside corners of members 26 and 27 are deformed to provide notches 32 into which the feet 30 and 31 of member 28 are snapped or forced into for interlocking or attaching members 26 and 27 into a firm rigid stud assembly.
As noted, feet 30 and 31 are formed into a substantially rectangular configuration which are in parallel spaced planes with the ends of the center portion 33 extending to and against the inside surface of members 26 and 27.
FIG. 7 illustrates a T-shaped hanger 34 the leg 35 of which is provided with a plurality of like or different size apertures 36 extending therethrough along its length for receiving and supporting one or more conduits, wires, pipes 37, slots 38 or the like which are shown in dash lines in FIG. 8 for purposes of illustration. Each hanger is provided with a catch or snap clamp 40 for snapping over the center portion of stiffener member 33 of the stud assembly.
FIGS. 9-12 illustrate a modification of the stud shown in FIGS. 2-8 wherein like parts are given the same reference characters. This stud 41 differs from stud 25 in the design configuration of the stiffener 42 which comprises an elongated V-shaped trough 43 having at each end thereof foot configurations 44 and 45 extending laterally thereof in parallel planar configurations. Each foot comprises a flat planar configuration the side edges of which fit into the interlock or attach with notches 32 formed in the corners of members 26 and 27, as heretofore described, for the structure shown in FIGS. 2-8.
FIGS. 13-15 disclose a further modification of the studs shown in FIGS. 2-12 wherein the stiffener 46 of stud 47 comprises a zig-zag or Z-shaped configuration formed by a strip of metal 48 bent in a Z-shaped configuration the legs 49 and 50 of which are formed in planar configurations with the side edges of each leg fitting into notches 32.
FIGS. 16-19 disclose further modifications of the studs shown in FIGS. 2-15 wherein like parts of other studs disclosed herein are given like reference characters with one stud therein differing from the other studs by the design configuration of the stiffener and the manner of its attachment to the inside surfaces of members 26 and 27.
In FIG. 16, stiffener 51 of stud 52 comprises a hollow elongated channel having a square cross sectional configuration with flat feet 54 and 55 at each end secured to the inside surface of members 26 and 27 by any suitable means such as, for example, welding.
FIG. 17 discloses a like configuration wherein stiffener 56 of stud 57 comprises a hollow elongated tubular configuration fastened to the inside surfaces of members 26 and 27 to form a rigid assembly.
FIG. 18 discloses a similar configuration wherein members 26 and 27 are held together in a spaced relationship by an inverted V-shaped trough 58 to form a stud configuration 59.
FIG. 19 discloses a similar configuration wherein members 26 and 27 are held together by an inverted U-shaped trough 60 showing trough 60A before its insertion in the stud assembly.
FIGS. 20 and 21 disclose a stud 61 comprising a pair of U-shaped members 62 and 63 which may be formed of a metallic material that are interconnected by bight 64 comprising an expandable mesh 65. The expandable mesh originally comprised a flat piece of metal stamped to form a mesh configuration the physical orientation of which may be varied by moving one of the members 62 and 63 away from or toward the other as indicated by the arrows in FIG. 21, to increase or decrease the width of the mesh.
FIG. 22 is a cross sectional view of FIG. 21 with a crease line or indentation 66 added to neck 65 to strengthen the mesh when the stud is in its expanded position.
Thus, the metal mesh has openings adapted to expand only in a direction transverse to the longitudinal axes of the channel members.
Although but a few embodiments have been illustrated and described, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims. | An assembly of parts which form a stud for construction use. This stud assembly greatly reduces the material content of the stud assembly and reduces heat transfer and noise transmission over the known prior art and comprises two parallely arranged U-shaped channels interconnected by a novel mesh connector which interconnects the channels at one or more points along their length and is expandable only in a direction transverse to the longitudinal axes of the channels. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a ferritic Fe—Ni—Cr—Al alloy having both of excellent oxidation resistance and high-strength, which is suitable for use mainly in the atmospheric environment around room temperature after formation of an oxide film on the surface of the alloy under exposure to a high-temperature oxidation atmosphere, and a plate made of the alloy.
2. Description of the Related Art
Conventionally, the electrothermic alloys of Fe—Cr and Ni—Cr as defined in JIS C2520 have been well known as those having excellent oxidation resistance used in the atmospheric environment at a temperature range of from room temperature to a high temperature. Those alloys are excellent in oxidation resistance, and widely used for high-temperature heating elements.
On the other hand, JP-A-9-263906 discloses a ferritic Fe—Ni—Cr—Al alloy and a method for manufacturing the same, the ferritic Fe—Ni—Cr—Al alloy having excellent properties of corrosion resistance to molten metal and wear resistance.
While, with regard to the electrothermic Fe—Cr alloys and Ni—Cr alloys defined in JIS C2520, the electric resistance thereof is an important factor because of those use, taking their use, around room temperature, into consideration, any particular attentions have not been paid to the strength thereof. Therefore, when the alloys are used for structural members or parts for which oxidation resistance and strength at room temperature are required, the members or parts can not help having an increased size, so that it is difficult to make the members or parts compact and light.
Further, the ferritic Fe—Ni—Cr—Al alloy of JP-A-9-263906 is a material which is improved in properties of oxidation resistance, corrosion resistance to molten metal, wear resistance and so on by forming a film primarily comprising aluminum oxides on the surface of the alloy by heating the alloy in an oxidizing atmosphere at a temperature in the range of 800 to 1300° C. As will be understood from embodiments of JP′906, the inner metal structure of the alloy has a very high Vickers hardness of not less than 413 HV.
However, since the alloy of JP′906 is directed to a tool material on which the film is formed primarily comprising aluminum oxides to improve properties of oxidation resistance, corrosion resistance to molten metal, wear resistance and so on, any particular attentions are not paid to tensile properties including 0.2% yield strength and elongation determined by a tensile test, such properties being required for structural members and parts.
An object of the present invention is to provide an Fe—Cr—Ni—Al alloy which can possess both of excellent oxidation resistance and good mechanical properties especially at room temperature and which can be applied to structural members and parts, and to provide an alloy plate made of the same alloy and a material for a substrate made of the same alloy.
With regard to the ferritic Fe—Cr—Ni—Al alloy, the present inventors made every effort to realize a balance among chemical components according to which the tensile strength is adjustable at a proper level while keeping good oxidation resistance. As a result, it has been found that, when the amounts of Ni, Cr and Al in the Fe—Ni—Cr—Al alloy are adjusted in proper ranges, it is possible to keep the matrix to have a single phase structure of ferrite, and to finely precipitate an intermetallic compound of Ni—Al, which greatly contributes to precipitation strengthening of the alloy, in the ferrite matrix, whereby a high strength can be realized without deterioration of good oxidation resistance, cold workability and ductility.
It has been also found that, when the alloy contains small amounts of C and Zr, carbides are formed to keep ferrite crystal grains of the Fe—Ni—Cr—Al fine, thereby enabling to improve the alloy in 0.2% yield strength while keeping ductility and toughness at proper levels.
Further, it has been found that, when optionally one or more elements selected from the group of Hf, V, Nb, Ta, Y and REM (rare earth metals) are added, an adhesiveness of an oxide film to the alloy base is improved, the oxide film being primarily composed of aluminum oxides and formed on the surface of the alloy when exposed to a high temperature.
Moreover, it has been found that it is necessary to adjust a Cr equivalent, which has been defined by an F value determined on the basis of a result of experimental investigation by the present inventors, to a specific value as well as adjustment of the amount of the respective alloying elements, and that it is necessary to adjust the amount of solute elements defined by an S value to a specific value in order to obtain good cold workability of the alloy, resulting in the present invention.
Thus, according to a first aspect of the invention, there is provided a ferritic Fe—Cr—Ni—Al alloy having excellent oxidation resistance and high strength, which consists essentially of, by mass, 0.003 to 0.08% C, 0.03 to 2.0% Si, not more than 2.0% Mn, from more than 1.0% to not more than 8.0% Ni, from not less than 10.0% to less than 19.0% Cr, 1.5 to 8.0% Al, 0.05 to 1.0% Zr, and the balance of Fe and incidental impurities, wherein an F value is not less than 12% and an S value is not more than 25%, where the F value is defined by the following equation (1) and the S value is defined by the following equation (2):
F =−34.3C+0.48Si−0.012Mn−1.4Ni+Cr+2.48Al, (1)
and
S=Ni+Cr+Al, (2)
and wherein
the Fe—Cr—Ni—Al alloy, after an annealing heat treatment at 600 to 1050° C., has 0.2% yield strength of 550 to 1,000 MPa by a tensile test at room temperature.
According to a second aspect of the invention, there is provided a ferritic Fe—Cr—Ni—Al alloy having excellent oxidation resistance and high strength, which consists essentially of, by mass, 0.003 to 0.06% C, 0.03 to 1.0% Si, not more than 2.0% Mn, from more than 1.0% to less than 5.0% Ni, 10.0 to 17.0% Cr, from not less than 1.5% to less than 4.0% Al, 0.05 to 0.8% Zr, and the balance of Fe and incidental impurities, wherein the F value is not less than 12% and the S value is not more than 25%, and wherein
the Fe—Cr—Ni—Al alloy, after an annealing heat treatment at 600 to 1050° C., has 0.2% yield strength of 550 to 1,000 MPa by a tensile test at room temperature.
In the above ferritic Fe—Cr—Ni—Al alloys having excellent oxidation resistance and high strength, preferably 0.05 to 1.0% in total of one or more elements selected from the group of Hf, V, Nb and Ta are added. It is also preferred to add 0.05 to 1.0% in total of one or more elements selected from the group of Hf, V, Nb and Ta, and/or 0.05 to 1.0% in total of at least one element selected from Y and REM to the ferritic Fe—Cr—Ni—Al alloys.
Preferably, the Fe—Cr—Ni—Al alloy, after an annealing heat treatment at 600 to 1050° C. of temperature, has a Vickers hardness of 250 to 410 HV.
Preferably, the Fe—Cr—Ni—Al alloy has a mean coefficient of thermal expansion 11×10 −6 to 14×10 −6 /° C. in a temperature range of 20 to 800° C.
The invention alloy is excellent in cold workability, so that a ferritic alloy plate and a plate for substrates can be produced.
It should be also noted that such a plate can be produced by the powder metallurgical method from a powder of the invention alloy.
DETAILED DESCRIPTION OF THE INVENTION
Herein below, there will be described functions of the alloying elements in the invention alloy.
C (carbon) forms carbides with Cr and Zr in the invention alloy to deteriorate effects of the additive alloying elements. Thus, the carbon amount is preferably low. Further, a much amount of carbon makes the ferrite phase unstable, since carbon is an austenite forming element. On the other hand, in the case where the carbon amount is small, ferrite grains of the alloy can be maintained fine since carbides restrain grain boundaries of the ferrite not to move while maintaining the ferrite structure. If the carbon amount is less than 0.003%, the refining effect by carbides cannot be obtained. If the carbon amount is more than 0.08%, coarse carbides increase to deteriorate ductility and workability of the alloy. Thus, the carbon amount is set to 0.003 to 0.08%, preferably from 0.003 to 0.06%.
Si is added in a small amount as a deoxidizer, and it has an effect of improving oxidation resistance. However, if the Si amount is less than 0.03%, the above effect cannot be enough obtained. On the other hand, even if the Si amount is more than 2.0%, any further marked improvement in the above effect can not be obtained. Thus, the Si amount is set to 0.03 to 2.0%, preferably from 0.03 to 1.0%.
Mn, which acts as a deoxidizing and desulfurizing agent, is added to improve the alloy in cleanliness. An excess amount of more than 2.0% Mn deteriorates hot workability of the alloy. The Mn amount is preferably not more than 2.0%, more preferably not more than 1.0%.
Ni is an indispensable alloying element to the invention alloy. It dissolves in the ferrite matrix to strengthen the same, while a part of Ni forms an intermetallic compound of Ni—Al together with Al to finely precipitate and disperse in the ferrite matrix whereby strengthening the matrix. If the Ni amount is not more than 1.0%, the above mentioned strengthening effects is insufficient. On the other hand, if the Ni amount is more than 8.0%, the alloy strength become too high resulting in deteriorated ductility of the alloy, and occasionally an austenite phase is formed at a high temperature to make the ferrite phase unstable. Thus, the Ni amount is set to a range of from more than 1.0% to not more than 8.0%, preferably from more than 1.0% to less than 5.0%.
Cr is a ferrite forming element, and indispensable for making the matrix of the Fe—Ni—Cr—Al alloy to be the ferrite structure. It is also important in order to obtain good oxidation resistance because it forms a uniform and fine oxide film on the alloy surface, the oxide film being primarily composed of aluminum oxides at a high temperature and having a good adhesiveness to the alloy surface. If the Cr amount is less than 10.0%, the enough effect cannot be obtained. On the other hand, if the Cr amount is not less than 19.0%, the alloy is deteriorated in cold and hot workability. Thus, the Cr amount is set to a range from not less than 10.0% to less than 19.0%, preferably 10.0% to 17.0%, more preferably 13.0 to 17.0%.
Al combines with Ni to form an intermetallic compound of Ni—Al which finely precipitates in the ferrite matrix to strengthen it. It is also important in order to obtain good oxidation resistance because it forms a uniform and fine oxide film on the alloy surface, the oxide film being primarily composed of aluminum oxides at a high temperature and having a good adhesiveness to the alloy surface. If the Al amount is less than 1.5%, the enough effect cannot be obtained. On the other hand, if the Al amount exceeds 8.0%, not only the alloy is deteriorated in cold and hot work-ability, but also it may have too high strength whereby it is deteriorated in ductility. Thus, the Al amount is set to 1.5 to 8.0%, preferably from not less than 1.5% to less than 4.0%.
Zr is indispensable because of an important effect of forming oxide particles in a ferrite phase closely under the film, which is primarily composed of aluminum oxides and formed on the alloy surface at a high temperature, to remarkably improve the adhesion property of the film being primarily composed of aluminum oxides, and because of forming carbides to refine ferrite grains thereby improving tensile properties. However, if the Zr amount is less than 0.05%, the above effects are not enough. On the other hand, if the Zr amount exceeds 1.0%, the oxide particles become coarse to inversely deteriorate the adhesion property of the film, and a part of Zr combines with carbon to form coarse carbides resulting in deteriorated cold workability and ductility. Thus, the Zr amount is set to 0.05 to 1.0%, preferably from 0.05% to 0.8%.
Hf, V, Nb and Ta are optional elements. They form carbides to refine the ferrite grains thereby improving tensile properties, and improve the adhesion property of the oxide film being primarily composed of Al. However, if those amount is less than 0.05%, the above effects are not enough. On the other hand, if those amount exceeds 1.0%, carbides become coarse thereby deteriorating the ductility. Thus, one or more of Hf, V, Nb and Ta is added in the alloy in a total amount of 0.05 to 1.0%.
Y and REM are optional elements and one or both thereof are added in the alloy. They form oxide particles in the ferrite phase closely under the film, which is primarily composed of aluminum oxides and formed on the alloy surface at a high temperature, to remarkably improve the adhesion property of the film being primarily composed of aluminum oxides. However, if those amount is less than 0.05%, the above effect is not enough. On the other hand, if those amount exceed 1.0%, oxide particles become coarse to inversely deteriorate the adhesion property of the film. Thus, one or both of Y and REM is added in the alloy in a total amount of 0.05 to 1.0%.
In order to make the matrix structure of the invention alloy to be a single phase of ferrite, it is necessary to not only adjust the components of the alloy within the specified amount ranges, respectively, but also optimize the balance among the components.
Here, the F value as defined by equation (1) is a Cr equivalent which indicates a stability of the ferrite phase of the invention alloy. The Cr equivalent defined by equation (1) is obtained by adding together values obtained by multiplying a mass % of each of Cr, Si and Al, which are the ferrite forming elements, by a coefficient of the each ferrite forming element representing a formation easiness of the ferrite phase, and by subtracting values obtained by multiplying a mass % of each of Ni, C and Mn, which are the austenite forming elements, by a coefficient of the each austenite forming element representing a formation easiness of the austenite phase from the former values. If the F value is lower than 12%, the matrix structure can not be a single phase of ferrite, and a martensite structure and/or an austenite phase coexist, so that any stable properties of the alloy can not be obtained. Thus, the F value is set to not less than 12%.
The S value as defined by equation (2) represents, the total amounts of, by mass %, Ni, Cr and Al which are the primary alloying elements of the invention alloy. In order to improve the cold and hot workability of the alloy and ensure good tensile ductility of the alloy, it is necessary to adjust amounts of the additive alloying elements to be low levels without deterioration of alloy properties. If the S value exceeds 25%, cracks are liable to occur during cold and hot working processes resulting in deterioration of a yield during working. Thus, the S value is set to not more than 25%, preferably not more than 23%.
Further, the invention alloy comprises a main component of Fe and incidental impurities. In the case where the invention alloy is required to have not only oxidation resistance at a high temperature but also a high temperature strength, the alloy may comprise one or more of Mo, W and Co in a total amount of not more than 2.0%.
In order to strengthen grain boundaries and form sulfides to fix sulfur for the purpose of improving hot workability, the alloy may comprise one or more of B, Mg and Ca in a total amount of not more than 0.05%.
With regard to impurity elements of P, S, N and O, although their contents are preferably as low as possible, because, in order to extremely reduce those amounts, strictly selected expensive raw materials are used, and refining melting causes a much cost, so long as the following amount ranges are satisfied, the alloy may contain those impurity elements: P≦0.04%, S≦0.01%, N≦0.04% and O≦0.01%, according to which no problems will arise in the material properties and the productivity.
After plastic working, which is hot or cold working, the invention alloy is preferably annealed at a proper temperature in a range of 600 to 1050° C. in order to remove non-uniform strain which occurs during plastic working thereby increasing the ductility of the alloy, and to make ferrite grains uniform and fine. If the annealing temperature is lower than 600° C., a longer time is needed for removal of the strain. On the other hand, if the annealing temperature is higher than 1050° C., the strain can be removed in a short time while crystalline grains become coarse to deteriorate toughness of the alloy. Thus, the annealing temperature is set in a range of from 600 to 1050° C. It should be noted that the annealing time is preferably adjusted so as to be longer at a low temperature and shorter at a high temperature.
For example, when the annealing treatment is carried out at 700° C., the alloy is preferably kept for 4 hours, and when it is carried out at 950° C., keeping about 3 minutes is enough. The proper annealing treatment permits regulating the 0.2% yield strength of the invention alloy to a range in which the alloy can be used for structural members and structural parts. If the 0.2% yield strength is less than 550 MPa, the strength is insufficient to use the alloy for the structural members and structural parts in which the high strength is required, and on the other hand, if it is more than 1000 MPa, the ductility and toughness deteriorate. In consequence, the 0.2% yield strength is set in a range from 550 to 1000 MPa.
Hardness is a property necessary to use the alloy for the structural members and structural parts similarly to the 0.2% yield strength. If the hardness is less than 250 HV, the hardness is insufficient to use the alloy for the structural members and structural parts in which the high strength is required, and on the other hand, if it is higher than 410 HV, the number of steps of cold working and machining increases, and there is a concern for deterioration of ductility and toughness of the alloy. In consequence, the hardness is set in a range from 250 to 410 HV.
A thermal expansion coefficient of the alloy is suitably close to that of a different material such as a carbon steel, an alloy steel, a ceramic material, a glass or a resin to be joined thereto, in the case that the alloy is used for the structural members or structural parts, particularly for an alloy plate for a substrate. However, in the alloy of the present invention, the suitable thermal expansion coefficient can be attained by bringing the matrix structure into the ferrite single phase. The thermal expansion coefficient is often usually represented by an average at temperatures of from room temperature to higher temperatures, and here, it is represented by a mean coefficient of thermal expansion from 20 to 800° C. When the matrix structure of the invention alloy is brought into the single phase of ferrite, the thermal expansion coefficient is in a range of 11×10 −6 to 14×10 −6 /° C.
Furthermore, the alloy of the present invention can relatively easily be plastic-worked into a plate by hot or cold working. In addition, when oxidized at a high temperature, the oxide film having good adhesive properties mainly comprising the oxide of aluminum can be formed on the surface of an alloy plate. Therefore, the above-mentioned plate can suitably be worked to obtain an alloy plate for a substrate, whereby there can be impart, to the plate, a feature that the alloy plate is scarcely delaminated from the different material even when it is bonded thereto.
EXAMPLE
Each of invention alloys and comparative alloys was molten in a vacuum induction melting furnace to prepare 10 kg of an ingot, followed by hot forging. During this hot forging, any cracks did not occur in any alloy, and the hot working was good. Furthermore, hot rolling was carried out to obtain an alloy plate of about 2 mm thick, and an annealing treatment was then done at 680° C. After the removal of an oxide scale from the surface of the alloy plate, cold rolling was carried out to prepare an alloy plate having a thickness of about 1 mm. Afterward, an annealing treatment was done by keeping a suitable temperature in a range of from 850° C. to 950° C. for 3 minutes, followed by rapid cooling.
Table 1 shows chemical compositions of alloy Nos. 1 to 12 of the present invention and comparative alloy Nos. 21 to 27.
Furthermore, Table 2 shows cold workability of the respective alloys when they were subjected to cold rolling, matrix structures after the annealing treatment, values of 0.2% yield strength, Vickers hardness and mean coefficient of thermal expansion from 20 to 800° C., and oxidation resistance in the case that heating was kept at 900° C. for 10 minutes. Here, the cold workability was judged by a state of occurred cracks during the cold working. The letter A represents a state where any cracks did not occur and the working was easily possible, B represents a state where any cracks did not occur but resistance to deformation was slightly large, and C represents a state where some cracks occurred. Moreover, the oxidation resistance was judged by the adhesive properties of an oxide scale after the keeping of heating and subsequent air cooling. The letter B represents a state where the adhesive properties of the oxide scale were good, and C represents a state where the oxide scale was delaminated.
TABLE 1
(mass %)
F
S
No.
C
Si
Mn
Ni
Cr
Al
Zr
Fe
Others
value
value
Remarks
1
0.047
0.30
0.49
3.95
17.94
2.96
0.20
Bal.
18.28
24.85
Invention
alloy
2
0.049
0.29
0.49
3.92
11.97
2.97
0.20
Bal.
12.30
18.86
Invention
alloy
3
0.047
0.29
0.49
3.92
14.98
2.95
0.20
Bal.
15.33
21.85
Invention
alloy
4
0.047
0.29
0.55
2.82
14.99
2.94
0.19
Bal.
16.85
20.75
Invention
alloy
5
0.046
0.31
0.53
2.57
14.97
2.93
0.19
Bal.
17.20
20.47
Invention
alloy
6
0.009
0.23
0.54
3.14
12.05
2.92
0.17
Bal.
14.69
18.11
Invention
alloy
7
0.014
0.42
0.63
3.16
14.88
3.07
0.05
Bal.
Nb = 0.07
17.78
21.11
Invention
alloy
8
0.035
0.34
0.47
2.93
14.97
2.98
0.11
Bal.
V = 0.12
17.22
20.88
Invention
alloy
9
0.034
0.24
0.54
3.17
15.16
3.04
0.12
Bal.
Hf = 0.11, Y = 0.08
17.20
21.37
Invention
alloy
10
0.041
0.16
0.48
3.18
15.35
3.13
0.14
Bal.
Ta = 0.07, REM = 0.06
17.33
21.66
Invention
alloy
11
0.023
0.29
0.55
3.06
14.84
2.86
0.21
Bal.
Y = 0.07
16.99
20.76
Invention
alloy
12
0.032
0.35
0.48
3.05
15.36
2.97
0.22
Bal.
REM = 0.06
17.52
21.38
Invention
alloy
21
0.004
0.14
0.49
10.32
18.57
5.10
0.17
Bal.
16.69
33.99
Comparative
alloy
22
0.005
0.27
0.56
16.18
17.94
4.90
0.21
Bal.
7.39
39.02
Comparative
alloy
23
0.023
0.11
0.61
4.07
18.26
5.12
0.23
Bal.
24.52
27.45
Comparative
alloy
24
0.017
0.33
0.54
10.19
18.17
2.92
0.14
Bal.
10.71
31.28
Comparative
alloy
25
0.011
0.24
0.52
3.98
11.85
1.39
0.20
Bal.
9.46
17.22
Comparative
alloy
26
0.008
0.26
0.53
1.04
12.09
0.48
0.19
Bal.
11.67
13.61
Comparative
alloy
27
0.041
0.28
0.51
0.11
15.00
2.95
—
Bal.
Ti = 0.28
20.88
18.06
Comparative
alloy
*Note: Bal. = balance
TABLE 2
Mean Thermal
0.2% Yield
Expansion
Cold
Annealing
Matrix
Strength
Vickers
Coefficient
Oxidation
No.
Workability
Temp. (° C.)
Structure
(MPa)
Hardness
(×10 −6 /° C.)
Resistance
Remarks
1
B
850
α
941
401
13.6
B
Invention
Alloy
2
B
950
α
902
394
13.5
B
Invention
Alloy
3
B
950
α
982
383
13.3
B
Invention
Alloy
4
A
950
α
765
359
13.3
B
Invention
Alloy
5
A
950
α
624
285
13.1
B
Invention
Alloy
6
A
950
α
579
258
13.0
B
Invention
Alloy
7
A
950
α
815
367
13.3
B
Invention
Alloy
8
A
900
α
766
349
13.2
B
Invention
Alloy
9
B
950
α
794
358
13.3
B
Invention
Alloy
10
B
850
α
829
370
13.2
B
Invention
Alloy
11
B
900
α
761
339
13.2
B
Invention
Alloy
12
B
950
α
773
357
13.3
B
Invention
Alloy
21
C
950
α
1042
443
13.6
B
Comparative
Alloy
22
C
950
α + γ
916
392
14.2
B
Comparative
Alloy
23
C
950
α
947
404
13.5
B
Comparative
Alloy
24
C
950
α + γ
644
287
14.1
B
Comparative
Alloy
25
A
950
α + α′
468
211
13.1
C
Comparative
Alloy
26
A
950
α + α′
310
135
13.0
C
Comparative
Alloy
27
A
850
α
323
174
13.0
B
Comparative
Alloy
Table 2 indicates that the alloy Nos. 1 to 12 of the present invention are all excellent in the cold workability, and the matrix structure after the annealing treatment is a ferrite (α) single phase. In addition, with regard to the alloy Nos. 1 to 12 of the present invention, values of the 0.2% yield strength are in a range from 550 to 1000 MPa, and values of the Vickers hardness are in a range from 250 to 410 HV. Furthermore, values of the thermal expansion coefficient of the alloys according to the present invention are in a range from 11×10 −6 to 14×10 −6 /° C., and the oxidation resistance is also excellent.
On the other hand, the comparative alloy Nos. 21 to 24 having S values of more than 25 are slightly poor in the cold workability. Furthermore, of the comparative alloys having F values of less than 12, each of Nos. 22 and 24 contains a ferrite (α) phase and an austenite (γ) phase together, and each of Nos. 25 and 26 contains a martensite (α′) phase in addition to a ferrite (α) phase. In these alloys, any ferrite single phase structure is not obtained. Moreover, in the comparative alloy No. 21 containing a large amount of Ni and having the ferrite single phase structure, the 0.2% yield strength and the hardness are too high. Each of the comparative alloy Nos. 22 and 24 containing much Ni and the austenite phase has the large thermal expansion coefficient. Inversely, in the comparative alloy Nos. 25, 26 and 27 containing a less amount of Ni or Al which has an effect of the precipitation strengthening, the 0.2% yield strength and the hardness are low. In addition, in the comparative alloy Nos. 25 and 26 containing a less amount of Al, the oxidation resistance is slightly poor.
As described above, a ferritic Fe—Ni—Cr—Al alloy of the present invention easily permits hot working and cold working, and possesses both of high strength and good oxidation resistance. When used for structural members and structural parts which are used in the atmospheric environment ranging from room temperature or so to a high temperature, this type of alloy contributes to the miniaturization and lightening of the parts, and has good durability. Accordingly, the alloy of the present invention is expected to have industrially remarkable effects. | Disclosed is a ferritic Fe—Cr—Ni—Al alloy having excellent oxidation resistance and high strength, which consists essentially of, by mass, 0.003 to 0.08% C, 0.03 to 2.0% Si, not more than 2.0% Mn, from more than 1.0% to not more than 8.0% Ni, from not less than 10.0% to less than 19.0% Cr, 1.5 to 8.0% Al, 0.05 to 1.0% Zr, and the balance of Fe and incidental impurities, wherein an F value is not less than 12% and an S value is not more than 25%, where the F value is defined by the following equation (1) and the S value is defined by the following equation (2): (1) F=−34.3C+0.48Si−0.012Mn−1.4Ni+Cr+2.48Al, and (2) S=Ni+Cr+Al. The Fe—Cr—Ni—Al alloy, after an annealing heat treatment at 600 to 1050° C., has 0.2% yield strength of 550 to 1,000 MPa by a tensile test at room temperature. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to an automatic apparatus for superimposing or pairing, folding and transferring pairs of stockings to a collection station.
No automatic machines are known at present for superimposing or pairing legs of collants, folding the panties along the center or median line, folding over the legs thus superimposed or paired and transferring the collant thus folded to a collection station for packaging thereof.
Neither are automatic machines known for superimposing or pairing socks or stockings in pairs of socks or stockings, then folding them over and transferring them to a collection station for packaging.
SUMMARY OF THE INVENTION
It is the primary object of the present invention to provide an entirely automatic machine for carrying out the above mentioned operations, that is superimposing or pairing two socks or stockings at a time, or the two legs of a collant, folding over the socks or stockings thus superimposed or paired and transferring them to a collection station.
It is another object of the invention to provide a machine which is of a very simple structure, reliable in operation and capable of operating at a high speed.
These and still further objects are achieved by an apparatus having a moving chain provided with stocking supporting grippers at a location of its path said chain forming a very narrow loop. A two by two stocking pairing device is located at said loop and includes two movable walls connected to operating members causing the same to be respectively moved to and away from one another, a movable arm positioned laterally of said chain and in front of said walls and provided with driving means causing the displacement thereof from a position, at which it is clear of the path or travel of said chain, to a position at which it traverses the path or travel of said chain, a picking up device for the pairs of stockings, carried by said movable arm and having a stem movable from a retracted position, at which it is moved away from said two walls, to a position at which it extends to such walls, in which a window or slot is formed for the passage of said stem and pair of stockings thereby drawn and transferred to a collection station, and members for controlling the opening of the two grippers which are located above said walls, as soon as the latter have been moved near each other.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the structure and characteristics of the apparatus be more clearly understood, an embodiment thereof will now be described as given by mere way of unrestrictive example, with reference to the accompanying drawings, in which:
FIG. 1 is a diagrammatic plan view showing the apparatus according to the invention;
FIG. 2 is a diagrammatic side elevational view, restricted to the representation of the movable walls forming part of the device and a portion of chain adjacent thereto;
FIG. 3 is a front view of the movable walls forming part of the apparatus, at a stage at which such walls are moved away from each other;
FIG. 4 is a view similar to that of FIG. 3, but with the movable walls being closed;
FIG. 5 is a view similar to those of FIGS. 3 and 4, but with the movable walls completely closed and stockings blocked therebetween and superimposed or paired with one another;
FIG. 6 is a front view of the movable walls at the beginning of the opening thereof and picking up of the pairs of stockings; and
FIG. 7 is a front view of the station for the device comprising the movable walls during the last or final step, at which the transfer of a pair of stockings onto a conveyor belt has occurred.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A device, according to the invention, includes a moving chain, designated by reference numeral 1 and shown by dashed line in the drawings, such a chain carrying a continuous series of grippers 2 (which, for the sake of simplicity, are not shown in FIGS. 6 and 7), each of which is for supporting the tip of a stocking, which accordingly is downward hanging.
In the drawings, each of the stockings have been shown as comprising a leg 3 of a collant 4 merely outlined in the various figures of the drawings, such a collant having a panties 5 at which the two legs 3 are interconnected.
As shown in FIGS. 1 and 2, said chain 1 travels through a narrow loop, at which two movable walls 6 and 7 are provided, hinged to each other along a vertical axis, which walls are connected to the rods of two hydraulic or pneumatic pistons 8 (FIG. 1), which can cause the opening or closing thereof, as it will be hereinafter explained.
In each of said two walls 6 and 7, a window or slot 9 is formed, as clearly shown in the drawings.
Laterally of said walls 6 and 7, a movable arm 10 is provided, for example comprising the rod of the piston of a pneumatic or hydraulic cylinder 11 which at its free end facing the chain carries a hydraulic or pneumatic cylinder 12, the movable piston of which carries a rod 13, which can selectively extend to a conveyor belt 14 juxtaposed to said walls 6 and 7 and operated by a motor 15.
Accordingly, assume that each pair of successive grippers have the two legs 3 of a collant hanging therefrom, as above mentioned. When the two involved grippers are at the loop formed by said chain 1 and correctely located side by side to each other, as particularly shown in FIG. 1, the two legs 3 of the involved collant will be juxtaposed to each other and positioned between the two movable walls 6 and 7, as shown in FIG. 3.
At this position, an air jet or a movable arm 100 will act on the collant panties 5, urging it to the hinge formed by the two movable walls 6 and 7, while at the same time said two walls will start to move near each other (due to pistons 8), so as to superimpose or pair the two legs 3 of the collant and the two equal portions of the collant panties, as it can be readily understood and as shown in FIG. 4.
During this stage at which said two movable walls start to be closed, the rod 10 of cylinder 11 will be entirely outward projected, thus carrying the cylinder 12 beyond the two walls 6 and 7, still as clearly shown in FIG. 4. At this stage, the rod 13 of cylinder 12 will be completely moved to one side, so as not to interfere with the collant legs positioned between the movable walls.
At the end of this stage, the two walls 6 and 7 will be completely closed (FIG. 5), very slightly pressing the two superimposed or paired legs and the folded panties of the collant. Now, a device (not shown) (for example, an electromagnetic device) 110 will cause the opening of the two pliers holding the leg tips of the collant blocked or clamped between the movable walls, while at the same time said cylinder 12 will be operated causing the displacement of rod 13 towards said walls, as shown in FIG. 5.
Now, a return stroke of stem 10 (and hence of cylinder 12) will be started to the original rest position, and during such a movement said rod 13 will pass through the windows or slots 9 formed in said walls 6 and 7, thus hooking or clasping the superimposed or paired legs of the collant, which as a result will be caused to move out of the two walls, the latter simultaneously starting to move away from each other, as shown in FIG. 6.
Then, the rod 13 will complete the transfer of the collant legs substantially folded up at midway or intermediate length thereof onto the conveyor belt 14, which will deliver such a collant to a collection station, such as a packaging station.
The collant, which is laid down on the conveyor belt 14, has its two legs superimposed or paired to each other, and such legs will be folded up, so that said collant is definitely ready for packaging.
At said walls 6 and 7, heating means could be provided, such as hot air jets or electrical resistances or the like, in order that the collant if wet can be thoroughly dried and prefixed, that is ironed, which operation is promoted in that the collant is slightly pressed between said two movable walls 6 and 7.
In the description given with reference to the drawings, the members controlling the movement of the various movable elements have been outlined as comprising rods forming part of hydraulic or pneumatic cylinders, but as apparent such members could be of different type, for example movable members of electrical solenoids, or equivalent mechanical members.
It is also apparent that the superimposed or paired and folded stockings could be unloaded from the stem 13 on a member other than said conveyor belt 14, for example the stockings could be directly inserted in a picking up tunnel.
In the description reference has been made to the folding for the packaging of a collant, but it clearly appears that the apparatus is also suitable to automatic superimposition or pairing and folding of common socks and stockings. It also appears that the forward motion of chain 1 should be of intermittent type, but the stop time, during which two grippers are at side by side relationship at said walls 6 and 7 is very short, that is only few seconds.
From the foregoing it clearly appears that all of the described operations can be carried out at high speed and completely automatically, with the obvious advantages issuing therefrom, while the apparatus being of extremely simple structure and low cost. | Apparatus for automatically superimposing and folding collants or stockings and transferring the same to packaging. The apparatus comprises a moving chain carrying grippers having the collants leg tips hanging thereon. The chain travels through a narrow loop, at which moving parts are provided and press the two legs of each collant against each other, whereupon a moving member picks up the stockings midway the length thereof, transferring the same as folded up to a collection station. | 3 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation-in-part of U.S. application Ser. No. 09/313,686, filed May 18, 1999, entitled “Measuring Cup.”
BACKGROUND
[0002] This invention relates to vessels for containing measurable contents. More specifically, this invention relates to a vessel having graduated indicia.
[0003] Vessels such as cups, bowls, spoons and the like which have a measuring capability are known. Such devices can be made from a variety of materials, including plastic, metal and glass. One of the most common measuring vessels found on the market today is a transparent measuring cup made of Pyrex® which is resistant to sudden changes in temperature to which it may be subjected during use.
[0004] The utility derived from a measuring vessel is related to the ease with which volumetric indicia on the measuring vessel's wall may be read by a user. Of course, any suitable units of measurement may be used to indicate the level to which contents have risen within a measuring vessel.
[0005] Traditional measuring vessels have indicia marked upon the measuring vessel wall in a manner which sometimes makes the indicia difficult to read, depending upon how precise a measurement is needed, the materials from which the measuring vessel is manufactured and the physical condition of the user, for example. In the case of a measuring cup which is made from transparent or translucent material, e.g., Pyrex®, the most precise way to measure the contents contained therein is to place the measuring cup upon a level surface, pour the contents to be measured into the measuring cup and then stoop down to the vertical level of the measuring cup to attempt to visually detect the bottom of a liquid meniscus or a level surface of solid contents. An alternative method of reading the level to which contents in a transparent or translucent measuring cup have risen is to lift the measuring cup to eye level and attempt to hold the measuring cup steady while visually detecting the volume. In either use, the observer is looking in a generally horizontal direction to detect the volume.
[0006] Prior art measuring cups that are opaque are more difficult to read than transparent or translucent measuring cups. In order to read the volume of contents held within an opaque measuring cup, a user must peer over the upper margin of the measuring cup to view, as closely as possible, the level to which contents have risen, either by stooping to the measuring cup's level or by lifting the measuring cup to eye level.
[0007] While the above-described methods for determining the volume of contents in a measuring cup may seem simple enough for most users, these methods can prove to be difficult for others. Users with bad knees, a bad back, or arthritis, for example, may not only have substantial difficulty in stooping over to accurately read the volume of contents in a measuring cup placed on a level surface, but may also have just as much difficulty in lifting a measuring cup to eye level and holding the cup steady to read the volume of contents held therein. When precise measurement of the volume of contents within a measuring cup is critical to a task, the simple actions of bending over or lifting a measuring cup to eye level, which seem easy to some users, may become difficult and uncomfortable for others.
[0008] Measuring the volume of cooking ingredients using prior art measuring cups can also be frustrating. As mentioned above, it can be difficult for a user to stoop over to read the level of contents when placed on a level surface or when lifted to eye level. An unsteady hand not only makes the volume of contents difficult to determine when a measuring cup is lifted to eye level, but a user may spill contents or even drop the measuring cup when attempting to do so.
[0009] Measuring vessels are not limited in their utility to the kitchen, of course. They may also be used for measuring proper ratios of solutions, e.g., antifreeze, the precise measurement of which is critical to its application and simplicity of determining a precise volume is necessary. Other common household solutions can be dangerous, e.g., toxic or caustic, and when a measuring vessel is filled with these solutions, the possibility of spilling them within the proximity of a child or a pet greatly increases when a measuring vessel must be raised to eye level to determine the volume of its contents.
[0010] It is an object of the present invention to simplify the way in which a person can accurately determine the volume of material held in a vessel.
[0011] It is another object of the invention to improve a measuring vessel to make it more conducive to a simple and accurate volume determination.
SUMMARY
[0012] The present invention achieves the above-stated objectives by including with a vessel at least one sloped ramp having an upwardly directed surface having indicia which are readily observable by an observer looking downwardly toward the open end of the vessel.
[0013] The structure simplifies volume determination because there is no need for the observer to move relative to the vessel in order to look in a horizontal direction at the vessel indicia. Thus, the possibility of spilling is reduced. Also, since the ramp preferably rises continuously and gradually from the bottom of the vessel, a user who is filling the vessel from above can actually see the volume indicia on the upwardly directed surface of the ramp while the vessel is being filled, looking along the same line of sight generally used during filling. These advantages result from the ability to visually determine the volume of the contents of the vessel by simply looking into the open upper end, and the gradual slope of the ramp.
[0014] According to a first preferred embodiment of the invention, a cup has wall structure including a bottom wall and an encircling vertical side wall, so that the cup is cylindrical in shape with an open upper end. Inside the cup, at least one ramp slopes continuously upward from the bottom wall toward the open upper end. The ramp includes an upwardly directed surface bearing printed volume indicia viewable through the open upper end to visually determine the volume of cup contents. Preferably the cup has two ramps formed integrally along the side wall, with one bearing standard English units of measurement and the other bearing metric units. The two ramps have oppositely located bottom ends and oppositely located top ends. The cup also has a handle and a spout, with the handle located adjacent one ramp and the spout located adjacent another.
[0015] In a second embodiment, the side wall is sloped somewhat, rather than vertical. The cup includes two integral, oppositely located ramps with adjacently located bottom ends and adjacently located top ends. The top ends feed toward the spout, and again, one ramp bears indicia in standard English units and the other bears metric indicia.
[0016] In another embodiment, the handle is cantilevered from the side wall and has a vertical grip portion terminating at a distal end in the plane of the bottom wall to provide additional self-support, and covered with an elastomeric grip sheath.
[0017] With any embodiment, the cup can be formed of any suitable material and via any suitable process, although transparent and moldable material is preferred and manufactured using a molding process is also preferred.
[0018] Certain ones of these and other features may be attained by providing a vessel comprising: a wall structure defining a cavity with an open upper end for receiving contents having a measurable volume, a continuous ramp extending upwardly from adjacent to a lower end of the wall structure, and indicia positioned on the ramp so as to be observable by a user looking downwardly toward the open upper end and providing a readily observable indication of the volume of the contents of the vessel.
[0019] These and other features will be more readily understood in view of the following detailed description and the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] [0020]FIG. 1 is a perspective view of a measuring cup according to a first preferred embodiment of the invention;
[0021] [0021]FIG. 2 is a top plan view of the measuring cup of FIG. 1;
[0022] [0022]FIG. 3 is a cross-sectional view of the measuring cup of FIG. 2 taken along lines 3 - 3 ;
[0023] [0023]FIG. 4 is a perspective view of a second embodiment of the present inventive measuring cup;
[0024] [0024]FIG. 5 is a top plan view of the measuring cup of FIG. 4;
[0025] [0025]FIG. 6 is a side view of the measuring cup of FIG. 4 illustrating the nesting feature thereof;
[0026] [0026]FIG. 7 is a top plan view of another embodiment of measuring cup; and
[0027] [0027]FIG. 8 is a side elevational view of the measuring cup of FIG. 7.
DETAILED DESCRIPTION
[0028] FIGS. 1 - 3 show a first preferred embodiment of the present inventive vessel in the form of a measuring cup 10 . Generally, the measuring cup 10 is integrally formed of a suitable material and has a handle 12 and a spout 14 integrally attached to a substantially vertical side wall 16 . The measuring cup 10 has a base or bottom wall 18 integrally attached around its perimeter to the bottom edge of the side wall 16 . The side wall 16 cooperates with the bottom wall 18 to form wall structure which defines a cavity which has an open upper end.
[0029] The wall 16 has an inside surface 20 and an outside surface 22 from which ramps 24 a , 24 b are formed in relief. The measuring cup is of unitary, one-piece construction, molded from any suitable food grade plastic known in the art. However, it will be understood that the measuring cup 10 may be manufactured by any suitable process. It will also be understood that the measuring cup 10 may be made of any other suitable material known in the art, e.g., Pyrex® or metal.
[0030] The ramps 24 a , 24 b are located on opposite sides of the cup 10 but are identical in construction. Therefore, only one such ramp is described. Each ramp has a ramp base, or bottom end 25 , and a ramp top or upper end 26 . The ramp base 25 is located proximate the bottom edge of the side wall 16 , and the ramp top 26 is located proximate the top edge of the side wall 16 . The ramps 24 a , 24 b have respective upper ramp surfaces 30 a , 30 b , which are generally upwardly directed and have a substantially constant slope between the ramp base 25 and the ramp top 26 . In the first preferred embodiment, the ramps 24 a , 24 b are oppositely disposed on the inside surface 20 of the wall 16 . Also, in the first preferred embodiment, the ramps 24 a , 24 b traverse substantially the same distance from the bottom margin of the wall 16 to the top margin of the wall 16 along the inside surface 20 . It will be understood by those skilled in the art that the ramps 24 a , 24 b may have a greater or lesser slope, which in turn would result in shorter or longer distances, respectively, traveled from the bottom margin to the top margin of the wall 16 .
[0031] The ramps 24 a , 24 b have a slope great enough so that the ramps 24 a , 24 b do not extend more than half the circumference of the wall 16 , as seen in FIG. 2. Also, the ramps 24 a , 24 b do not overlap each other. That is, the ramp 24 a does not rise over the ramp 24 b on the inside surface 20 of the wall 16 . In the first preferred embodiment of the measuring cup 10 , the side wall 16 is substantially normal to the base 18 , so that the cup 10 is generally cylindrical in shape. In the illustrated embodiment the side wall 16 is slightly oval in transverse cross section but it could be circular or have other shapes. It will be understood by those skilled in the art that the wall 16 may angle away from the perimeter of the base 18 so that the measuring cup 10 may receive a second measuring cup (not shown) therein, i.e., allow plural measuring cups 10 to stack inside each other.
[0032] Each of the ramps 24 a , 24 b is provided with volume indicia 27 a , 27 a , on the upwardly directed surface 30 a , 30 b , so a user may easily look down toward the measuring cup 10 from above and view the volume level of the contents 28 within the cup 10 . In the first preferred embodiment, the ramp 24 a is provided with metric indicia 27 a on ramp surface 30 a , and ramp 24 b is provided with standard English indicia 27 a on ramp surface 30 b . It will be understood by those skilled in the art that the indicia 27 a , 27 a may be spaced differently relative to each unit of measurement on respective ramps 24 , 24 b , depending on the desired slope of the ramps 24 a , 24 b.
[0033] The side wall 16 has portions below the ramps 24 a , 24 b integral with the lateral inner edges of the ramp surfaces 30 a , 30 b , and portions above the ramps integral with the lateral outer edges of the ramp surfaces 30 a , 30 b.
[0034] FIGS. 4 - 6 show a second preferred embodiment of an inventive measuring cup 100 . The measuring cup 100 has wall structure including a side wall 116 integral with a bottom wall or base 118 for cooperation therewith to define a cavity with an open upper end 132 having a width A larger than the width B of the bottom wall or base 118 . Thus, the side wall 116 slopes outwardly away from the base 118 as the side wall 116 rises from its bottom edge to its top edge so that at least a second measuring cup 100 ′ (FIG. 6) can be stacked within the measuring cup 100 . The cup 100 has a handle 112 projecting from the side wall 116 adjacent to its upper end, and a spout 114 projecting from the upper end of the side wall 116 opposite the handle 112 , the spout 114 having a lower entry end and an upper exit end at the open upper end 132 . The measuring cup 100 has a pair of oppositely located, but identically sloped ramps 124 which are substantially continuous around the side wall inside surface 120 from the ramp bottom 125 toward the ramp top 126 . That is, both ramps 124 rise symmetrically along the inside surface 120 of the side wall 116 from about the bottom edge of the side wall inside surface 120 generally opposite the spout 114 to near the top edge of the side wall 116 adjacent to the base of the spout 114 .
[0035] Because the open upper end 132 has a greater width A than the width B of the base 118 , upper surfaces 130 of the ramps 124 bear indicia 127 a , 127 a which are not spaced in equal intervals. That is, a given rise in level 128 of the contents near the bottom edge of the side wall 116 requires a smaller volume than an equal rise in the level of the contents near the upper edge of the side wall 116 . As a result, the indicia 127 a , 127 a are spaced upon the ramps 124 closer together near the top edge of the side wall 116 than at the bottom edge for an equivalent volume of contents 128 . It will be understood by those skilled in the art that the progressive change in the diameter of the measuring cup 100 from the base 118 to the upper edge of the side wall 116 may also be accommodated by decreasing the slope of the ramps 124 from the lower edge of the side wall 116 to the upper edge of the side wall 116 while maintaining the spacing between indicia 127 a , 127 a along the ramps 124 .
[0036] Also in this embodiment, the ramp tops 126 are continuous with an inner surface of the spout 114 to allow a user to more easily pour contents from the measuring cup 100 without spilling.
[0037] The side wall 116 has a lower portion 116 a below the ramps 124 which is offset inwardly by the width of the ramp upper surfaces 130 from an upper portion 116 b of the side wall 116 . This offset allows other measuring cups 100 ′ to nest within the measuring cup 100 and each other when stacked. More specifically, the lower portion 116 a of the side wall 116 , which is below the ramps 124 , is integral with the lateral inner edges of the ramps, while the upper portion 116 b , which is above the ramps, is integral with the lateral outer edges of the ramps.
[0038] [0038]FIGS. 7 and 8 show another embodiment of an inventive measuring cup 200 . The measuring cup 200 has wall structure including a side wall 216 integral with a bottom wall or base 218 for cooperation therewith to define a cavity with an open upper end 232 having a width larger than the width of the bottom wall or base 218 . Thus, the side wall 216 slopes outwardly away from the base 218 as the side wall 216 rises from its bottom edge to its top edge. The cup 200 has a handle 212 projecting from the side wall 216 adjacent to its upper end, and a spout 214 projecting from the upper end of the side wall 216 opposite the handle 212 , the spout 214 having a lower entry end and an upper exit end at the open upper end 232 . The measuring cup 200 has a pair of oppositely located, but identically sloped ramps 224 which are substantially continuous around the side wall inside surface 220 from the ramp bottom 225 toward the ramp top 226 . That is, both ramps 224 rise symmetrically along the inside surface 220 of the side wall 216 from about the bottom edge of the side wall inside surface 220 generally opposite the spout 214 to near the top edge of the side wall 216 adjacent to the base of the spout 214 .
[0039] Because the open upper end 232 has a greater width than the width of the base 218 , upper surfaces 230 of the ramps 224 bear indicia 227 a , 227 a which are not spaced in equal intervals for the same reasons indicated above for the cup 100 . It will be understood by those skilled in the art that the progressive change in the diameter of the measuring cup 200 from the base 218 to the upper edge of the side wall 216 may also be accommodated by decreasing the slope of the ramps 224 from the lower edge of the side wall 216 to the upper edge of the side wall 216 while maintaining the spacing between indicia 227 a , 227 a along the ramps 224 .
[0040] The side wall 216 has a lower portion 216 a below the ramps 224 which is offset inwardly by the width of the ramp upper surfaces 230 from an upper portion 216 b of the side wall 216 . More specifically, the lower portion 216 a of the side wall 216 , which is below the ramps 224 , is integral with the lateral inner edges 224 a of the ramps, while the upper portion 216 b , which is above the ramps, is integral with the lateral outer edges 224 b of the ramps.
[0041] The periphery of the bottom wall 218 lies in a base plane P to provide a stable support on an underlying support surface. The handle 212 is generally L-shaped, having a short arm 213 projecting laterally outwardly from the side wall 216 and integral at the outer end thereof with an elongated depending grip portion 215 which extends substantially perpendicular to the base plane P and terminates at a generally flat distal end 217 which lies substantially in the base plane P. Thus, when the measuring cup 200 is resting on its base or bottom wall 218 , the end 217 provides an additional support point. Furthermore, the depending portion 215 of the handle 212 is covered with a grip sheath 219 , preferably formed of a suitable flexible and cushioning elastomeric material, such as that sold under the trade name SANTOPRENE. This affords a comfortable, non-slip, frictional grip surface to facilitate grasping of the handle 212 .
[0042] While in the disclosed embodiments the ramps have fixed or constant slopes, it will be appreciated that the slopes could vary. Also, while each of the disclosed embodiments has two ramps, a single ramp could suffice. Preferably, the entire measuring cup is formed of a transparent material, but, if desired, the ramps could be translucent to enhance contrast with the vessel side walls.
[0043] While the illustrated embodiments are cups, it will be appreciated that the principles of the invention are applicable to other vessels, such as bowls, ladles, spoons and the like and, indeed, to any vessel-defining structure, whether or not self-supporting and whether or not provided with a handle or a spout, and of any size or shape.
[0044] The matter set forth in the foregoing description and accompanying drawings is offered by way of illustration only and not as a limitation. While particular embodiments have been shown and described, it will be apparent to those skilled in the art that changes and modifications may be made without departing from the broader aspects of applicants' contribution. The actual scope of the protection sought is intended to be defined in the following claims when viewed in their proper perspective based on the prior art. | A measuring vessel has cavity-defining wall structures and at least one ramp which rises from about the bottom of the wall structure toward the top of the wall structure. The at least one ramp has an upwardly directed surface with a lateral inner edge integral with portions of the wall structure below the ramp and a lateral outer edge integral with portions of the wall structure below the ramp. Indicia on the upwardly directed surface of the at least one ramp allows a user to look downwardly into the measuring vessel to visually detect the volume level of the contents in the vessel, thereby eliminating the need to look horizontally at the vessel at eye level. Preferably the vessel has two ramps, with at least one bearing indicia of standard English units, and another bearing indicia of metric units. In one embodiment a handle, covered with a cushioning grip sheath, is cantilevered from the top of the wall structure and has a distal end at the level of the bottom of the wall structure for cooperation therewith to support the vessel on an underlying support surface. | 6 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a system for delivering a content by transmitting and receiving encrypted data through a network.
[0002] A system for executing a pay broadcast adopt a measure for preventing illegal viewing of a user. Conventionally, a station for executing the pay broadcast (hereafter, referred to as pay broadcast station) instructs a viewer to buy a receiving apparatus dedicated to each station. The viewer can view the pay broadcast of each station, by using the bought receiving apparatus. For example, data scrambled with a scrambling code is transmitted by the station, and the data scrambled with the scrambling code can be decoded only by a scramble key installed in the receiving apparatus, and the viewing becomes possible. The viewer makes a contract about a payment of a viewing fee and the like, with the station for executing the pay broadcast when buying the receiving apparatus. In this way, the illegal viewing of the user was prevented.
[0003] However, this system had several problems. Firstly, since the user needed to buy the receiving apparatus before starting the viewing, an initial installation cost was enormous. This enormous initial installation cost caused the user to hesitate to start the viewing of the pay broadcast.
[0004] Also, since the conventional receiving apparatus was the apparatus dedicated to each station, the user needed to buy the receiving apparatus for each broadcast station. That is, the user, when viewing a broadcast program of a broad cast station (another broadcast station) different from the station having a contract with the user himself, needed to buy a new receiving apparatus. This caused the user hesitate to start the viewing of the pay broadcast of the different broadcast station.
[0005] Also, when the receiving apparatus is exchanged, the exchange needs to be performed for all of the viewers. Thus, enormous labors and costs are required. For this reason, the same receiving system has been operated for a long time without any change. Hence, in association with the elapse of the long operation period, there was a problem that an unauthenticated viewer could easily and illegally obtain the scramble key.
[0006] As a solution to the foregoing problem, there is a system for executing the pay broadcast on IP (Internet Protocol). For example, there is a system for executing the pay broadcast through the Internet. In the system, a dedicated virtual communication path is set by unicast, and a typical encrypting technique such as IPSEC (IP Security) is used to prevent the illegal viewing. Thus, the user does not need to buy the receiving apparatus dedicated to each station, and the viewing is possible by using a personal computer connected to a network. Also, the data on the scramble key and the like can be easily changed, thereby making it difficult for the unauthenticated viewer to obtain the key.
[0007] Also, as the conventional techniques, there are the following. Firstly, there is a technique in which a broadcast company broadcasts the information on an access point of a particular free provider that does not require a subscription contract and an authentication procedure specified by the broadcast company through a data broadcast, together with a normal broadcast, and at the time of selecting a two-way communication, irrespective of whether or not the viewer signs up with the provider, a communication line is connected to the free provider, thereby accessing the Internet (refer to Patent Document 1).
[0008] Also, secondly, there is a system including a broadcast station, a database, a receiving apparatus, a data communication apparatus and a user terminal apparatus, in which a secret key method, a public key method and a digital signature method are used as an encryption key method, and those keys are supplied by the broadcast while they are encoded or not encoded (refer to Patent Document 2).
[0009] [Patent Document 1]
[0010] Japanese Patent Application Laid-Open Publication No. 2000-13524.
[0011] [Patent Document 2]
[0012] Japanese Patent Application Laid-Open Publication No. 8-288940.
BRIEF SUMMARY OF THE INVENTION
[0013] However, the conventional system that carries out the pay broadcast on the IP has the following problem. Since the pay broadcast on the IP used the unicast in order to prevent the illegal viewing, the processes in a server of the broadcast station and a relay apparatus on a route were increased. Thus, depending on the abilities of the server of the broadcast station and the relay apparatus on the route, the number of viewers simultaneously accessing there was limited.
[0014] The present invention has an object to provide a system, which solves the above-mentioned problems, and prevents illegal viewing and simultaneously reduces a processing load on the server of the broadcast station and the relay apparatus on the route.
[0000] [First Aspect]
[0015] In order to solve the above-mentioned problems, the present invention has the following configuration. A first aspect of the present invention provides a distribution system including a management apparatus and a receiving apparatus.
[0016] According to the first aspect, the management apparatus includes: a receiving unit receiving a code request including an electronic sign generated in accordance with a first key data; an authentication unit authenticating a transmission source of the code request by using a second key data corresponding to the first key data and the electronic sign; a reply unit, when the authentication unit authenticates the transmission source, transmitting a code response which included at least a decryption code and is encrypted in accordance with a third key data; an encryption unit encrypting data of a content to be multicasted, by using an encryption code corresponding to the decryption code; and distribution unit multicasting the data encrypted by the encryption unit.
[0017] According to the first aspect, the receiving apparatus includes: an addition unit adding the electronic sign to the code request by using the first key data; a transmission unit transmitting the code request including the electronic sign generated by the addition unit; a receiving unit receiving an encrypted data which is multicasted by the management apparatus and the code response which is transmitted by the management apparatus; an obtainment unit decrypting and obtaining the decryption code included in the code response received by the receiving unit, by using a fourth key data corresponding to the third key data; and a decryption unit decrypting the encrypted data received by the receiving unit by using the decryption code obtained by the obtainment unit, and passing a decryption data to an output unit.
[0018] The first key data and the second key data may have any configuration if an electronic sign generated in accordance with the first key data can be authenticated by the second key data. For example, the first key data and the second key data may be configured by using a public key and a secret key which are generated in accordance with a public key method. Also, for example, the first key data and the second key data may be configured by using the same secret key. However, when the second key data is configured by using the public key, a user of an apparatus (for example, a receiving apparatus) serving as a transmission source of a code request can confirm a content of the transmitted code request by decrypting the code request using the second key data. In the case where the second key data is configured by using the public key, there is no influence on an authenticating operation with the authentication unit, even if the second key data is published to the user as mentioned above.
[0019] Also, the first key data and the fourth key data may be configured by using the same key data. In this case, the second key data and the third key data are configured by using the same key data. With this configuration, the number of key data used can be reduced. Thus, the management of the key data becomes easy.
[0020] Also, the first key data and the fourth key data may be able to be referred to only by addition unit and the obtainment unit. With this configuration, it is possible to prevent the user of the receiving apparatus from obtaining the first key data and the fourth key data and prevent this key data from being illegally used.
[0021] According to the first aspect of the present invention, the addition unit of the receiving apparatus uses the first key data and adds the electronic sign to the code request, and transmission unit transmits this code request to a management apparatus.
[0022] When receiving unit of the management apparatus receives this code request, authentication unit uses the electronic sign and second key data which are included in this code request and authenticates the transmission source (for example, the receiving apparatus) of the code request. If the transmission source is authenticated, reply unit sends a code response including a decryption code encrypted by the third key data to the authenticated transmission source. At this time, the code response may be configured such that the entire code response is encrypted by the third key data.
[0023] When the receiving unit of the receiving apparatus receives this code response, the obtainment unit obtains the decryption code included in this code response by using the fourth key data.
[0024] Encryption unit of the management apparatus uses an encryption code and encrypts data of a content which is multicasted. This encryption code corresponds to the decryption code included in the code response sent by the reply unit. That is, the data encrypted by this encryption code can be decrypted by this decryption code. Distribution unit multicasts the data encrypted by the encryption unit.
[0025] When the receiving unit of the receiving apparatus receives this data, the decryption unit decrypts this data. At this time, the decryption unit uses the decryption code obtained by the obtainment unit and decrypts the received data. Then, the decryption unit passes the decrypted data (plaintext) to output unit.
[0026] According to the first aspect of the present invention, the data to be multicasted by the management apparatus, namely, the data to be delivered is decrypted by the decryption code. Then, the decryption code for decrypting this data is transmitted to the receiving apparatus authenticated by the first key data and the second key data. Moreover, this decryption code is transmitted and received by using the encrypted communication based on the third key data and the fourth key data. Thus, unless the first key data and the fourth key data are leaked, the illegal obtainment of the delivered data can be prevented. Thus, the illegal obtainment of the delivered data can be prevented without any transmission from the management apparatus to the receiving apparatus through the unicast transmission. Hence, for example, if the delivered data is the content data of image data or the like, according to the first aspect of the present invention, the illegal viewing can be prevented.
[0027] Also, the delivered data is transmitted through the multicast communication. Thus, unlike the conventional transmission by unicast, the processing loads on the apparatus (management apparatus) serving as the data transmission source and the relay apparatus on the route can be reduced.
[0028] Also, the management apparatus according to the first aspect of the present invention may be configured so as to further include: a key generation unit newly generating the first key data and the second key data; and a key transmission unit transmitting the first key data generated by the key generation unit to the receiving apparatus. In this case, the authentication unit carries out the authentication by using the newly generated second key data after the key generation unit newly generates the second key data. Also, in this case, the addition unit of the receiving apparatus carries out the addition of the electronic sign by using the received new first key data, after the receiving of the new first key data from the management apparatus. With this configuration, it is possible to update the first key data and the second key data, and prevent the leakage of the first key data and the second key data.
[0029] Similarly, the first aspect of the present invention may be configured so as to update the third key data and the fourth key data. In this case, the key generation unit further generates the third key data and the fourth key data. The key transmission unit transmits the fourth key data generated by the key generation unit to the receiving apparatus. The authentication unit carries out the authentication by using the newly generated third key data, after the key generation unit newly generates the third key data. Then, the obtainment unit of the receiving apparatus obtains the decryption code by using the received new fourth key data, after the receiving of the new fourth key data from the management apparatus.
[0030] Further, according to the first aspect of the present invention, the addition unit of the receiving apparatus may further add an identification data to identify a user of its own apparatus to the code request. As an example of the identification data, there are a number of a credit card of a user, an electronic sign based on a key data uniquely used by a user, and the like. A manager, an operator and the like of the management apparatus can identify and authenticate the user of the receiving apparatus, by using this identification data. Moreover, a download fee, a viewing fee, and the like of the delivered data can be collected from the user by using this identification data.
[0031] Further, according to the first aspect of the present invention, the addition unit, the obtainment unit, and the decryption unit may be implemented on the receiving apparatus when a program is executed by the receiving apparatus. The management apparatus according to the first aspect of the present invention may further include a publication unit publishing the program in a form of being downloadable by the receiving apparatus through a network.
[0032] With this configuration, the user who desires the obtainment (viewing) of the delivered data can implement the addition unit, the obtainment unit and the decryption unit on the receiving apparatus, by downloading a program from the management apparatus. Thus, the user can easily obtain the delivered data without any necessity of buying a new dedicated apparatus in order to obtain the delivered data. Also, the publication unit may be configured so as to publish the first key data and the fourth key data in a form of being downloadable by the receiving apparatus. In this case, the first key data and the fourth key data may be configured so as to be included in the aforementioned program.
[0000] [Second Aspect]
[0033] A second aspect of the present invention provides a distribution system including a management apparatus, a distribution apparatus, and a receiving apparatus. An according to the second aspect of the present invention, the unit included in the management apparatus according to the first aspect of the present invention are separately held by the management apparatus and the distribution apparatus.
[0034] That is, according to the second aspect of the present invention, the management apparatus includes: a receiving unit receiving a code request including an electronic sign generated in accordance with a first key data; an authentication unit for authenticating a transmission source of the code request by using a second key data corresponding to the first key data and the electronic sign; and a reply unit for, when the authentication unit authenticates the transmission source, transmitting a code response which includes at least a decryption code and is encrypted in accordance with a third key data.
[0035] Further, according to the second aspect of the present invention, the distribution apparatus includes: an encryption unit encrypting data of a content to be multicasted, by using an encryption code corresponding to the decryption code; and a distribution unit multicasting the data encrypted by the encryption unit.
[0036] Further, according to the second aspect of the present invention, the receiving apparatus includes: an addition unit adding the electronic sign to the code request by using the first key data; a transmission unit transmitting the code request including the electronic sign generated by the addition unit; a receiving unit receiving an encrypted data which is multicasted by the distribution apparatus and the code response which is transmitted by the management apparatus; an obtainment unit decrypting and obtaining the decryption code included in the code response received by the receiving unit, by using a fourth key data corresponding to the third key data; and a decryption unit decrypting the encrypted data received by the receiving unit by using the decryption code obtained by the obtainment unit, and passing a decrypted data to an output unit.
[0037] Further, according to the second aspect of the present invention, the addition unit, the obtainment unit, and the decryption unit may be implemented on the receiving apparatus when a program is executed by the receiving apparatus. Further, the distribution system according to the second aspect of the present invention may further include a publication apparatus for publishing the program in a form of being downloadable by the receiving apparatus through a network.
[0038] With this configuration, the user who desires the obtainment (viewing) of the delivered data can implement the addition unit, the obtainment unit and the decryption unit on the receiving apparatus, by downloading the program from the publication apparatus. Thus, the user can easily obtain the delivered data without any necessity of buying the new dedicated apparatus in order to obtain the delivered data. Also, the publication apparatus may be configured so as to publish the first key data and the fourth key data in the form of being downloadable by the receiving apparatus. In this case, the first key data and the fourth key data may be configured so as to be included in the above program.
[0000] [Third Aspect]
[0039] A third aspect of the present invention provides management apparatus including: a receiving unit receiving a code request including an electronic sign generated in accordance with a first key data; an authentication unit authenticating a transmission source of the code request using a second key data corresponding to the first key data and the electronic sign; a reply unit, when the authentication unit authenticates the transmission source, transmitting a code response which includes at least a decryption code and is encrypted in accordance with a third key data; an encryption unit encrypting data of a content to be multicasted, by using an encryption code corresponding to the decryption code; and a distribution unit multicasting the data encrypted by the encryption unit.
[0000] [Fourth Aspect]
[0040] A fourth aspect of the present invention provides a receiving apparatus including: an addition unit adding an electronic sign to a code request by using a first key data corresponding to a second key data of a management apparatus which is a transmission destination of the code request; a transmission unit transmitting the code request including the electronic sign generated by the addition unit; a receiving unit receiving an encrypted data which is multicasted and the code response which is transmitted in response to the code request; an obtainment unit decrypting and obtaining the decryption code, which is included in the code response received by the receiving unit and encrypted in accordance with a third key data, by using a fourth key data corresponding to the third key data; and a decryption unit decrypting the encrypted data received by the receiving unit, by using the decryption code obtained by the obtainment unit and passing to output unit.
[0041] According to the fourth aspect of the present invention, the first key data and the fourth key data may be configured so as to be able to be referred to only by the addition unit and the obtainment unit.
[0000] [Fifth Aspect]
[0042] A fifth aspect of the present invention provides a program for controlling an information processing apparatus to execute: adding an electronic sign to a code request by using a first key data corresponding to a second key data of a management apparatus which is a transmission destination of the code request; transmitting the code request to which the electronic sign is added; receiving the code response transmitted in response to the code request; decrypting and obtaining the decryption code, which is included in the received code response and encrypted in accordance with a third key data, by using a fourth key data corresponding to the third key data; receiving the encrypted data which is multicasted; and decrypting the encrypted data which is received, by using the obtained decryption code, and passing to an output unit, wherein the first key data, the fourth key data, and the decryption code are not able to be referred to by a user of the information processing apparatus and a different programs executed by the information processing apparatus.
[0043] Further, in the program according to the fifth aspect of the present invention, the first key data and the fourth key data may be provided.
[0044] Further, in the program according to the fifth aspect of the present invention, the first key data and the fourth key data may be configured by using the same key data, and the second key data and the third key data may be configured by using the same key data.
[0045] According to the present invention, by preventing the illegal viewing of the delivered data as well as delivering through the multicast communication, it is possible to reduce the processing load on the distribution apparatus (for example, the server of the broadcast station) and the relay apparatus existing between this apparatus and the receiving apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
[0046] FIG. 1 is a diagram showing a schema of a broadcast system according to the present invention;
[0047] FIG. 2 is a functional block diagram of a client and a local station according to a first embodiment;
[0048] FIG. 3 is a diagram showing contents of a message of a decryption code request;
[0049] FIG. 4 is a diagram showing contents of a message of a decryption code response;
[0050] FIG. 5 is a diagram showing stored contents of a key storage section;
[0051] FIG. 6 is a diagram showing decryption information;
[0052] FIG. 7 is a diagram showing publication destination information;
[0053] FIG. 8 is a diagram showing encryption information;
[0054] FIG. 9 is a diagram showing contents of encrypted data;
[0055] FIG. 10 is a flowchart showing an operation example of a decryption code obtainment section;
[0056] FIG. 11 is a flowchart showing an operation example of a decryption section;
[0057] FIG. 12 is a flowchart showing an operation example of an applet generation section;
[0058] FIG. 13 is a flowchart showing an operation example of a viewer authentication section;
[0059] FIG. 14 is a flowchart showing an operation example of an encryption section;
[0060] FIG. 15 is a diagram showing a sequence example of a receiving start process;
[0061] FIG. 16 is a diagram showing sequence example of a receiving continuation process;
[0062] FIG. 17 is a functional block diagram of a client and a local station according to a second embodiment;
[0063] FIG. 18 is a diagram showing contents of a switching client key set table;
[0064] FIG. 19 is a diagram showing contents of a switching local station key set table;
[0065] FIG. 20 is a diagram showing contents of encrypted data;
[0066] FIG. 21 is a flowchart showing an operation example of an encryption section;
[0067] FIG. 22 is a flowchart showing an operation example of an encryption section;
[0068] FIG. 23 is a flowchart showing an operation example of an encryption section;
[0069] FIG. 24 is a flowchart showing an operation example of an encryption section;
[0070] FIG. 25 is a flowchart showing an operation example of a switching key generation section;
[0071] FIG. 26 is a flowchart showing an operation example of a decryption section;
[0072] FIG. 27 is a flowchart showing an operation example of a decryption section;
[0073] FIG. 28 is a diagram showing a process with regard to a switching client key set; and
[0074] FIG. 29 is a diagram showing a process with regard to a switching local station key set.
DETAILED DESCRIPTION OF THE INVENTION
[0075] A system and apparatus in embodiments of the present invention will be described below by using the drawings. Incidentally, the explanation of the embodiments is an exemplification, and the configuration of the present invention is not limited to the following explanation.
First Embodiment
[0076] [System Configuration]
[0077] FIG. 1 is a diagram showing a schema of a broadcast system 1 according to a first embodiment of the present invention. The broadcast system 1 will be explained by using FIG. 1 .
[0078] The broadcast system 1 is composed of with a relay station 2 a , local stations 2 , a key station 3 and a plurality of clients 4 . IP communications of a one-to-one relationship are carried out between the key station 3 and the relay station 2 a and between the relay station 2 a and each local station 2 . Also, IP communications based on multicast are carried out between the relay station 2 a and the local station 2 , and each client 4 .
[0079] In the broadcast system 1 , data of contents transmitted by the key station 3 is delivered by the relay station 2 a or local station 2 to each client 4 . At this time, the relay station 2 a or local station 2 encrypts the data of the contents, uses the IP communication based on the multicast and delivers the data of the content. In the following explanations, the data of the content transmitted by the key station 3 is assumed to be streaming data. Actually, the data of the content transmitted by the key station 3 may be any data depending on a usage field.
[0080] FIG. 2 is a block diagram showing configurations of the local station 2 and the client 4 . The configurations of the local station 2 and the client 4 will be described below by using FIG. 2 . Although, in the explanation of FIG. 2 and the subsequent explanation, the configuration of the local station 2 will be described, the relay station 2 a has the similar configuration. That is, the client 4 can also obtain the data of the content by carrying out the communications similar to the communications in the following explanation, with the relay station 2 a . Incidentally, the relay station 2 a has a function of delivering the data of the content to the plurality of local stations 2 , in addition to the configuration of the local station 2 which will be described below.
[0000] Client
[0081] At first, the configuration of the client 4 is explained. The client 4 is configured by using information processing apparatus having a communication function, such as a personal computer, a workstation, or PDA (Personal Digital Assistants). The client 4 includes a CPU connected through a bus, a main memory (RAM), and an auxiliary storage (a hard disk, a flash memory, or the like) as hardware. The client 4 functions as the apparatus including a Web browser execution section 5 , a broadcast receiving section 6 , and a display section 11 , when various programs (OS, applications, and the like) stored in the auxiliary storage are loaded to the main memory and executed by the CPU. Also, the client 4 includes a communication apparatus (not shown). The Web browser execution section 5 , the broadcast receiving section 6 , and the display section 11 use the communication apparatus to communicate with the local station 2 or another apparatus through a network.
[0000] Web Browser Execution Section
[0082] The Web browser execution section 5 is attained when the program of the Web browser is executed by the CPU. The program to be executed may be a program of any Web browser, for example, Internet Explore or Netscape (registered trademarks). The Web browser execution section 5 provides the functions of the Web browser to the client 4 . The user uses the Web browser execution section 5 to download a broadcast receiving applet from the local station 2 .
[0000] Broadcast Receiving Section
[0083] The broadcast receiving section 6 is attained when an execution code of the broadcast receiving applet stored in the client 4 is executed by the CPU. Also, the broadcast receiving section 6 writes data to the main memory or auxiliary storage in the client 4 , in order to hold the data as necessary. The broadcast receiving section 6 receives the data of the content from the local station 2 and converts the received data into data that can be displayed on the display section 11 . The broadcast receiving section 6 includes a decryption code obtainment section 7 , a key storage section 8 , a decryption information storage section 9 , and a decryption section 10 , in order to carry out the foregoing processes. The respective configurations of the broadcast receiving section 6 will be described below.
[0000] Decryption Code Obtainment Section
[0084] The decryption code obtainment section 7 generates a decryption code request and transmits the generated decryption code request to the local station 2 , and consequently receives a decryption code response. The decryption code obtainment section 7 decrypts the received decryption code response by using a client secret key stored in the key storage section 8 . The decryption code obtainment section 7 obtains the decryption code included in the decrypted decryption code response and writes the obtained decryption code to the decryption information storage section 9 .
[0085] FIG. 3 is a diagram showing the configuration of the data of the decryption code request. The decryption code request includes user information, a client public key, additional information and a client electronic sign.
[0086] The user information includes information of the user of the client 4 . For example, if the content delivered to the client 4 by the local station 2 is charged, credit information for collecting a viewing fee and the like are included in the user information. Also, the user information may be a matter that can authenticate the user itself, such as the electronic sign prepared by the user. Incidentally, this embodiment is assumed such that the content delivered to the client 4 from the local station 2 is charged, so the user information includes the credit information of the user. The user information is inputted by the user through an input device connected to or installed in the client 4 . Also, the user information may be the data that is stored in advance in the auxiliary storage of the client 4 .
[0087] The client public key is public key data, which is capsulated together with the corresponding client secret key and held in the applet, as the data of the broadcast receiving applet stored in the client 4 . For this reason, the client public key can be basically read out or changed only by using the function of the broadcast receiving applet, namely, the configuration of the broadcast receiving section 6 . The client secret key corresponding to the client public key is similarly capsulated and stored in the client 4 . In the client public key and the client secret key, the same data is used by a plurality of users receiving the broadcast receiving applet. In other words, the plurality of users receive the broadcast receiving applet and consequently use the common client public key and client secret key.
[0088] The additional information is the data that is not related to the attainment of the broadcast system 1 according to the present invention, and it can be freely used by the matter that attains the broadcast system 1 .
[0089] The client electronic sign is the electronic sign generated by using the client secret key stored in the client 4 . This electronic sign is generated by the decryption code obtainment section 7 .
[0090] FIG. 4 is a diagram showing a configuration of the data of the decryption code response. The decryption code response includes a broadcast address, a decryption code, a decryption code expiration date, and a local station electronic sign.
[0091] The broadcast address indicates a multicast address of contents that is currently being delivered by the local station 2 .
[0092] The decryption code is the data used to decrypt the data of the contents delivered from the local station 2 .
[0093] The decryption code expiration date is the data corresponding to the decryption code and indicates the expiration date of the corresponding decryption code. The decryption code and its expiration date may be configured such that the plurality of them is included in one decryption code response, as necessary.
[0094] The local station electronic sign is the electronic sign generated by the local station 2 . The local station electronic sign is used by the decryption code obtainment section 7 to authenticate the decryption code response. The decryption code obtainment section 7 correlates the decryption code included in the authenticated decryption code response and its expiration date and writes them to the decryption information storage section.
[0000] Key Storage Section
[0095] FIG. 5 is a diagram showing data stored in the key storage section 8 . The key storage section 8 stores a key set of the client public key and the client secret key. Also, the key storage section 8 stores the public key (local station public key) of the local station 2 . The key storage section 8 correlates and stores the key set and the local station public key which are included in one broadcast receiving applet. The data stored in the key storage section 8 is read and written by the decryption code obtainment section 7 .
[0000] Decryption Information Storage Section
[0096] FIG. 6 is a diagram showing data (decryption information) stored in the decryption information storage section 9 . The decryption information storage section 9 stores information to decrypt the data of the contents delivered by the local station 2 . Concretely, the decryption information storage section 9 correlates and stores the decryption code and the decryption code expiration date. The decryption code is used by the decryption section 10 only for the decryption code expiration date.
[0000] Decryption Section
[0097] The decryption section 10 decrypts the data of the contents which is delivered by the local station 2 and received by the client 4 . The decryption section 10 uses the decryption code stored in the decryption information storage section 9 to decrypt the data of the received contents. The decryption section 10 passes the data (plaintext data) of the decrypted contents to the display section 11 .
[0000] Display Section
[0098] The display section 11 is configured by using a display such as a liquid crystal monitor, or a CRT (Cathode Ray Tub). Also, the display section 11 may be configured as needed by further using a sound output device such as a speaker, and a sound input device such as a microphone. The display section 11 outputs the plaintext data received from the broadcast receiving section 6 .
[0000] Local Station
[0099] The configuration of the local station 2 will be described below. The local station 2 is configured by using the information processing apparatus having the communication function such as a personal computer or a workstation, or a dedicated apparatus. The local station 2 includes a CPU connected through a bus, a main memory (RAM), and an auxiliary storage (a hard disk, a flash memory, or the like), as hardware. The local station 2 functions as the apparatus including a Web server function execution section 12 , an applet generation section 13 , a source file storage section 14 , an applet storage section 15 , a publication destination information storage section 16 , a viewer authentication section 17 , an encryption information storage section 18 , and an encryption section 19 , when the various programs (OS, applications, and the like) stored in the auxiliary storage are loaded to the main memory and executed by the CPU. Also, the local station 2 has a communication apparatus (not shown). The Web server function execution section 12 , the applet generation section 13 , the source file storage section 14 , the applet storage section 15 , the publication destination information storage section 16 , the viewer authentication section 17 , the encryption information storage section 18 , and the encryption section 19 use the communication apparatus to communicate with the client 4 or another apparatus through the network.
[0000] Web Browser Function Execution Section
[0100] The Web server function execution section 12 is attained when a program as the Web server (for example, HTTPD (Hypertext Transfer Protocol Daemon)) is executed by the CPU. The program to be executed may be a program as any Web server, for example, CERN Httpd or Apatch. The Web server function execution section 12 provides the functions as the Web server to the local station 2 .
[0101] The Web server function execution section 12 publishes the broadcast receiving applet stored in the applet storage section 15 to the Internet. That is, the Web server function execution section 12 holds the broadcast receiving applet in a form of being downloadable through the Internet to unspecified users. The Web server function execution section 12 may be configured such that with the execution of a different program, a different protocol such as FTP (File Transfer Protocol) is used to publish the broadcast receiving applet. As examples of the different programs, there are FTPD (FTP Daemon) and the like.
[0000] Applet Generation Section
[0102] The applet generation section 13 uses a source file stored in the source file storage section 14 to generate a broad cast receiving applet. The applet generation section 13 is attained when a program for generating the broadcast applet is executed by the CPU.
[0103] The applet generation section 13 generates a client key set. The applet generation section 13 capsules and embeds the generated client key set in the broadcast receiving applet. The applet generation section 13 writes the generated broadcast receiving applet to the applet storage section 15 .
[0000] Source File Storage Section
[0104] The source file storage section 14 is configured by using the auxiliary storage included in the local station 2 . The source file storage section 14 stores a source code to generate the broadcast receiving applet, as a source file. The source file stored in the source file storage section 14 is read out by the applet generation section 13 .
[0000] Applet Storage Section
[0105] The applet storage section 15 is configured by using the auxiliary storage, RAM, or the like included in the local station 2 . The applet storage section 15 stores the broadcast receiving applet generated by the applet generation section 13 . The broadcast receiving applet stored in the applet storage section 15 is published to the Internet by the Web server function execution section 12 .
[0000] Publication destination Information Storage Section
[0106] The publication destination information storage section 16 is configured by using the auxiliary storage, the RAM, or the like included in the local station 2 . The publication destination information storage section 16 stores the publication destination information. FIG. 7 is a diagram showing an example of the publication destination information. The publication destination information has the client public key and an expiration date of each client public key while they are correlated. The publication destination information is written by the applet generation section 13 .
[0000] Viewer Authentication Section
[0107] The viewer authentication section 17 is attained when a program to carry out the viewer authentication is executed by the CPU. The viewer authentication section 17 uses the client public key and client electronic sign, which are included in the decryption code request received from the client 4 , to authenticate the client 4 . If the client 4 is authenticated, the viewer authentication section 17 generates the decryption code response and transmits the generated decryption code response to the client 4 . At this time, the viewer authentication section 17 encrypts the generated decryption code response by using the received client public key.
[0000] Encryption Information Storage Section
[0108] The encryption information storage section 18 is configured by using the auxiliary storage, the RAM, or the like included in the local station 2 . FIG. 8 is a diagram showing an example of data (encryption information) stored in the encryption information storage section 18 . The encryption information storage section 18 correlates and stores the encryption code, the decryption code, and the expiration date. The data encrypted in accordance with the encryption code can be decrypted in accordance with the correlated and stored decryption code. The encryption code is used for encrypting the data of the contents, for the corresponding expiration date.
[0000] Encryption Section
[0109] The encryption section 19 is attained when a program to encrypt the plaintext data of the streaming data is executed by the CPU. The encryption section 19 generates an encrypted data and transmits the generated encrypted data to the client 4 . FIG. 9 is a diagram showing contents of the encrypted data. The encrypted data includes a timestamp, the additional information, and an encryption streaming data.
[0110] The encryption section 19 encrypts the plaintext data supplied by a supply section 20 . The encryption section 19 uses the encryption code stored in the encryption information storage section 18 , executes the encryption of the plaintext data, and generates the encryption streaming data. The encryption section 19 selects an effective encryption code in accordance with the corresponding expiration date, from the encryption codes, and uses the selected encryption code. The encryption streaming data generated by the encryption section 19 is transmitted together with the timestamp and additional information, as the encrypted data to the client 4 .
[0000] Supply Section
[0111] The supply section 20 stores the plaintext data of the streaming data and passes the stored plaintext data to the local station 2 . The plaintext data includes the data of the contents delivered to the client 4 . The supply section 20 is included in, for example, the key station 3 . The plaintext data stored in the supply section 20 is transmitted to the relay station 2 a or local station 2 , depending on the communication ability of the key station 3 .
OPERATION EXAMPLE
[0112] An operation example of the configuration of the broadcast system 1 will be described below. At first, an operation example of the client 4 is explained.
[0000] Client
[0113] The Web browser execution section 5 is operated as typical browser software. The display section 11 is operated as a typical output device. Also, the key storage section 8 and the decryption information storage section 9 are operated as the target from and to which the data is read and written. In this way, although those configurations have the characteristic parts in the stored contents of the data and the like, their operations are not the characteristic ones based on the present invention. For this reason, the detailed explanations with regard to the operation examples of the Web browser execution section 5 , the key storage section 8 , the decryption information storage section 9 , and the display section 11 are omitted.
[0000] Decryption Code Obtainment Section
[0114] FIG. 10 is a flowchart showing an operation example of the decryption code obtainment section 7 . FIG. 10 is used to explain the operation example of the decryption code obtainment section 7 .
[0115] The decryption code obtainment section 7 decrypts the decryption code response received from the local station 2 by using the client secret key (S 01 ). The decryption code obtainment section 7 , if the decryption is failed (S 02 -No), reports the failure of the decryption code obtainment to the user (S 03 ).
[0116] On the other hand, the decryption code obtainment section 7 , if the decryption is successful (S 02 -Yes), uses the local station public key and authenticates a generator of the received decryption code response (S 04 ). The decryption code obtainment section 7 , if the authentication is failed (S 05 -NG), reports the failure of the decryption code obtainment to the user (S 03 ).
[0117] On the other hand, the decryption code obtainment section 7 , if the authentication is successful (S 05 -OK), reports the broadcast address included in the received decryption code response to the decryption section 10 (S 06 ). Then, the decryption code obtainment section 7 sets the decryption code and decryption code expiration date, which are included in the received decryption code response, as the decryption information, in the decryption information storage section 9 (S 07 ).
[0000] Decryption Section
[0118] FIG. 11 is a flowchart showing an operation example of the decryption section 10 . FIG. 11 is used to explain the operation example of the decryption section 10 .
[0119] The decryption section 10 receives the encrypted data, from the broadcast address reported by the decryption code obtainment section 7 (S 08 ). That is, the decryption section 10 receives the encrypted data transmitted to the multicast address included in the broadcast address. The decryption section 10 obtains the timestamp from the received encrypted data (S 09 ). Next, the decryption section 10 uses the obtained timestamp as a key, retrieves the expiration date stored in the decryption information storage section 9 , and obtains the corresponding decryption code. That is, the decryption section 10 obtains the decryption code that is effective at the date and time which are indicated by the obtained timestamp (S 10 ). Next, the decryption section 10 uses the obtained decryption code, decrypts the encryption streaming data included in the received encrypted data, and obtains the plaintext data of the streaming data (S 11 ). Then, the decryption section 10 passes the obtained plaintext data to the display section 11 (S 12 ). In this way, the display section 11 displays the streaming data received from the local station 2 .
[0000] Local Station
[0120] The operation example of the local station 2 will be described below. The Web server function execution section 12 is operated as a typical Web server. Also, the source file storage section 14 , the applet storage section 15 , the publication destination information storage section 16 and the encryption information storage section 18 are operated as the target from and to which the data is read and written. In this way, although those configurations have the characteristic parts in the stored contents of the data and the like, their operations are not the characteristic ones based on the present invention. For this reason, the detailed explanations with regard to the operation examples of the Web server function execution section 12 , the source file storage section 14 , the applet storage section 15 , the publication destination information storage section 16 , and the encryption information storage section 18 are omitted.
[0000] Applet Generation Section
[0121] FIG. 12 is a flowchart showing an operation example of the applet generation section 13 . FIG. 12 is used to explain the operation example of the applet generation section 13 .
[0122] The applet generation section 13 is periodically actuated in response to the setting of the local station 2 . The applet generation section 13 , when actuated, generates the broadcast receiving applet in accordance with the flowchart shown in FIG. 12 .
[0123] At first, the applet generation section 13 reserves a work region called a work on the memory region. The region where the client public key, the client secret key, and the local station public key are stored as the key data is generated inside the work. The applet generation section 13 copies the source file from the source file storage section 14 to the work (S 13 ).
[0124] The applet generation section 13 sets the public key (local station public key) of the local station 2 preliminarily generated by the manager or the like of the local station 2 , to the local station public key inside the work (S 14 ). Next, the applet generation section 13 generates the key set of the client public key and the client secret key (S 15 ). The applet generation section 13 sets the generated key set to the client public key and client secret key inside the work (S 16 , S 17 ). Next, the applet generation section 13 sets the expiration date of the generated key set (S 18 ). The applet generation section 13 correlates the generated client public key and expiration date and writes as the publication destination information to the publication destination information storage section 16 (S 19 ).
[0125] The applet generation section 13 compiles the data inside the work and generates the broadcast receiving applet. The applet generation section 13 writes the generated broadcast receiving applet to the applet storage section 15 for the publication (S 20 ) Then, the applet generation section 13 discards the work (S 21 ).
[0000] Viewer Authentication Section
[0126] FIG. 13 is a flowchart showing an operation example of the viewer authentication section 17 . FIG. 13 is used to explain the operation example of the viewer authentication section 17 .
[0127] The viewer authentication section 17 , when receiving the decryption code request, uses the client electronic sign included in the received decryption code request, and authenticates a generator of the received decryption code request (S 22 ). The viewer authentication section 17 , if the authentication is failed (S 23 -NG), replies the data indicating a rejection to the client 4 (S 31 ).
[0128] On the other hand, the viewer authentication section 17 , if the authentication is successful (S 23 -OK), retrieves whether or not the client public key included in the received decryption code request is registered in the publication destination information (S 24 ). The viewer authentication section 17 , if it is not registered (S 25 -No), replies the data indicating the rejection to the client 4 (S 31 ).
[0129] On the other hand, the viewer authentication section 17 , if it is registered (S 25 -Yes), stores the content of the user information included in the received decryption code request, as a charging destination information (S 26 ). The collection of the charging to the user of the client 4 is executed by using this charging destination information. The collection of the charging may be executed by using any of existing methods.
[0130] The viewer authentication section 17 sets the multicast address of the content currently delivered by the local station 2 , as the broadcast address of the decryption code response (S 27 ). The viewer authentication section 17 sets the decryption code and expiration date, which are stored in the encryption information storage section 18 , to the decryption code of the decryption code response and the decryption code expiration date (S 28 ). At this time, the viewer authentication section 17 checks the expiration date with regard to the decryption codes to be stored in the encryption information storage section 18 , and uses the decryption code and expiration date which can be used currently and/or in future, for the setting.
[0131] The viewer authentication section 17 uses the secret key (local station secret key) of the local station 2 , generates the local station electronic sign. The viewer authentication section 17 sets the generated local station electronic sign to the local station electronic sign of the decryption code response (S 29 ) At this time, the viewer authentication section 17 uses the local station secret key corresponding to the local station public key reported to the client 4 and generates the local station electronic sign. Then, the viewer authentication section 17 uses the client public key included in the received decryption code request, encrypts the decryption code response, and transmits it to the client 4 (S 30 ).
[0000] Encryption Section
[0132] FIG. 14 is a flowchart showing an operation example of the encryption section 19 . FIG. 14 is used to explain the operation example of the encryption section 19 .
[0133] The encryption section 19 receives the plaintext data of the streaming data as the content from the supply section 20 (S 32 ). At this time, the encryption section 19 receives the plaintext data of one packet sentence. Next, the encryption section 19 receives a current time from a timer section (not shown) of the local station 2 (S 33 ). The encryption section 19 retrieves and obtains the encryption code whose expiration date corresponds to the received current time, from the encryption codes stored in the encryption information storage section 18 (S 34 ). The encryption section 19 uses the obtained encryption code, encrypts the received plaintext data, and generates the encryption streaming data (S 35 ). The encryption section 19 sets the received current time to the timestamp of the encrypted data (S 36 ). Also, the encryption section 19 sets the generated encryption streaming data, as the encryption streaming data of the encrypted data (S 37 ). Then, the encryption section 19 broadcasts (multicast transmits) the generated encrypted data to the broadcast address (S 38 ).
[0000] [Operation Sequence]
[0134] Among the operation sequences of the broadcast system 1 , the sequences of a receiving start process and a receiving continuation process will be described below.
[0000] Receiving Start Process
[0135] The receiving start process is the process executed when the client 4 starts receiving the content delivered by a certain local station 2 . FIG. 15 is a diagram showing a sequence example of the receiving start process. FIG. 15 is used to explain the sequence example of the receiving start process.
[0136] At first, the Web browser execution section 5 of the client 4 transmits a broadcast receiving applet download request to the Web server function execution section 12 of the local station 2 (Seq 01 ). That is, the client 4 requests the local station 2 to download the broadcast receiving applet. In response to this request, the Web server function execution section 12 executes the broadcast receiving applet download to the Web browser execution section 5 (Seq 02 ). That is, from the local station 2 to the client 4 , the broadcast receiving applet is downloaded. The downloaded broadcast receiving applet is executed by the Web browser execution section 5 , thereby actuating the broadcast receiving section 6 . At this time, since the broadcast receiving section 6 has not obtained the decryption code, the encrypted data delivered by the encryption section 19 of the local station 2 is not decrypted by the decryption section 10 (Seq 03 ).
[0137] When the user inputs the user information, the decryption code obtainment section 7 of the broadcast receiving section 6 transmits the decryption code request to the local station 2 (Seq 04 ). The viewer authentication section 17 of the local station 2 transmits the decryption code response to the client 4 , with regard to the received decryption code request (Seq 05 ) Even at this time, since the broadcast receiving section 6 has not obtained the decryption code, the encrypted data delivered by the encryption section 19 of the local station 2 is not decrypted by the decryption section 10 (Seq 06 ).
[0138] The decryption code obtainment section 7 obtains the decryption code included in the received decryption code response, and writes the decryption code to the decryption information storage section 9 , to thereby notify the decryption section 10 of the obtained decryption code. After that, the encrypted data delivered by the encryption section 19 of the local station 2 is decrypted by the decryption section 10 , and the decrypted streaming data is outputted by the display section 11 (Seq 07 , Seq 08 ).
[0000] Receiving Continuation Process
[0139] A receiving continuation process is a process executed when the client 4 continues to receive the content delivered by a certain local station 2 . The encryption code and decryption code which are used by the local station 2 are changed in association with the elapse of a time. This change may be periodically executed or may be executed at any time depending on the convenience of the local station 2 . In this way, the change of the encryption code and decryption code to be used can prevent the illegal viewer from carrying out the illegal viewing. In the receiving continuation process, in association with this change, a new decryption code is reported to the client 4 , and the client 4 continues to receive the content in which the new decryption code is used.
[0140] FIG. 16 is a diagram showing the sequence example of the receiving continuation process. FIG. 16 is used to explain the sequence example of the receiving continuation process.
[0141] Until the expiration of the expiration date of the decryption code used by the decryption section 10 , the encrypted data transmitted by the encryption section 19 is decrypted by the decryption section 10 and outputted by the display section 11 (Seq 09 , Seq 10 ). When the expiration date of the decryption code used by the decryption section 10 is expired, the decryption code obtainment section 7 of the broadcast receiving section 6 transmits the decryption code request to the local station 2 , in order to obtain a new decryption code (Seq 11 ). The viewer authentication section 17 of the local station 2 responds to the received decryption code request and transmits the decryption code response to the client 4 (Seq 12 ). At this time, since the broadcast receiving section 6 has not obtained the new decryption code, an encrypted data to which the new encrypted data is applied by the encryption section 19 of the local station 2 is not decrypted by the decryption section 10 (Seq 13 ).
[0142] The decryption code obtainment section 7 of the client 4 obtains the decryption code included in the received decryption code response and writes the decryption code to the decryption information storage section 9 , to thereby notify the decryption section 10 of the obtained decryption code. After that, the encrypted data delivered by the encryption section 19 of the local station 2 is decrypted by the decryption section 10 , and the decrypted streaming data is outputted by the display section 11 , and the receiving is continued (Seq 14 , Seq 15 ).
[0000] [Action/Effect]
[0143] In the first embodiment, the broadcast receiving applet in which the client key set and the local station public key are contained (embedded by the capsulation) is operated on the client 4 . The broadcast receiving applet transmits the decryption code request including the electronic sign in order to obtain the decryption code. The local station 2 uses the electronic sign included in the decryption code request and authenticates the client 4 that is the transmission source of the decryption code request. At this time, the data of the key contained in the broadcast receiving applet used to generate this electronic sign is capsulated, which basically disables the user's reference. Thus, the viewer authentication section 17 of the local station 2 can discriminate between the illegally transmitted decryption code request without using the broadcast receiving applet and the legally transmitted decryption code request by using the broadcast receiving applet. Hence, since the decryption code is designed so as not to be transmitted to the illegal viewer who does not use the broadcast receiving applet, the illegal viewing can be prevented.
[0144] Also, the decryption code response including the decryption code is encrypted and transmitted so as to be able to be decrypted in accordance with the key contained in the broadcast receiving applet. As mentioned above, the data of the key contained in the broadcast receiving applet is capsulated, which basically disables the user's reference. For this reason, even if the illegal viewer illegally succeeds in obtaining the decryption code response, it is difficult to decrypt this decryption code response. Thus, in the first embodiment, it is possible to doubly prevent the illegal viewing together with the foregoing illegal viewing prevention measures. That is, unless the data of the key contained in the broadcast receiving applet is leaked, it is possible to prevent the illegal viewing of the broadcast.
[0145] Also, since the illegal viewing can be prevented as mentioned above, the data of the content can be delivered from the local station 2 to the client 4 , through the multicast communication without using the unicast communication. Thus, the load on the communication process in the communication apparatus in the local station 2 and in the communication apparatus (relay) existing between the local station 2 and the client 4 is reduced.
[0146] Also, the user does not need to buy the special receiving apparatus and can view the broadcast by downloading the broadcast receiving applet through the Internet. Thus, the initial installation cost for the user can be reduced, which will stimulate demand.
[0147] Also, the update of the decryption code is attained by the decryption code request and decryption code response through the Internet. Thus, the update of the decryption code in the client 4 can be easily attained. Hence, the decryption code can be frequently updated, which enables the prevention of the occurrence of the illegal viewing caused by the continuous usage of the decryption code.
[0148] Also, the broadcast station for delivering the content through the local station 2 can collect the fee from the viewer in accordance with the user information included in the received decryption code request. Thus, the viewer can view anytime he/she wants, and pay the fee corresponding to the viewing time. Also, the broadcast station can arbitrarily set the fee for each content or viewing time, and charge the fee to the individual viewer on the basis of the viewing status of the content.
[0149] Also, the broadcast station can easily gather the viewing information, such as a viewing program and a viewing time, through the broadcast receiving applet.
VARIATION EXAMPLE
[0150] In the broadcast system 1 , the local station 2 is installed under the control of the relay station 2 a . However, without any installation of the local station 2 , the content distribution to the client 4 may be configured so as to be carried out by the relay station 2 a and the key station 3 . Also, in the broadcast system 1 , the relay station 2 a is installed under the control of the key station 3 . However, without any installation of the relay station 2 a , the content distribution to the client 4 may be configured so as to be carried out only by the key station. In this case, the key station 3 has the respective functions to carry out the content distribution to the client 4 , similarly to the relay station 2 a and the local station 2 .
[0151] Also, in the Seq 13 of the sequence example, the encrypted data which is not transiently decrypted by the decryption section 10 is induced owing to an update of the encryption code. However, the adjustment of the timing when the client 4 starts the receiving continuation process enables the decryption section 10 to seamlessly decrypt the received encrypted data. Specifically, a time necessary for the receiving continuation process is estimated, and the receiving continuation process may be started a given period in advance of a time point preceding the expiration date of the decryption code in use by the estimated time.
[0152] Also, in the first embodiment, the Internet is used to attain the broadcast system 1 . However, independently of the Internet, if the two-way communication is possible between the broadcast side (the local station 2 , the relay station 2 a , and the key station 3 ) and the client 4 , any different network may be used to attain the broadcast system 1 . As examples of any different network, there are a BS digital broadcast and a ground wave digital broadcast.
[0153] Also, among the data of the key contained in the broadcast receiving applet, the client public key may be referred to by the user. That is, the broadcast receiving applet may be configured so as to make the client public key public. With this configuration, the user can confirm the content of the data to be transmitted to the local station 2 in accordance with the program of the broadcast receiving applet.
[0154] Also, the local station 2 in the first embodiment of the present invention may be divided into a plurality of functions and installed. For example, the installation of: a first server (corresponding to the publication apparatus) having the Web server function execution section 12 , the applet generation section 13 , the source file storage section 14 , and the applet storage section 15 ; a second server (corresponding to the management apparatus) having the publication destination information storage section 16 and the viewer authentication section 17 ; and a third server (corresponding to the distribution apparatus) having the encryption information storage section 18 and the encryption section 19 may be configured to replace the local station 2 .
Second Embodiment
[0000] [System Configuration]
[0155] FIG. 17 is a diagram showing a schema of a broadcast system 1 A according to a second embodiment of the present invention. In the broadcast system 1 A, the client public key, the client secret key, the local station public key, and the local station secret key are arbitrarily switched to new keys (key switching process). FIG. 17 shows only a configuration required for explaining the key switching process. That is, a client 4 A and a local station 2 A shown in FIG. 17 have the configurations shown in FIG. 2 , respectively, in addition to the configurations shown in FIG. 17 . The broadcast system 1 A will be described below by using FIG. 17 .
[0000] Local Station
[0156] At first, the configuration of the local station 2 A is explained. The local station 2 A has an encryption section 19 A, instead of the encryption section 19 in the local station 2 . Also, the local station 2 A has a switch key storage section 21 and a switch key generation section 22 . Except for the foregoing points, the configuration of the local station 2 A has the configuration similar to that of the local station 2 .
[0000] Switch Key Storage Section
[0157] The switch key storage section 21 is configured by using the auxiliary storage in the local station 2 A. The switch key storage section 21 stores a switch client key set table and a switch local station key set table.
[0158] FIG. 18 is a diagram showing an example of the switch client key set table. FIG. 18 is used to explain the switch client key set table. Incidentally, hereafter, data “A” encrypted by a key of “Pa# 1 ” is represented by “X(Pa# 1 , A)”.
[0159] The switch client key set table is used when the local station 2 A changes the client key set (the client public key and the client secret key) used by the client 4 A. The switch client key set table has: the client public key which is currently used by the client 4 A and the local station 2 A; the switch client key set (the switch client public key and the switch client secret key) to be used in future by the client 4 A and the local station 2 A (after the key switching process); and a switch completion time, in such a manner that the client public key, the switch client key set and a switch completion time are correlated with each other. The switch client key set table holds as the switch client secret key the data encrypted by the client public key.
[0160] FIG. 19 is a diagram showing an example of the switch local station key set table. FIG. 19 is used to explain the switch local station key set table. The switch local station key set table has: the local station key set (the local station public key and the local station secret key) which is currently used by the client 4 A and the local station 2 A; the switch local station key set (the switch local station public key and the switch local station secret key) to be used in future by the client 4 A and the local station 2 A (after the key switching process); and the switch completion time, in such a manner that the client public key, the switch client key set and a switch completion time are correlated with each other.
[0161] The client key set and the local station key set are used until the corresponding switch completion time. After the switch completion time, the switch client key set and the switch local station key set are used.
[0000] Encryption Section
[0162] The encryption section 19 A is different from the encryption section 19 included in the local station 2 , in that the electronic sign is added to the encrypted data and that the key switching process is executed. Except the foregoing two points, the encryption section 19 A has the same configuration as the encryption section 19 included in the local station 2 .
[0163] The encryption section 19 A uses the local station secret key to add the electronic sign to the encrypted data. With this electronic sign, the client 4 authenticates that the received encrypted data is the data which is encrypted and transmitted by the local station 2 A.
[0164] Also, the encryption section 19 A executes the key switching process. FIG. 20 is a diagram showing the content of the encrypted data generated by the encryption section 19 A at the time of the key switching process. The encryption section 19 A, when executing the key switching process, adds the switch key data to the encrypted data. The switch key data includes the switch client public key, the switch client secret key, and the switch local station public key. The data of the key included in the switch key data is reported as the encrypted data to the client 4 , and held and used in the client 4 .
[0000] Switch Key Generation Section
[0165] The switch key generation section 22 is attained when a program for generating a new record in the switch client key set table and switch local key set table is executed by the CPU of the local station 2 A. Here, the record in the switch client key set table indicates an entry (having the client public key, the switch client public key, the encrypted switch client secret key and the switch completion time in a correlated form) of the switch client key set table. Also, the record of the switch local station key set table indicates an entry having the switch local station key set, the local station key set, and the switch completion time in a correlated form.
[0166] The switch key generation section 22 selects any client public key stored in the publication destination information storage section 16 . The switch key generation section 22 generates the record corresponding to the selected client public key. That is, the switch key generation section 22 generates the switch client key set corresponding to the selected client public key. Then, the switch key generation section 22 writes the generated record to the switch key storage section 21 .
[0167] Also, the switch key generation section 22 generates a new local station key set. At this time, the switch key generation section 22 substitutes the switch local station public key and switch local station secret key, which are stored in the switch key storage section 21 , for the local station public key and local station secret key. Then, the switch key generation section 22 sets the newly generated local station key set for the switch local station public key and switch local station secret key of the switch key storage section 21 .
[0168] The operation of the switch key generation section 22 may be configured so as to be periodically executed or may be configured so as to be executed by considering the expiration date of each key.
[0000] Client
[0169] The configuration of the client 4 A will be described below. The client 4 A includes a decryption section 10 A to replace the decryption section 10 in the client 4 . Except for the foregoing points, the configuration of the client 4 A is similar to that of the client 4 .
[0000] Decryption Section
[0170] The decryption section 10 A is different from the decryption section 10 in that the electronic sign is used to authenticate the encrypted data and that the key switching process is executed. The decryption section 10 A, when the encrypted data is received from the local station 2 A, authenticates a generator of the received encrypted data. The decryption section 10 A carries out the authentication by using the local station electronic sign included in the received encrypted data and the local station public key stored in the key storage section 8 of the self apparatus 4 .
[0171] Also, the decryption section 10 A, when receiving the encrypted data including the switch key data from the local station 2 , executes the key switching process. The decryption section 10 A reflects the data of the received switch key data on the key storage section 8 , at the time of the key switching process. In this case, the decryption section 10 A substitutes the client public key, client secret key, and local station public key, which are stored in the key storage section 8 , for the switch client public key, switch client secret key, and switch local station public key of the received switch key data.
OPERATION EXAMPLE
[0172] An operation example of the configuration of the broadcast system 1 A will be described below only with regard to the different points from the operation example in the broadcast system 1 . At first, an operation example of the local station 2 A is explained.
[0000] Local Station
[0173] The switch key storage section 21 is operated as the target from and to which the data is read and written. In this way, although the operation of the switch key storage section 21 has the characteristic parts in the memory content of the data and the like, its operation is not the characteristic part based on the present invention. Also, the configuration of the local station 2 A is similar to that of the local station 2 except for the configuration of the switch key storage section 21 , switch key generation section 22 , and encryption section 19 A. Thus, hereafter, only operation examples of the encryption section 19 A and switch key generation section 22 are explained.
[0000] Decryption Section
[0174] FIGS. 21 to 24 are flowcharts showing the operation examples of the encryption section 19 A. FIGS. 21 to 24 are used to explain the operation examples of the encryption section 19 A.
[0175] The encryption section 19 A generates a variable referred to as an index, on the memory region, and initializes the index (S 39 : refer to FIG. 21 ). The concrete process for the initialization may be arbitrarily configured depending on the actual installation of the program. Here, as an example, the index is assumed to be the variable having any of integer values, and the initialization of the index is assumed to substitute 0 for the index.
[0176] The encryption section 19 A examines the presence or absence of the record (entry) corresponding to the index, in the switch client key set table. If there is not the corresponding record (S 40 -No), the encryption section 19 A initializes the index (S 41 ). On the other hand, if there is the corresponding record (S 40 -Yes) or after the process of S 41 , the encryption section 19 A receives the plaintext data corresponding to one packet from the supply section 20 (S 42 ) Next, the encryption section 19 A receives the current time from the timer section (not shown) of the local station 2 A (S 43 ). The encryption section 19 A retrieves and obtains the encryption code whose expiration date corresponds to the received current time, from the encryption codes stored in the encryption information storage section 18 (S 44 ). The encryption section 19 A uses the obtained encryption code, encrypts the received plaintext data and generates the encryption streaming data (S 45 ). The encryption section 19 A sets the received current time for the timestamp of the encrypted data (S 46 ). Also, the encryption section 19 A sets the generated encryption streaming data, as the encryption streaming data of the encrypted data (S 47 ).
[0177] Then, the encryption section 19 A examines the presence or absence of the record (entry) corresponding to the index, in the switch client key set table. If there is no corresponding record (S 48 -No: refer to FIG. 22 ), the encryption section 19 A carries out the processes on and after S 56 (refer to FIG. 23 ). These processes will be described later.
[0178] On the other hand, if there is the corresponding record (S 48 -Yes: refer to FIG. 22 ), the encryption section 19 A examines whether or not the switch completion time is set with regard to the record corresponding to the index. If the switch completion time is not set (S 49 -No), the encryption section 19 A uses the current time to calculate the switch completion time, and sets the calculated switch completion time (S 50 ). Specifically, a time period (for example, several minutes) over which the key switching process is assumed to be completed in all of the clients 4 A is added to the current time, thereby calculating the switch completion time. In other words, the decryption section 10 A executes the key switching process during this additional period. On the other hand, if the switch completion time is set (S 49 -Yes) or after the process of S 50 , the encryption section 19 A sets the client public key of the corresponding record, for the client public key of the encrypted data (S 51 ). Also, the encryption section 19 A sets the switch client public key and switch client secret key of the corresponding record, for the switch client public key and switch client secret key of the encrypted data (S 52 ).
[0179] Next, the encryption section 19 A compares the switch completion time of the corresponding record and the current time. If the switch completion time is ahead of the current time (S 53 -No: refer to FIG. 23 ), the encryption section 19 A updates the index (S 54 ). The update of the index is, specifically, to change the value of the index so that the index indicates a different record from the corresponding record in the switch client key set table. On the other hand, if the switch completion time is behind the current time (S 53 -Yes), the encryption section 19 A deletes the corresponding record from the switch client key set table (S 55 ).
[0180] After the process of S 54 , or after the process of S 55 , or in the case of S 48 -No (refer to FIG. 22 ), the encryption section 19 A confirms whether or not the local station public key and the local station secret key are registered in the switch local station key set table. If there is no registration (S 56 -No), the encryption section 19 A executes the processes on and after S 64 (refer to FIG. 24 ). These processes will be described later. On the other hand, if there is the registration (S 56 -Yes: refer to FIG. 23 ), the encryption section 19 A confirms whether or not the switch completion time is set for the switch local station key set table. If the switch completion time is not set (S 57 -No), the encryption section 19 A calculates and sets the switch completion time (S 58 ). On the other hand, if the switch completion time is set (S 57 -Yes), or after the process of S 55 , the encryption section 19 A sets the switch local station public key of the switch local station key set table, for the switch local station public key of the encrypted data (S 59 : refer to FIG. 24 ).
[0181] Next, the encryption section 19 A uses the local station secret key of the switch local station key set table to add the electronic sign to the encrypted data (S 60 ). Then, the encryption section 19 A transmits the encrypted data to which the electronic sign is added, to the client 4 A (S 61 ).
[0182] Next, the encryption section 19 A compares the switch completion time of the switch local station key set table with the current time. If the switch completion time is behind the current time (S 62 -Yes), the encryption section 19 A initializes the local station public key, local station secret key, and switch completion time of the switch local station key set table (S 63 ). Concretely, the encryption section 19 A substitutes the value (for example, a zero value, NULL) indicating that the local station public key, the local station secret key, and the switch completion time are not set, for each value.
[0183] On the other hand, if the switch completion time is ahead of the current time (S 62 -No), or after the process of S 63 , or the case of S 56 -No (refer to FIG. 23 ), the encryption section 19 A uses the switch local station secret key of the switch local station key set table to add the electronic sign to the encrypted data (S 64 ). Here, the encrypted data to which the electronic sign is added is the data similar to the encrypted data transmitted at the process of S 61 , except for having the different electronic sign. Then, the encryption section 19 A transmits the encrypted data to which the electronic sign is added, to the client 4 A (S 65 ) and executes the processes on and after S 40 (refer to FIG. 21 ).
[0000] Switch Key Generation Section
[0184] FIG. 25 is a flowchart showing the operation example of the switch key generation section 22 . FIG. 25 is used to explain the operation example of the switch key generation section 22 .
[0185] The switch key generation section 22 selects any client public key (for example: Pa# 2 ) from the client public key stored in the publication destination information storage section 16 (S 79 ). For example, the switch key generation section 22 selects the client public key whose expiration date is expiring (for example, several minutes until the expiration date).
[0186] Next, the switch key generation section 22 generates the switch client public key (for example: Pa# 3 ) and the switch client secret key (for example: Pa# 3 ) (S 80 ). The switch key generation section 22 encrypts the generated switch client secret key by using the selected client public key (S 81 ). Then, the switch key generation section 22 correlates the selected client public key, the generated switch client public key, and the encrypted switch client secret key (for example: X(Pa# 2 , Pa# 3 )), and writes those to the switch key storage section 21 (S 82 ).
[0000] Client
[0187] The configuration except for the decryption section 10 A of the client 4 A is equal to the configuration of the client 4 . Thus, only the operation example of the decryption section 10 A will be described below.
[0000] Decryption Section
[0188] FIGS. 26 and 27 are flowcharts showing the operation example of the decryption section 10 A. FIGS. 26 and 27 are used to explain the operation example of the decryption section 10 A.
[0189] The decryption section 10 A, when receiving the encrypted data (S 66 : refer to FIG. 26 ), uses the local station public key stored in the key storage section 8 to authenticate a generator of the encrypted data (S 67 ). If the authentication is failed (S 68 -NG), the decryption section 10 A returns to the process of S 66 . On the other hand, if the authentication is successful (S 68 -OK), the decryption section 10 A confirms whether or not the switch local station public key is set for (included in) the received encrypted data. If the switch local station public key is set (S 69 -Yes), the decryption section 10 A sets this switch local station public key, as the local station public key of the key storage section 8 of the client 4 A (S 70 ).
[0190] On the other hand, if the switch local station public key is not set for the encrypted data (S 69 -No), or after the process of S 70 , the decryption section 10 A confirms whether or not the client public key included in the encrypted data and the client public key stored in the key storage section 8 of the client 4 A are coincident. If they are not coincident (S 71 -No), the decryption section 10 A executes the processes on and after S 75 (refer to FIG. 27 ).
[0191] On the other hand, if they are coincident (S 71 -Yes: refer to FIG. 26 ), the decryption section 10 A decrypts the switch key data stored in encrypted data by using the client secret key stored in the key storage section 8 of the client 4 A (S 72 ). The decryption section 10 A carries out the processes on and after S 75 , if the decryption failed (S 73 -NG: refer to FIG. 27 ). On the other hand, if the decryption was successful (S 73 -OK), the decryption section 10 A sets the content of the decrypted switch key data, for the key storage section 8 (S 74 ). That is, the decryption section 10 A sets the switch client public key, switch client secret key, and switch local station public key which are included in the decrypted switch key data, for the client public key, client secret key, and switch local station public key which are stored in the key storage section 8 .
[0192] After the process of S 74 , or in the case of S 73 -NG, or in the case of S 71 -No (refer to FIG. 26 ), the decryption section 10 A reads out and obtains the timestamp included in the encrypted data (S 75 ). Next, the decryption section 10 A defines the obtained timestamp as the key, retrieves the expiration date stored in the decryption information storage section 9 and obtains the corresponding decryption code. That is, the decryption section 10 obtains the decryption code that is effective on the date and time indicated by the obtained timestamp (S 76 ). Next, the decryption section 10 A uses the obtained decryption code to decrypt the encryption streaming data included in the received encrypted data and obtains the plaintext data of the streaming data (S 77 ) Then, the decryption section 10 A passes the obtained plaintext data to the display section 11 (S 78 ). In this way, the display section 11 displays the streaming data received from the local station 2 A. After the process of S 78 , the decryption section 10 A executes the processes on and after S 66 .
[0000] [Operation Sequence]
[0193] Next, among the operation sequences of the broadcast system 1 A, the process when the switch client key set and the switch local station key set are switched respectively is explained.
[0000] Case of Switch Client Key Set
[0194] FIG. 28 is a sequence diagram showing the process when the switch client key set is switched. When the switch key generation section 22 registers a new record in the switch key storage section 21 , the encryption section 19 A transmits the encrypted data, to which the client public key (Pa# 1 ), the switch client public key (Pa# 4 ) and the switch client secret key (Pa# 4 ) are added, to the client 4 A (Seq 16 ). The decryption section 10 A of the client 4 A, when this encrypted data is received, uses the added information to update the data of the key stored in the key storage section 8 . Hereafter, for a certain time (until the switch completion time set for the switch client key set table), the foregoing encrypted data is transmitted (Seq 17 ).
[0000] Case of Switch Local Station Key Set
[0195] FIG. 29 is a sequence diagram showing the process when the switch local station key set is switched. The encryption section 19 A, when transmitting the encrypted data, uses the local station secret key (PB# 1 ) to add an electronic sign (S(PB# 1 )) (Seqs 19 , 20 ). When the switch key generation section 22 registers the new record in the switch key storage section 21 , the encryption section 19 A adds the newly generated switch local station public key (Pb# 4 ) to the encrypted data and transmits the data (Seq 21 ).
[0196] The decryption section 10 A of the client 4 A, when receiving the encrypted data to which the switch local station public key is added, uses the added switch local station public key to update the content of the key storage section 8 .
[0197] After the new record is generated in the switch key storage section 21 , the encrypted data to which the electronic sign (S(PB# 4 )) based on the switch local station secret key (PB# 4 ) and the encrypted data to which the electronic sign based on the local station secret key (PB# 1 ) and the switch local station public key (Pb# 4 ) are added are transmitted to the encryption section 19 A (Seqs 22 , 23 and 24 ).
[0198] After the elapse of the switch completion time, the encryption section 19 A transmits the encrypted data to which the electronic sign (S(PB# 4 )) based on the public key (PB# 4 ) in the new record is added (Seqs 25 , 26 ).
[0000] [Action/Effect]
[0199] In the second embodiment of the present invention, the switching between the client key set and the local station key set is executed. Typically, in the encryption key (the public key and the secret key), as the usage period becomes longer, the possibility of the leakage becomes higher. Thus, the execution of the switching between the client key set and the local station key set enables the prevention of the leakage.
[0200] Also, the report to the client 4 A of the switch client key set and switch local station public key is carried out by using the current local station secret key. Thus, unless the current local station secret key is leaked, the leakage of the switch client key set and switch local station public key is prevented.
[0201] Also, the report to the client 4 A of the switch client key set and switch local station public key is carried out as the encrypted data. That is, the encrypted data including the data of those keys is transmitted to the client 4 A. Then, the decryption section 10 A of the client 4 A uses the data of those keys included in the encrypted data and updates the memory content of the key storage section 8 . Thus, the user of the client 4 A, if the key is updated, does not need to again download the broadcast receiving applet. Similarly, the user of the client 4 A does not need to carry out the procedure for updating the key.
[0202] The disclosures of international application PCT/JP2003/001932 filed on Feb. 21, 2003 including the specification, drawings and abstract are incorporated herein by reference.
INDUSTRIAL APPLICABILITY
[0203] The present invention can be applied to industries that provide services for delivering contents which need to be protected against illegal obtainment (for example, the content of the pay broadcast) to an unspecified large number of persons. | A distribution system comprising an adding unit adding an electronic sign to a code request by using first key data corresponding to second key data possessed by a managing device to which a code request is sent; a transmitting unit transmitting the code request which the electronic sign generated by the adding unit; a receiving unit receiving encrypted data to be multicast and a code response transmitted in response to the code request; an acquiring unit decrypting decrypting code included in the code response received by the receiving unit and encrypted by third key data, by using fourth key data corresponding to the third key data acquiring the decrypted decrypting data; and a decrypting unit decrypting encrypted data received by the receiving unit by using decrypting data acquire by the acquiring unit and delivering the decrypted data to output unit. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to a sample servo type optical information medium capable of recording and reproducing information optically, the information medium indicating a replica plate or a stamper or master for fabricating a replica plate.
As tracking servo methods adoptable in an optical disc capable of recording and reproducing information there are two methods which are a continuous groove servo method and a sample servo method. The sample servo method is described, for example, in U.S. Pat. No. 4,402,061.
Further, as a patent application relating to sample servo control there has been filed Japanese Patent Application No. 62-42522 (Feb. 27, 1987), which has also been filed in the U.S. and Europe.
The continuous groove servo method has long been developed, while the sample servo method has recently been developed actively because of high tracking stability.
According to the sample servo method, sector address portions and sample mark areas are disposed in places along an imaginary track beforehand on a replica plate of an optical disc. It is necessary that about 30 sector address portions be present on one circle of the imaginary track and 1,000 to 3,000, usually 1,376, sample mark areas present thereon.
And in each sample mark area there are present two sample marks and a clock pit, as a pair, along the center line of the imaginary track.
The sample marks are formed as wobble pits wobbled symmetrically right and left from the center line of the imaginary track. The clock pit is formed so that the center thereof is positioned on the center line of the imaginary track. The sample marks will hereinafter be referred to as wobble pits.
These wobble and clock pits each have a length, t, of 90 nsec on time base. For example, the pit length, t, is 0.5 μm at a disc radius of 30 mm and a disc revolution of 1,800 rpm. An optical depth of each pit is λ/4 (λrepresents the wavelength of laser light used in information recording and playback, usually 830 nm).
For recording or reproducing information using such sample servo type optical disc, laser light is radiated onto the replica plate from a recording/playback head (not shown), then the reflected light is detected and a tracking control is performed for the recording/playback head so that the head occupies a position in which the quantities of reflected lights from the wobble pits are the same. By so doing, the recording/playback head can trace over the center line of the imaginary track passing through the center of the clock pit. And the detection of clock data is effected by detecting the quantity of reflected light from the clock pit.
Of most importance in the sample servo type optical disc is in which positions wobble pits are to be formed. If the positions where wobble pits are formed are not symmetrical right and left with respect to the center line of the imaginary track passing through the center of the clock pit, the wobble pits will become different in size (shape) from each other under the wobble pit forming method available.
That the wobble pits are not in positions symmetrical right and left with respect to the center line of the imaginary track and are different in size (shape) from each other, means that it is impossible to effect an accurate tracking control.
Therefore, during the optical disc fabricating process, it is a very important matter to measure the wobble width (wobble quantity) of each wobble pit, namely, the distance from the center line of the imaginary track to the center of each wobble pit, to estimate the condition of each wobble pit being formed.
In the prior art, however, there are present only pits on the sample servo type optical disc, so for measuring the wobble width of each wobble pit referred to above, there is no other way than measuring it with reference to the clock pit through the center of which the center line of the imaginary track passes. However, since there is a considerable distance between each clock pit and each wobble pit, it is difficult to even judge which clock pit and wobble pit are in a pair. Thus, it has been very difficult to actually measure the wobble width of each wobble pit.
SUMMARY OF THE INVENTION
It is therefore the object of the present invention to solve the above-mentioned problem of the prior art and provide a replica plate or a stamper or master, as an optical information medium, capable of measuring the wobble width (wobble quantity) of each wobble pit and estimating the condition of the wobble pit being formed during a sample servo type optical disc fabricating process.
In the present invention, in order to achieve the above-mentioned object, a groove or a pit serving as a reference line for measuring and estimating the wobble quantity of each wobble pit is formed on and along the center line of an imaginary track in a certain area of a replica plate which constitutes the sample servo type optical disc, or of a stamper or master which is for fabricating the replica plate.
In the prior art, as mentioned above, for measuring the wobble width (wobble quantity) of each wobble pit, there has been no other method than measuring it with reference to a clock pit through the center of which the center line of an imaginary track passes, because there are present only pits on the sample servo type optical disc.
In the present invention, in view of the point just mentioned above, a groove or pit is formed as a reference line for measuring and estimating the wobble quantity of each wobble pit, on and along the center line of an imaginary track in a certain area of the replica plate or of a stamper or master.
By using such groove or pit as a reference line in the sample servo type optical disc fabricating process, the wobble width (wobble quantity) can be measured easily and so it becomes possible to estimate the condition of the wobble pit being formed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are each a partially enlarged view showing, on a larger scale, a certain area of a glass master according to an embodiment of the present invention;
FIG. 2 is a construction diagram schematically showing a laser exposurer for forming a continuous groove or pits, which are illustrated in FIG. 1, on a glass master;
FIGS. 3A and 3B are plan views showing a replica plate according to another embodiment of the present invention; and
FIG. 4 is an explanatory view shown another concrete example of a reference line formed in the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description is now provided about an example of application of the present invention to a glass master for fabricating a replica disc in an optical disc according to an embodiment of the present invention.
In FIGS. 1A and 1B, which are partially enlarged views showing on a larger scale a certain area of a glass master embodying the invention, the reference numeral 5 denotes a clock pit; numerals 6 and 7 each denote a wobble pit; numeral 8 denotes a continuous groove; and numeral 9 represents the center line of an imaginary track. The difference between FIGS. 1A and 1B will be explained later.
According to this embodiment, in a glass plate for fabricating a replica plate, a continuous groove 8 serving as a reference line for measuring the wobble width (wobble quantity) of the wobble pits 6 and 7 and estimating the condition of the pits being formed, is formed in addition to the wobble pits 6, 7 and clock pit 5 in an area outside the user area of the optical disc, as shown in FIGS. 1A and 1B.
FIG. 2 is a construction diagram schematically showing a laser exposurer for forming the aforesaid continuous groove as well as wobble and clock pits on the glass master. In FIG. 2, the numeral 20 denotes a laser light source; numerals 21 and 33 each denote a half mirror; numerals 22, 29, 30, 32 and 34 each denote a mirror; numerals 23, 24, 27, 28 and 35 each denote a lens; numerals 25 and 26 each denote a signal modulator (hereinafter referred to as "AOM" (Acoustic Optical Modulator)); numeral 31 denotes a beam deflector ("AOD" (Acoustic Optical Deflector) hereinafter); and numeral 36 denotes a glass master, with a resist layer being formed by application onto the glass master 36. AOM's 25, 26 and AOD 31 are each constituted by an acousto-optical element.
As shown in FIG. 2, a laser beam emitted from the laser light source 20 is split into two by the half mirror 21, one of which then passes along an optical path, m, while the other passes along an optical path, n.
The laser beam traveling along the optical path, m, is incident on the AOM 25 through lens 23, where it is modulated according to pits to be formed (wobble and clock pits). More specifically, in a place where a pit is to be formed, the AOM 25 allows the incident laser beam to pass, while in a place where a pit is not to be formed, the AOM 25 shuts off the incident laser beam. Next, the laser beam which has passed through the AOM 25 is incident on the AOD 31 through lens 27 and mirror 29, where deflection of beam is made according to a pit to be formed. More specifically, only in a place where a wobble pit is to be formed, the AOD 31 deflects the incident laser beam in a predetermined direction and does not deflect the beam in a place where a clock pit is to be formed. Thereafter, the laser beam which has passed through the AOD 31 is applied onto the glass master 36 through mirror 32, half mirror 33, mirror 34 and lens 35 to form wobble and clock pits.
On the other hand, the laser beam traveling along the optical path, n, is incident on the AOM 26 through mirror 22 and lens 24. Upon arrival at an area outside the area to serve as the user area, the AOM 26 allows the incident laser beam to pass therethrough continuously. The laser beam thus from the AOM 26 is applied onto the glass master 36 through lens 28, mirror 30, half mirror 33, mirror 34 and lens 35, to form a continuous groove. In this case, adjustment is made in advance so that the radiated position of the laser beam from the AOM 26 is coincident with that of the laser beam from the AOD 31 when the AOD does not perform the deflection of beam. By so doing, a continuous groove is sure to be formed on the center line of an imaginary track passing through the center of a clock pit.
In this way, by using the laser exposurer shown in FIG. 2, wobble pits 6, 7 and a clock pit 5 are formed in the area to serve as the user area on the glass master 36, and outside the area to serve as the user area there is formed such a continuous groove 8 extending along the center line 9 of the imaginary track as shown in FIG. 1.
Since in this embodiment the continuous groove 8 is never fail to be formed on the imaginary track center line 9 as noted above, the wobble width (wobble quantity) of the wobble pits 6 and 7 can be measured easily by using the continuous groove 8 as a reference line.
For example, it is here assumed that the thus-formed wobble pits 6, 7, clock pit 5 and continuous groove 8 are in such a state as shown in FIG. 1A. In this case, by measuring the wobble widths l 1 and l 2 of the wobble pits 6 and 7 using the continuous groove 8 as a reference line, l 1 is found equal to l 2 and it is possible to estimate that the forming conditions are appropriate or normal (in other words, the wobble pits 6 and 7 are symmetric right and left with respect to the imaginary track center line 9 and the same in size and shape and contact the continuous groove 8, as shown in the normal condition).
If it is assumed that the thus-formed wobble pits 6, 7, clock pit 5 and continuous groove 8 are in such a state as shown in FIG. 1B then upon measurement the wobble widths of the wobble pits 6 and 7 are found to be in the relation of l 1 >l 2 and it is possible to estimate that the forming conditions are not appropriate (in other words, the wobble pits 6, 7 are asymmetrical with respect to the imaginary track center line 9 and different in size and shape and wobble pit 7 does not contact continuous groove 8, as shown). A probable cause is that the adjustment of the AOD 31 shown in FIG. 2 is not sufficient.
Such inconvenience can be remedied by adjusting the AOD 31 correctly so that the wobble widths l 1 and l 2 of the wobble pits 6 and 7 measured above satisfy the relation of l 2 =l 2 .
Thus, by forming the continuous groove 8 along the imaginary track center line 9 and using it as a reference line, it is possible to easily measure the wobble widths of the normal or abnormal wobble pits 6 and 7 and estimate the condition of the wobble pits being formed. Further, a paired relation between wobble and clock pits becomes clear.
In FIG. 2, as previously noted, adjustment is made in advance so that the radiated position on the glass master 36 of the laser beam from the AOM 26 is coincident with that of the laser beam from the AOD 31 when the AOD does not perform the beam deflection. If the adjustment should not be made correctly for some reason or other, the continuous groove 8 would be formed somewhat off the imaginary track center line 9 to either the right or the left. However, even if there should be formed such a continuous groove 8, as long as it is formed in parallel with the center line 9, it is possible to measure the wobble widths of the wobble pits 6 and 7 by measuring the deviation between the thus-formed continuous groove 8 and the clock pit 5 through the center of which the center line 9 of the imaginary track passes and by using the continuous groove 8 as a reference line while taking such deviation into consideration.
The following description is now provided about an example of application of the present invention to a replica plate which constitutes a 5.25-inch dia. postscript type optical disc according to another embodiment of the present invention.
FIG. 3 is a plan view showing a replica plate according to another embodiment of the present invention, in which FIG. 3A schematically shows the whole of the replica plate and FIG. 3B shows a principal portion of the replica plate on a larger scale.
The replica shown in FIG. 3A, indicated at 1, is fabricated by first producing a stamper on the basis of a glass master obtained in such a manner as in the previous embodiment and then injection-molding polycarbonate using the stamper thus fabricated. The replica plate 1 has an inside diameter of 15 mm (in diameter), an outside diameter of 130 mm (in diameter) and a thickness of 1.2 mm.
On the replica plate 1 are formed sector address portions 2 and sample mark areas 3 in places along an imaginary track. The area from a 29 mm position up to a 61 mm position in the disc radius serve as a user area 4.
In the user area 4 of each sample mark area 3 are formed in a pair sample marks 6, 7 and a clock pit 5 along a center line 9 of the imaginary track, as shown in FIG. 3B. Further, in each sample mark area 3 outside the user area 4, a continuous groove 8 serving as a reference line is formed on the imaginary track center line 9 in addition to the sample marks 6, 7 and clock pit 5 with respect to about ten imaginary tracks in the inner and outer peripheral portions of the user area 4.
The wobble pits 6, 7 and clock pit 5 have an optical depth of about λ/4 (λrepresents the wavelength of laser beam used in information recording and playback, usually 30 nm). The track pitch, indicated at P, is 1.5 μm and the pit width is 0.6 μm. As to the continuous groove 8 serving as a reference line, in order to minimize its interference with other pits, its width and depth are set at about 0.4 μm and about 300 Å, respectively. The groove depth is not specially limited if only the presence of the groove can be seen through a microscope; a depth of λ/16 or so is sufficient.
As to the number of the continuous groove to be formed, it may be at least one. However, forming two such grooves is advantageous in that the amount of deviation of wobble pits can be visually seen quantitatively because the spacing between the grooves correspond to the track pitch. Actually, 30 to 35 such grooves are formed. The reason is that thirty such grooves result in a width of approximately 50 μm because the track pitch is 1.5 μm and so their presence can barely be recognized visually. In the case of thirty continuous grooves, the time required for cutting is about 5 seconds. The time required for cutting the entire disc is about 60 minutes.
In the outer periphery of each continuous groove is formed at a width of about 1 mm such a double transfer preventing groove as described in the foregoing Japanese Patent Application No. 62-42522.
Thus in this embodiment the continuous groove 8 is formed along the imaginary track center line 9 in addition to wobble pits 6, 7 and clock pit 5 in the area outside the user area on the replica plate 1 and it is used as a reference line, whereby during the manufacturing process the wobble width (wobble quantity) of each of the wobble pits 6 and 7 can be measured and the condition of the wobble pit being formed can be grasped, so it can be easily judged whether the pit is being formed in an appropriate condition or not.
It is preferable that the continuous grooves be formed in either the inner or the outer periphery of the user area. They may be formed in both such inner and outer peripheries. It was experimentally confirmed that the deviation at the inner periphery and that at the outer periphery were equal. From this standpoint, it is sufficient to provide the continuous grooves in either the inner or the outer periphery of the user area. However, where the adjustment of the apparatus is not satisfactory, it is necessary to provide the continuous grooves in both such peripheries.
Although in the above embodiments the present invention was applied to the replica plate constituting the optical disc or to the glass master for fabricating the replica plate, the present invention is also effective in its application to a stamper obtained from the glass master.
Thus, in the present invention, all that is required is to merely form a reference line for measuring and estimating the wobble quantities of wobble pits on the center line of an imaginary track along the center line of the said track in a certain area of a replica plate or of a stamper or a master. The size and shape of such reference line are not specially limited.
For example, in the embodiment illustrated in FIG. 3, even if the width and depth of the continuous groove 8 serving as a reference line are set at about 0.5 μm and λ/8, respectively, (λ represents the wavelength of laser beam used in information recording and playback, usually 830 nm), there will be obtained a similar effect.
The reference line may be in such a shape of pit 10 formed along the imaginary track center line 9, as shown in FIG. 4, and it may be formed only in the portions of the wobble pits 6 and 7.
Effect of the Invention
According to the present invention, during the manufacturing process of a sample servo type optical disc it is possible to measure the wobble width (wobble quantity) of each wobble pit and easily estimate the condition of wobble pits being formed, whereby the time required for judging whether the optical disc being manufactured is good or not can be shortened and it is possible to obtain an optical disc of high accuracy. | The present invention relates to an optical information medium for recording and reproducing information optically. Particularly, it is concerned with a so-called sample servo type optical information medium wherein an optical head traces over the center line of an imaginary track on the basis of information obtained from at least a pair of wobble pits disposed on both sides of the said imaginary track center line. A continuous groove is formed between the paired wobble pits along the imaginary track center line in a certain area of the optical information medium so that the deviation of each wobble pit from the imaginary track center line can be easily grasped and the conditions of the wobble pits being formed can be estimated. The quality of the medium being manufactured can be easily judged by the presence of such continuous groove. | 6 |
PRIORITY CLAIM
This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 61/440,287, filed Feb. 7, 2011, which is expressly incorporated by reference herein.
BACKGROUND
The present disclosure relates to tubes, and particularly to tubes for storing and discharging fluid materials. More particularly, the present disclosure relates to a squeeze tube comprising a fluid-storage container and a fluid-dispensing closure coupled to the fluid-storage container.
SUMMARY
A squeeze tube in accordance with the present disclosure includes a squeezable fluid-storage container and a fluid-dispensing closure mated to the fluid-storage container. The fluid-dispensing closure is coupled to one end of the fluid-storage container and configured to control discharge of fluid stored in the fluid-storage container through a discharge aperture formed in the fluid-dispensing closure.
In illustrative embodiments, the fluid-dispensing closure includes a base having a ring, a fluid-discharge deck formed to include the discharge aperture, and a generally cone-shaped nozzle interposed between and coupled to the ring and the fluid-discharge deck. The cone-shaped nozzle includes an upper portion coupled to the fluid-discharge deck and a lower portion interposed between and coupled to the upper portion and the ring. The lower portion of the cone-shaped nozzle is formed to provide a recessed channel extending about the circumference of the lower portion.
In illustrative embodiments, an upper end of the fluid-storage container provides a tubular closure-mount sleeve that lies in a stationary and fixed position in the recessed channel formed in the lower portion of the cone-shaped nozzle in the base of the fluid-dispensing closure to support a tubular receptacle coupled to the tubular closure-mount sleeve below the fluid-dispensing closure. The fluid-dispensing closure includes a base formed to include a discharge aperture opening into an interior region bounded by the tubular closure-mount sleeve and the tubular receptacle and, in illustrative embodiments, a flip-top cap and a hinge for supporting the flip-top cap for movement relative to the base between opened and closed positions.
In illustrative embodiments, the tubular closure-mount sleeve of the fluid-storage container is nested in the recessed channel formed in the base of the fluid-dispensing closure. The result is that an exterior surface of a visible upper portion of the cone-shaped nozzle is arranged to mate and merge in smooth alignment with an abutting outer surface of the tubular closure-mount sleeve at an annular junction established between those exterior and outer surfaces to provide substantially smooth and continuous outside wall of the squeeze tube at the annular junction. In other words, a top rim and a fluid-discharge deck included in the fluid-dispensing closure are visible and located outside of the fluid-storage container while a bottom rim of the fluid-dispensing closure is hidden and located inside the fluid-storage container and is configured to cause the exterior surface of the top rim and the outer surface of the tubular closure-mount sleeve to mate end-to-end in smooth alignment with one another to provide the squeeze tube with a substantially smooth and continuous outer wall around a circumference of the squeeze tube.
In illustrative embodiments, the fluid-storage container comprises a tubular sleeve made of a multi-layer sheet. The sheet comprises an inner tubular layer, an outer tubular layer, and a middle tubular layer interposed between and coupled to the inner and outer tubular layers.
An upper portion of the inner tubular layer includes a bottom section that has an interior surface that mates with an exterior surface of the ring and a top section that is coupled to a top perimeter edge of the bottom section and is arranged to extend upwardly therefrom. The top section extends into the recessed channel to mate with a portion of the lower portion of the cone-shaped nozzle defining a floor of the recessed channel. The outer tubular layer extends through and lies in the recessed channel formed in the lower portion of the cone-shaped nozzle to cause an exterior surface of the upper portion of the cone-shaped nozzle to mate in smooth alignment with an exterior surface of the outer tubular layer to provide a substantially smooth and continuous exterior wall of the squeeze tube around the circumference of the squeeze tube at the junction between the fluid-dispensing closure and the fluid-discharge tube.
Additional features of the present disclosure will become apparent to those skilled in the art upon consideration of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.
BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description particularly refers to the accompanying figures in which:
FIG. 1 is a front elevation view of a squeeze tube in accordance with the present disclosure showing an elongated squeezable fluid-storage container formed to include an interior region and showing that the squeezable fluid-storage container is coupled to a lower portion of a fluid-dispensing closure and provided with a tubular upper end that is arranged to surround and cover that lower portion;
FIG. 2 is an enlarged perspective top view of a portion of the squeeze tube of FIG. 1 showing a flip-top cap included in the fluid-discharge closure of the squeeze tube in a closed position;
FIG. 3 is a view similar to FIG. 3 showing the flip-top cap after the flip-top cap has been moved to an opened position to expose a discharge aperture formed in a base of the fluid-discharge closure and suggesting that the base provides the lower portion of the fluid-dispensing closure that is surrounded and covered by the tubular upper end of the squeezable fluid-storage container;
FIG. 4 is an enlarged sectional view of a portion of the squeeze tube taken along line 4 - 4 of FIG. 3 showing that the base of the fluid-discharge closure includes a generally cone-shaped nozzle and an underlying cylinder-shaped ring and the squeezable fluid-storage container includes (1) a tubular closure-mount sleeve coupled to and arranged to surround and cover the cylinder-shaped ring and a lower portion of the generally cone-shaped nozzle and (2) a thin-walled tubular receptacle coupled to the tubular closure-mount sleeve and arranged to extend downwardly therefrom to provide most of the interior region of the squeezable fluid-storage container;
FIG. 5 is an enlarged view taken from the circled region of FIG. 4 showing that the cylinder-shaped ring and a lower portion of the generally cone-shaped nozzle included in the base of the fluid-dispensing closure is positioned to lie in the interior region formed in the squeezable fluid-storage container and also showing that an outer surface of the tubular closure-mount sleeve of the squeezable fluid-storage container is arranged to mate and merge in smooth alignment with an overlying exposed exterior surface of the upper portion of the generally cone-shaped nozzle of the base of the fluid-discharge closure to provide a substantially smooth and continuous outside wall of the squeeze tube around a circumference of the squeeze tube at a junction between the fluid-dispensing closure and the upper end of the squeezable fluid-storage container;
FIG. 6 is an enlarged view of the portion of the base of the fluid-discharge closure shown in FIG. 5 before the upper end of the fluid-storage container is coupled to the base of the fluid-dispensing closure as suggested, for example, in FIGS. 7-9 and showing (from bottom to top) the ring and lower, middle, and upper portions of the generally cone-shaped nozzle and showing that the middle portion is formed to include an exposed annular lip arranged to lie between exterior surfaces of the upper and lower portions;
FIG. 7 is a view similar to FIG. 6 showing a first assembly step in accordance with the present disclosure in which a tubular closure-mount sleeve included in the fluid-storage container is moved upwardly by a sleeve former (shown diagrammatically) to cause an inner surface of a bottom part of the tubular closure-mount sleeve to mate with the exterior surface of the ring included in the base of the fluid-dispensing closure;
FIG. 8 is a view similar to FIG. 7 showing a second assembly step in accordance with the present disclosure in which a top part of the tubular closure-mount sleeve is moved towards the generally cone-shaped nozzle included in the base of the fluid-dispensing closure by a mover included in the sleeve former;
FIG. 9 is a view similar to FIGS. 7 and 8 showing a third assembly step in accordance with the present disclosure in which heat is applied to the top part of the tubular closure-mount sleeve by a heater included in the sleeve former after an inner surface of the top part mates with the exterior surface of the lower portion of the generally cone-shaped nozzle to fluidize an annular tip of the tubular closure-mount sleeve;
FIG. 10 is a view similar to FIGS. 7-9 showing that the fluidized annular tip of the tubular closure-mount sleeve has solidified and been mated with the exposed annular lip provided in the middle portion of the generally cone-shaped nozzle of the fluid-dispensing closure to cause the outer surface of the tubular closure-mount sleeve to mate and merge in smooth alignment with the exterior surface of the upper portion of the generally cone-shaped nozzle of the base of the fluid-dispensing closure as suggested in greater detail in FIG. 12 ;
FIG. 11 is an enlarged sectional view of a portion of the squeeze tube taken from a first circled region of FIG. 10 ; and
FIG. 12 is an enlarged sectional view of a portion of the squeeze tube taken from a second circled region of FIG. 10 showing that the annular tip included in the tubular closure-mount sleeve is arranged to interconnect the inner and outer surfaces of the tubular closure-mount sleeve and mate with the exposed annular tip to cause the outer surface of the tubular closure-mount sleeve to mate and merge in smooth alignment with the exterior surface of the generally cone-shaped nozzle to provide a substantially smooth and continuous outside wall of the squeeze tube around a circumference of the squeeze tube at the junction between the fluid-dispensing closure and the upper end of the squeezable fluid-storage container as suggested in FIGS. 1-3 .
DETAILED DESCRIPTION
A squeeze tube 10 in accordance with the present disclosure is shown, for example, in FIGS. 1-3 . Squeeze tube 10 includes a fluid-dispensing closure 11 having a base 30 that is formed to include a discharge aperture 14 as suggested in FIG. 3 . Squeeze tube 10 also includes a fluid-storage container 16 having a tubular upper end that surrounds and mates with only a bottom rim 30 B of the base 30 that is included in fluid-dispensing closure 12 to cause discharge aperture 14 of fluid-dispensing closure 12 to open into an interior region 16 I formed in fluid-storage container 16 as suggested in FIGS. 4 and 5 . Fluid-storage container 16 also includes a tubular receptacle 19 that is closed at a lower end and coupled at an upper end to tubular closure-mount sleeve 18 to form interior region 16 I as suggested in FIG. 1 .
An exterior surface 12 E of a top rim 30 T included in base 30 of fluid-dispensing closure 12 is arranged as shown in FIG. 5 to mate and merge in smooth alignment with an outer surface 18 O of tubular upper end of fluid-storage container 16 to provide a substantially smooth and continuous outside wall of squeeze tube 10 at a junction 20 between top rim 30 T of base 30 of fluid-dispensing closure 12 and tubular upper end of fluid-storage container 16 as shown, for example, in FIGS. 1-3 . Tubular upper end is configured to define a tubular closure-mount sleeve 18 that is adapted to mate with and surround bottom rim 30 B of fluid-dispensing closure 12 as suggested in FIGS. 1 , 4 , and 5 .
As suggested in FIGS. 1 , 4 , and 5 , top rim 30 T of base 30 of fluid-dispensing closure 12 is exposed and visible while the underlying bottom rim 30 B of fluid-dispensing closure 12 is surrounded and covered by the tubular upper end (e.g., closure-mount sleeve 18 ) of fluid-storage container 16 and thus hidden from view once fluid-storage container 16 is coupled to bottom rim 30 B of base 30 . In an illustrative embodiment, base 30 includes a fluid-discharge deck 30 D formed to include discharge aperture 14 , a bottom rim 30 B coupled to tubular upper end of fluid-storage container 16 and arranged to lie in interior region 16 I of fluid-storage container 16 , and a visible and exposed top rim 30 T arranged to interconnect the overlying fluid-discharge deck 30 D and the underlying bottom rim 30 B as shown in FIG. 4 .
An illustrative coupling process is shown, for example, in FIGS. 6-10 . Once the coupling process has been completed to mount fluid-storage container 10 on bottom rim 30 B of base 30 of fluid-dispensing closure 12 , a smooth visible outside interface is established at the annular junction 20 provided between neighboring and abutting portions of the top rim 30 B of base 30 of fluid-dispensing closure 12 and the tubular upper end (e.g., closure-mount sleeve 18 ) of fluid-storage container to 16 as suggested in FIGS. 5 , 10 , and 12 .
Bottom rim 30 B of base 30 of fluid-dispensing closure 12 includes a first annular section 31 , a second annular section 32 L located above and coupled to first annular section 31 , and a third annular section 32 M located above and coupled to second annular section 32 L as shown, for example, in FIG. 5 . First annular section 31 is cylinder-shaped and each of second and third annular sections 32 L, 32 M has a frustoconical shape in an illustrative embodiment shown in FIG. 6 .
Top rim 30 T of base 30 of fluid-dispensing closure 12 is located above and coupled to third annular section 32 M as shown, for example, in FIGS. 4 and 5 . Fluid-discharge deck 30 D of base 30 is coupled to a top edge of top rim 30 T and formed to include discharge aperture 14 as suggested in FIG. 3 .
Tubular upper end of fluid-storage container 16 is arranged to surround and mate with exterior surfaces 83 , 82 , and 81 of first, second, and third annular sections 31 , 32 L, and 32 M of bottom rim 30 B of base 30 in an illustrative embodiment so that an outer surface 12 E of top rim 30 T of base 30 is visible and exposed to a consumer handling squeeze tube 10 as suggested in FIGS. 1-5 . A substantially smooth and continuous outside wall of squeeze tube 10 is formed around a circumference of squeeze tube 10 at the junction 20 between top rim 30 T of base 30 of fluid-dispensing closure 12 and an outer surface 18 O of tubular upper end of fluid-storage container 16 as suggested in FIGS. 1-5 .
Fluid-dispensing closure 12 is coupled to the tubular upper end of fluid-storage container 16 as shown, for example, in FIGS. 4 and 5 . In an illustrative embodiment, fluid-dispensing closure 12 includes a base 30 adapted to mate with tubular upper end of fluid-storage container 16 , a flip-top cap 40 , and a hinge 50 for supporting flip-top cap 40 for pivotable movement between a closed position closing discharge aperture 14 shown in FIG. 2 and an opened position opening discharge aperture 14 shown in FIG. 3 . Fluid-dispensing closure 12 is configured to control discharge of fluid stored in an interior region 16 I of the squeezable fluid-storage container 16 through a discharge aperture 14 formed in fluid-discharge deck 30 D of base 30 .
Base 30 of fluid-dispensing closure 12 can also be described to include a ring 31 , a generally cone-shaped nozzle 32 , and a fluid-discharge deck 30 D. Ring 31 is located inside interior region 16 I of the squeezable fluid-storage container 16 . Fluid-discharge deck 30 D is located outside interior region 16 I of the squeezable fluid-storage container 16 and formed to include discharge aperture 14 .
Cone-shaped nozzle 32 includes upper, middle, and lower portions 32 U, 32 M, and 32 L as shown, for example, in FIGS. 4-6 . Ring 31 and lower and middle portions 32 L, 32 M of cone-shaped nozzle 32 cooperate to define bottom rim 30 B of base 30 . Upper portion 32 U of cone-shaped nozzle 32 defines top rim 30 T of base 30 .
Upper portion 32 U ( 30 T) of cone-shaped nozzle 32 is coupled to fluid-discharge deck 30 D and located outside of interior region 16 I of fluid-storage container 16 as shown, for example, in FIGS. 1-4 . Lower portion 32 L of cone-shaped nozzle 32 is coupled to ring 31 and located inside interior region 16 I of fluid-storage container 16 . Middle portion 32 M of cone-shaped nozzle 32 is interposed between and coupled to each of upper and lower portions 32 U, 32 L and located inside interior region 16 I of fluid-storage container 16 as shown, for example, in FIGS. 4 and 5 . Middle portion 32 M of cone-shaped nozzle 32 is formed to include an exposed annular lip 81 arranged to lie between exterior surfaces 12 E, 82 of upper and lower portions 32 U, 32 L of cone-shaped nozzle 32 as shown, for example, in FIG. 6 . Exposed annular lip 81 is arranged to cooperate with exterior surface 82 of lower portion 32 L of cone-shaped nozzle 32 to form an obtuse included angle 81 A therebetween as shown, for example, in FIG. 6 , in part, to provide a large annular space for receiving fluidized annular tip 18 T during a heating step as suggested in FIG. 9 . Exposed annular lip 81 has a frustoconical shape in an illustrative embodiment as suggested in FIG. 6 .
Tubular upper end of fluid-storage container 16 is configured to define a tubular closure-mount sleeve 18 as suggested in FIGS. 4 and 5 . Tubular closure-mount sleeve 18 includes (1) an inner surface 18 I arranged to mate with exterior surface 82 of lower portion 32 L of cone-shaped nozzle 32 and exterior surface 83 of ring 31 , (2) an outer surface 18 O arranged to face away from exterior surface 82 of lower portion 32 L of cone-shaped nozzle 32 and exterior surface 83 of ring 31 , and (3) an annular tip 18 T arranged to interconnect inner and outer surfaces 18 I, 18 O of tubular closure-mount sleeve 18 . Annular tip 18 T is arranged to mate with the exposed annular lip 81 of cone-shaped nozzle 32 to cause outer surface 18 O of tubular closure-mount sleeve 18 to mate and merge in smooth alignment with an abutting exterior surface 12 E of upper portion 32 U of cone-shaped nozzle 32 included in base 30 to provide a substantially smooth and continuous outside wall of squeeze tube 10 around a circumference of squeeze tube 10 at an annular junction 20 between fluid-dispensing closure 12 and tubular closure-mount sleeve 18 of fluid-storage container 16 .
Receptacle 19 of fluid-storage container 16 is formed to define part of interior region 16 I of fluid-storage container 16 as suggested in FIG. 4 . Receptacle 19 is coupled to tubular closure-mount sleeve 18 to depend therefrom without providing any visible outer gap between an exterior surface 83 of ring 31 of fluid-dispensing closure 12 and an outer surface 18 O of tubular closure-mount sleeve 18 of fluid-storage container 16 as suggested in FIGS. 1 , 4 , and 5 .
Base 30 of fluid-discharge closure 12 includes a generally cone-shaped nozzle 32 and an underlying cylinder-shaped ring 31 as suggested in FIGS. 4 and 5 . Squeezable fluid-storage container 16 includes (1) a tubular closure-mount sleeve 18 coupled to and arranged to surround and cover the cylinder-shaped ring 31 and a lower portion 30 L of the generally cone-shaped nozzle 32 and (2) a thin-walled tubular receptacle 19 coupled to tubular closure-mount sleeve 18 and arranged to extend downwardly therefrom to provide most of interior region 16 I of the squeezable fluid-storage container 16 as suggested in FIGS. 1-5 .
Cylinder-shaped ring 31 and a lower portion 32 L of generally cone-shaped nozzle 32 included in base 30 of fluid-dispensing closure 12 is positioned to lie in interior region 16 I formed in the squeezable fluid-storage container 16 . An outer surface 18 O of tubular closure-mount sleeve 18 of fluid-storage container 16 is arranged to mate and merge in smooth alignment with an overlying and abutting exposed exterior surface 12 E of upper portion 32 U of the generally cone-shaped nozzle 32 of base 30 of fluid-discharge closure 12 to provide a substantially smooth and continuous outside wall of squeeze tube 10 around a circumference of squeeze tube 10 at an annular junction 20 between fluid-dispensing closure 12 and tubular upper end of the squeezable fluid-storage container 16 .
Outer surfaces 18 O, 19 O of tubular closure-mount sleeve 18 and receptacle 19 cooperate to define an uninterrupted skin devoid of visible gaps therebetween as suggested in FIGS. 1-3 . A single tubular band 17 is formed to define tubular closure-mount sleeve 18 and receptacle 19 . Singular tubular band 17 includes an upper section 17 U arranged to mate with the exposed annular lip 81 and the exterior surface 82 of lower portion 32 L of cone-shaped nozzle 32 and a middle section 17 M arranged to mate with the exterior surface 83 of ring 31 as suggested in FIG. 5 . A lower section 17 L of singular tubular band 17 is arranged to extend downwardly away from ring 31 as suggested in FIG. 5 . Upper section 17 U is substantially cone-shaped. Middle section 17 M is substantially cylinder-shaped. Outer surfaces of the upper and middle sections of the singular tubular band 17 cooperate to define an obtuse included angle 17 A therebetween as shown, for example, in FIG. 5 . Exterior surface 12 E of upper portion 32 U of cone-shaped nozzle 32 L of fluid-dispensing closure 12 cooperates with the outer surfaces 18 O of the upper and middle sections 17 U, 17 M of the single tubular band 17 to provide a substantially smooth and continuous outside wall of squeeze tube 10 around the circumference of squeeze tube 10 at the annular junction 20 between fluid-dispensing closure 12 and fluid-storage container 16 .
Tubular closure-mount sleeve 18 includes a top part 17 U and a bottom part 17 M as suggested in FIG. 5 . Top part 17 U has an end surface 18 T arranged to mate with the exposed annular lip 81 of cone-shaped nozzle 32 and an inner surface 18 I arranged to mate with upper portion 32 U of cone-shaped nozzle 32 . Bottom part 17 M has an inner surface 18 I arranged to mate with lower portion 32 L of cone-shaped nozzle 32 . Top and bottom parts 17 U, 17 M of tubular closure-mount sleeve 18 cooperate to define an obtuse included angle 18 A therebetween as suggested in FIG. 5 .
Tubular closure-mount sleeve 18 of fluid-storage container 16 comprises a multi-layer sheet including an inner tubular layer L 1 , an outer tubular layer L 3 , and a middle tubular layer L 2 interposed between and coupled to inner and outer tubular layers L 1 , L 3 in an illustrative embodiment as suggested in FIGS. 9 and 11 . Inner tubular layer L 1 includes the inner surface that is arranged to mate with the exterior surfaces 82 , 83 of ring 31 and lower portion 32 L of cone-shaped nozzle 32 of fluid-dispensing closure 12 . Outer tubular layer L 3 includes the outer surface that is arranged to mate and merge in smooth alignment with exterior surface 12 E of upper portion 32 U of cone-shaped nozzle 32 of fluid-dispensing closure 12 . It is within the scope of this disclosure to form tubular closure-mount sleeve 18 from a single sheet or from any suitable number of material layers.
Exposed ends of each of inner, middle, and outer tubular layers L 1 , L 2 , L 3 of tubular closure-mount sleeve 18 cooperate to define the tip 18 T of tubular closure-mount sleeve 18 and mate with the exposed annular lip 81 of fluid-storage container 16 . Each of the exposed ends of the inner, middle, and outer tubular layers L 1 , L 2 , L 3 has a frustoconical shape when mated with the exposed annular lip 81 .
As suggested in FIG. 6 , the base 30 of fluid-discharge closure 12 is shown before upper end (e.g., tubular closure-mount sleeve) 18 of fluid-storage container 16 is coupled to base 30 of fluid-dispensing closure 12 as suggested, for example, in FIGS. 7-9 . The ring 31 and lower, middle, and upper portions 32 L, 32 M, 32 U of the generally cone-shaped nozzle 32 of base 30 are shown before fluid-storage container 16 is coupled to base 30 . Middle portion 32 M is formed to include an exposed annular lip 81 that is arranged to lie between exterior surfaces 12 E, 82 of upper and lower portions 32 U, 32 L.
A first assembly step in accordance with the present disclosure is shown in which a tubular closure-mount sleeve 18 of fluid-storage container 16 is moved upwardly by a sleeve former 90 (shown diagrammatically) to cause an inner surface 18 I of a bottom part 17 M of tubular closure-mount sleeve 18 to mate with the exterior surface 83 of ring 31 included in base 30 of fluid-dispensing closure 12 . A second assembly step is shown in FIG. 8 in which a top part 17 U of the tubular closure-mount sleeve 18 is moved towards the generally cone-shaped nozzle 32 included in base 30 of fluid-dispensing closure 12 by a mover 91 included in sleeve former 90 . A third assembly step is shown in FIG. 9 in which heat is applied to the top part 17 U of tubular closure-mount sleeve 18 by a heater 92 included in sleeve former 90 after an inner surface 18 I of the top part 17 U mates with the exterior surface 82 of lower portion 32 L of the generally cone-shaped nozzle 32 to fluidize an annular tip 18 T of tubular closure-mount sleeve 18 . As suggested in FIG. 10 , the fluidized annular tip 18 T of tubular closure-mount sleeve 18 has solidified and been mated with the exposed annular lip 81 provided in middle portion 32 M of cone-shaped nozzle 32 of base 30 of fluid-dispensing closure 12 to cause the outer surface 18 O of tubular closure-mount sleeve 18 to mate and merge in smooth alignment with exterior surface 12 E of upper portion 32 U of the generally cone-shaped nozzle 32 of base 30 of fluid-dispensing closure 12 as suggested in greater detail in FIG. 12 .
An enlarged sectional view of a portion of the squeeze tube 10 is provided in FIG. 12 and taken from a second circled region of FIG. 10 showing that the annular tip 18 T included in tubular closure-mount sleeve 18 is arranged to interconnect the inner and outer surfaces 18 I, 18 O of tubular closure-mount sleeve 18 . Annular tip 18 T is arranged to mate with the exposed annular tip 81 to cause the outer surface 18 O of the tubular closure-mount sleeve 18 to mate and merge in smooth alignment with the exterior surface 12 E of the generally cone-shaped nozzle 32 to provide a substantially smooth and continuous outside wall of squeeze tube 10 around a circumference of the squeeze tube 10 at the annular junction 20 between fluid-dispensing closure 12 and tubular closure-mount sleeve 18 of the squeezable fluid-storage container 16 as suggested in FIGS. 1-3 . | A tube is configured to store and discharge fluid materials. The tube includes a container and a closure formed to include a fluid-discharge port and coupled to the container to place the fluid-discharge port in communication with any fluid stored in an interior region formed in the container. In illustrative embodiments, the closure includes a base coupled to the container and formed to include the fluid-discharge port, a flip-top cap, and a hinge arranged to interconnect the base and the flip-top cap. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an vital sign box housing a plurality of vital sensors such as an electrocardiograph and a blood pressure monitor.
2. Description of the Related Art
Recently, in connection with high concern about health and the coming of super aged society, for the grip of health conditions, for example, electrocardiographs and blood pressure monitors that can measure electrocardio and blood pressure in home have been developed. Medical care equipment such an electrocardiograph or a blood pressure monitor is called a vital sensor, and the vital sensor utilized in home is miniaturized, and hence can be carried. Furthermore, vital sign boxs, each of which houses such a plurality of miniaturized vital sensors in one housing, have been also developed. FIG. 36 is a perspective view showing an vital sign box used in Medi Data that is an online medical check system developed by SECOM Co. Ltd./SECOM home medical care system Co., Ltd.
In addition, in connection with the diffusion of multimedia, systematization of home medical care, telemedicine, and remote house visit is requested.
As a system for such requests, the above-described Medi Data. of SECOM Co., Ltd./SECOM home medical care system Co., Ltd. is known. Medi Data is a system that the above-described vital sign box is connected to a nurse center via a communication line, for example, a patient in home medical care measures the Patient's own blood pressure with using a vital sensor contained in the vital sign box to transmit the measurement to the nurse center. Furthermore, in the nurse center, the measurement is received and stored, and the transition of the measurements is reported to a doctor, who performs telemedicine with using a telephone and the like on the basis of the measurements that the doctor are reported.
In addition, as another system performing the home medical care and telemedicine, a home medical care support system by Fukuda Denshi Co., Ltd. is also known. The system consists of home terminal equipment that is installed in home and to which a plurality of vital sensors and a camera to take a picture of patient's appearance such as a face and the like in home medical care are connected, and transmits the patient's images via a communication line with measurements measured by the vital sensors to a center. The center grips not only the measurements measured by the vital sensors, but also the patient's appearance. In addition, by providing a camera in the center and letting faces of a doctor and a nurse in the center know the patient, it is possible to remove the patient's anxiety for the telemedicine. Furthermore, by providing each talking unit in the home terminal equipment and the center, it is possible to perform communication by voice.
However, a camera for taking a picture of patient's appearance such as a face and the like is not provided in the conventional vital sign box used in Medi Data that is an online medical check system made by SECOM Co., Ltd./SECOM home medical care system Co., Ltd. On the other hand, in the home medical care support system made by Fukuda Denshi Co., Ltd., a camera can be connected to home terminal equipment. But, since the camera is used with being fixed in substance and is not a handy type camera, after it is fixed once, it is possible just to take a picture of an object in a viewing angle range to some extent. Nevertheless, it is not possible to take a picture of, for example, a patient's face sometimes, and to take a picture of the patient's foot locally in another time.
In addition, in the above-described conventional vital sign boxs, an input of a measurement measured by each vital sensor is performed by manually inputting the measurement with using a ten-key pad after a user confirms the measurement. The manual input of the measurement using the ten-key pad in this manner is troublesome work for a user, and a mishit may be performed. Furthermore, there is also a possibility of false inputting a measurement.
Moreover, each of the above-described conventional vital sign boxs includes memory to record measurements measured by each vital sensor, and a display for displaying, for example, the transition of measurements for 30 days in a graph. Nevertheless, daily drifts of measurements may not be expressed clearly in the graph displayed in the display. For example, in case a display area is too large in comparison with the largeness of drifts or a display scale is not suitable, daily drifts of measurements are not expressed clearly.
In addition, in a conventional vital sign box, although it is possible to display a measurement measured by each vital sensor in a display, for example, a user having poor eyesight may feel resistance to looking at a displayed measurement. Thus, depending on a user or a using status, it may be more convenient to let the user auditorily inform the measurement by sound than to visually display the measurement in a display.
Furthermore, in the above-described conventional vital sign box, it is possible to transmit a measurement, measured by each vital sensor, to an administration section such as a nurse center via a communication line. Nevertheless, since, for example, a camera for taking a picture of an affected part and the like of a patient in home medical care is not provided, it is not possible to transmit such an image to the administration section.
Furthermore, in the above-described conventional vital sign box, it is possible to transmit a measurement, measured by each vital sensor, to an administration section such as a nurse center via a communication line. Nevertheless, in case of telemedicine, after having received a measurement, it is necessary for a doctor and a nurse in the administration section to inquire a user of the vital sign box, who transmitted the measurement, about health conditions with a telephone or the like. However, if answers to inquiry items have been transmitted to the administration section with the measurements, measured by each vital sensor, beforehand, it becomes unnecessary for a doctor and a nurse in the administration section to inquire the sender. Hence they can have a time margin for medical practice.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an vital sign box which has means of being able to take a picture of an object with changing the object and/or an imaging angle flexibly, in consideration of a subject that, in a conventional vital sign box, a camera taking a picture of an object is not provided, and even if home terminal equipment has a capability for connecting a camera, it is not possible to flexibly change an imaging object and/or an imaging angle.
In addition, another object of the present invention is to provide an vital sign box, having vital sensors which can input measurements into memory without letting a user manually input the measurements, in consideration of a subject that, in a conventional vital sign box, a use is made to manually input the measurements when inputting the measurements, measured by the vital sensors, into memory.
Furthermore, still another object of the present invention is to provide an vital sign box, having a display to clearly display drifts of measurements which have been measured by the vital sensors and have been recorded in a predetermined period, in consideration of a subject that, in a display of a conventional vital sign box, the drifts of the measurements measured and recorded in the predetermined period may not be clearly displayed.
Moreover, a further object of the present invention is to provide an vital sign box having a speaker, outputting measurements, measured by vital sensors, with using sound, in consideration of a subject that measurements measured by vital sensors are not outputted by sound in a conventional vital sign box.
In addition, a still further object of the present invention is to provide an vital sign box not only having means of taking a picture of an object but also being able to transmit an image of the object, that is taken by the imaging means, to a communication partner, in consideration of a subject that, in a conventional vital sign box, for example, a camera taking a picture of an affected part and the like of a patient in home medical care is not provided. Furthermore, an object of the present invention is also to provide an vital sign box that receives information from a communication partner and can perform bi-directional communication.
Moreover, another object of the present invention is also to provide an vital sign box that inquires a user of the vital sign box about health conditions, in consideration of a subject that a conventional vital sign box does not inquire the user of the vital sign box about health conditions.
The 1 st invention of the present invention (corresponding to claim 1 ) is an vital sign box comprising: a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body; an camera taking a picture of a predetermined object; and a housing containing the plurality of vital sensors and the camera.
The 2 nd invention of the present invention (corresponding to claim 2 ) is the vital sign box according to 1 st invention, further comprising a base that is rotatable, can be fixed at a predetermined angle, and houses the camera at the time of detachment.
The 3 rd invention of the present invention (corresponding to claim 3 ) is the vital sign box according to 1 st invention, wherein the camera is rotatable, and can be fixed at a predetermined angle.
The 4 th invention of the present invention (corresponding to claim 4 ) is the vital sign box according to 1 st invention, wherein the camera is detachable.
The 5 th invention of the present invention (corresponding to claim 5 ) is the vital sign box according to 4 th invention, wherein the camera is a fixed focus type camera.
The 6 th invention of the present invention (corresponding to claim 6 ) is the vital sign box according to 5 th invention, wherein the camera comprises:
a string-like or rod-like body that indicates whether distance between the imaging object and a predetermined section of the camera becomes predetermined length, and is attached at the predetermined section of the camera, and has predetermined length;
instruction receiving means of receiving an imaging instruction of the imaging object; and
imaging means of taking a picture of the imaging object when the instruction receiving means receives the imaging instruction.
The 7 th invention of the present invention (corresponding to claim 7 ) is the vital sign box according to 5 th invention, wherein the camera comprises:
range-finding means of detecting distance between the imaging object and the predetermined section of the camera;
comparing means of comparing distance, detected by the range-finding means, with predetermined length;
result output means of outputting a comparison result, obtained by the comparing means, by a sound and/or an image;
instruction receiving means of receiving an imaging instruction of the imaging object; and
imaging means of taking a picture of the imaging object when the instruction receiving means receives the imaging instruction.
The 8 th invention of the present invention (corresponding to claim 8 ) is the vital sign box according to 5 th invention wherein the camera comprises:
range-finding means of detecting distance between the imaging object and a predetermined section of the camera;
comparing means of comparing distance, detected by the range-finding means, with predetermined length; and
imaging means of taking a picture of the imaging object when distance, detected by the range-finding means, substantially coincides with the predetermined length.
The 9 th invention of the present invention (corresponding to claim 9 ) is the vital sign box according to 1 st invention, wherein the camera has a lighting section emitting light to the object.
The 10 th invention of the present invention (corresponding to claim 10 ) is the vital sign box according to 1 st invention, further comprising a display displaying an object whose image is taken by the camera.
The 11 th invention of the present invention (corresponding to claim 11 ) is an vital sign box comprising:
a plurality of vital sensors that measures predetermined biological, chemical, or physical conditions of a living body, and transmits measurements, obtained by the measurement, with using an electric wave;
a reception sensor receiving measurements from the plurality of vital sensors;
memory recording measurements received by the reception sensor; and
a housing containing the plurality of vital sensors, the reception sensor, and the memory.
The 12 th invention of the present invention (corresponding to claim 12 ) is the vital sign box according to 11 th invention, wherein the electric wave is an infrared ray having a predetermined wavelength.
The 13 th invention of the present invention (corresponding to claim 13 ) is an vital sign box comprising: a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body; and a housing with a lid that contains at least the plurality of vital sensors, wherein the lid has a shank that becomes a substantially shaft when the lid is opened and closed;
wherein the shank is provided in the housing so that a main body of the housing has a front section and a rear section to the shank; and
wherein the lid can be fixed in a status that the lid stands to a bottom section of the vital sign box with using the shank when the vital sign box is used.
The 14 th invention of the present invention (corresponding to claim 14 ) is the vital sign box according to 13 th invention further comprising a display that is provided and fixed inside the lid of the housing, and displays measurements measured by the vital sensors.
The 15 th invention of the present invention (corresponding to claim 15 ) is an vital sign box comprising: a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body; a display displaying measurements measured by the vital sensors; and a housing with a lid that contains the plurality of vital sensors and the display.
The 16 th invention of the present invention (corresponding to claim 16 ) is the vital sign box according to 15 th invention, wherein the display is movable;
wherein the housing has a display fixing section to fix the display; and
wherein the display lies in a bottom section of the housing at the time of non-use and can be fixed in a status that the display stands to the bottom section of the housing with using the display fixing section at the time of use.
The 17 th invention of the present invention (corresponding to claim 17 ) is an vital sign box comprising:
a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body;
memory recording measurements measured by the vital sensors;
a display that displays measurements measured by the vital sensors, and/or a plurality of measurements recorded in the memory, and determines a display range and/or a display scale with each of the measurements, which are displayed, being as a reference; and
a housing that contains the plurality of vital sensors, the memory, and the display.
The 18 th invention of the present invention (corresponding to claim 18 ) is the vital sign box according to 17 th invention wherein each of the measurement to be a reference is a newest measurement and the item to be determined is a display range.
The 19 th invention of the present invention (corresponding to claim 19 ) is the vital sign box according to 17 th invention, wherein, when at least one of the plurality of vital sensors measures upper and lower limits of the predetermined condition substantially at the same time, the display simultaneously displays the measurements, which are measured and are upper and lower limits, and/or a plurality of measurements, which are recorded in the memory, with classifying the measurements into the upper limits and the lower limits whose display areas are divided separately.
The 20 th invention of the present invention (corresponding to claim 20 ) is an vital sign box comprising:
a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body;
a speaker outputting measurements, measured by the vital sensors, by sound; and
a housing containing the plurality of vital sensors, and the speaker.
The 21 st invention of the present invention (corresponding to claim 21 ) is a vital sign box comprising:
a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body;
an camera taking a picture of a predetermined object;
memory recording measurements measured by the vital sensors and/or objects whose images are taken by the camera;
a communication terminal of transmitting all or part of measurements measured by the vital sensors, an object whose image is taken by the camera, measurements recorded in the memory, and objects recorded in the memory; and
a housing containing the plurality of vital sensors, the camera, the memory, and the communication terminal.
The 22 nd invention of the present invention (corresponding to claim 22 ) is the vital sign box according to 21 st invention, wherein the communication terminal receives predetermined information from a communication partner, and wherein the vital sign box comprises a display that is contained in the housing, and not only displays all or part of measurements measured by the vital sensors, an object whose image is taken by the camera, measurements recorded in the memory, and objects recorded in the memory, but also displays information from the communication partner inputted by the communication terminal.
The 23 rd invention of the present invention (corresponding to claim 23 ) is the vital sign box according to 22 nd invention, wherein one of information from the communication partner, which is displayed in the display, is arrowhead information for specifying a predetermined position of the display, and the arrowhead is displayed in the display with all or part of measurements measured by the vital sensors, an object whose image is taken by the camera, measurements recorded in the memory, and objects recorded in the memory that are displayed in the display.
The 24 th invention of the present invention (corresponding to claim 24 ) is the vital sign box according to 23 rd invention wherein the arrowhead information is coordinate information of the position when the arrowhead is let to be displayed in the display, and the display has shape information of the arrowhead to be displayed and displays the arrowhead on the basis of the coordinate information from the communication partner.
The 25 th invention of the present invention (corresponding to claim 25 ) is an vital sign box comprising:
a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body;
a power supply section that is provided so as not to contact with the vital sensors and supplies electric power from the outside of the vital sign box to all or part of the plurality of vital sensors with using an electromagnetic wave by electromagnetic induction; and
a housing containing the plurality of vital sensors, and the power supply section.
The 26 th invention of the present invention (corresponding to claim 26 ) is an vital sign box comprising:
a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body;
a microphone inputting sound;
a communication terminal transmitting sound inputted by the microphone; and
a housing containing the plurality of vital sensors, the microphone, and the communication terminal.
The 27 th invention of the present invention (corresponding to claim 27 ) is an vital sign box comprising:
a display displaying inquiry items to a user;
an inquiry result input section of inputting an inquiry result to inquiries in the display;
a communication terminal transmitting the inquiry result inputted by the inquiry result input section; and
a housing containing the display, the inquiry result input section, and the communication terminal.
The 28 th invention of the present invention (corresponding to claim 28 ) is the vital sign box according to 27 th invention, wherein the communication terminal is a device inputting predetermined information from a communication partner to whom the inquiry result is sent and the display also displays information from the communication partner that is inputted by the communication terminal.
The 29 th invention of the present invention (corresponding to claim 29 ) is the vital sign box according to 27 th invention wherein the communication terminal is a device inputting predetermined information from a communication partner to whom the inquiry result is sent, and the vital sign box further comprises a speaker that is contained in the housing and outputs information from the communication partner, which is inputted by the communication terminal, with using sound.
The 30 th invention of the present invention (corresponding to claim 30 ) is an vital sign box comprising:
a speaker outputting inquiry items to a user by sound;
an inquiry result input section inputting an inquiry result to inquiries from the speaker;
a communication terminal transmitting the inquiry result inputted by the inquiry result input section; and
a housing containing the speaker, the inquiry result input section, and the communication terminal.
The 31 st invention of the present invention (corresponding to claim 31 ) is the vital sign box according to 30 th invention wherein the communication terminal is a device inputting predetermined information from a communication partner to whom the inquiry result is sent, and the speaker also outputs information from the communication partner, which is inputted by the communication terminal, with using sound.
The 32 nd invention of the present invention (corresponding to claim 32 ) is the vital sign box according to 30 th invention, wherein the communication terminal is a device inputting predetermined information from a communication partner to whom the inquiry result is sent, and the vital sign box further comprises the display that is contained in the housing and displays information from the communication partner that is inputted by the communication terminal.
The 33 rd invention of the present invention (corresponding to claim 33 ) is the vital sign box according to any one of 1 st , 11 th , 13 th , 15 th , 17 th , 20 th , 21 st , 25 th , 26 th , 27 th , and 30 th inventions, wherein the housing has a lid; wherein a clamp for closing the lid and fixing the lid to the main body of the housing is provided in each of a main body of the housing and the lid; and wherein a handle is provided in the main body of the housing.
The 34 th invention of the present invention (corresponding to claim 34 ) is the vital sign box according to any one of 1 st to 32 nd inventions, further comprising a password input section of inputting a password of a user, wherein measurements measured by the vital sensors, and/or an object whose image is taken by the camera are managed with being associated with a password inputted in the password input unit.
The 35 th invention of the present invention (corresponding to claim 35 ) is the vital sign box according to any one of 1 st to 32 nd inventions, wherein all or part of the plurality of vital sensors and/or the camera each have an electric power storage section storing electric power.
The 36 th invention of the present invention (corresponding to claim 36 ) is the vital sign box according to any one of 1 st to 32 nd inventions, further comprising a display displaying usage of an vital sign box.
The 37 th invention of the present invention (corresponding to claim 37 ) is the vital sign box according to 36 th invention, wherein all or part of the usage is displayed by an image.
The 38 th invention of the present invention (corresponding to claim 38 ) is the vital sign box according to 37 th invention, wherein the image is a graphic image of measurements measured by a vital sensor.
The 39 th invention of the present invention (corresponding to claim 39 ) is the vital sign box according to 36 th invention, wherein the display is a touch panel type liquid crystal display and changes display contents by a predetermined portion of the liquid crystal display being touched by a user.
The 40 th invention of the present invention (corresponding to claim 40 ) is the vital sign box according to any one of 1 st to 32 nd inventions, further comprising a speaker outputting usage of an vital sign box by sound.
The 41 st invention of the present invention (corresponding to claim 41 ) is the vital sign box according to 40 th invention, further comprising: a display displaying usage of an vital sign box; and a change instruction input section of inputting an instruction for changing an output of the usage from an output where sound from the speaker is used to an output where display in the display is used.
The 42 nd invention of the present invention (corresponding to claim 42 ) is the vital sign box according to any one of 10 th , 14 th , 15 th , 17 th , 22 nd , 27 th , 32 nd , 36 th , and 41 st inventions, wherein the display is a touch panel type display having a software keyboard function.
The 43 rd invention of the present invention (corresponding to claim 43 ) is the vital sign box according to any one of 10 th , 14 th , 15 th , 17 th , 22 nd , 27 th , 32 nd , 36 th , and 41 st inventions, wherein at least part of the housing consists of metallic material, and the vital sign box comprises a connecting section that consists of metallic material and connects a heating section, generating heat in connection with image display to the display, with a metallic material section of the housing.
The 44 th invention of the present invention (corresponding to claim 44 ) is the vital sign box according to any one of 20 th , 30 th , and 40 th inventions, wherein at least part of the housing consists of metallic material, and the vital sign box comprises a connecting section that consists of metallic material and connects a heating section, generating heat in connection with a sound output from the speaker, with a metallic material section of the housing.
The 45 th invention of the present invention (corresponding to claim 45 ) is the vital sign box according to any one of 21 st , 26 th , 27 th , and 30 th inventions, wherein at least part of the housing consists of metallic material, and the vital sign box comprises a connecting section that consists of metallic material and connects a heating section, generating heat in connection with information communication in the communication terminal, with a metallic material section of the housing.
The 46 th invention of the present invention (corresponding to claim 46 ) is a medium that bears a program and/or data for letting a computer execute all or part of functions of the vital sign box according to any one of 36 th to 41 st inventions, the medium with which a computer can perform processing.
The 47 th invention of the present invention (corresponding to claim 47 ) is an information aggregation, wherein the information aggregation is a program and/or data for letting a computer execute all or part of functions of the vital sign box according to any one of 36 th to 41 st inventions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an vital sign box when a lid of the vital sign box according to a first embodiment of the present invention is opened;
FIG. 2 is a side view of the vital sign box when the lid of the vital sign box according to the first embodiment of the present invention is opened;
FIG. 3 is a top view of the vital sign box when viewing the vital sign box, the lid of which is opened, according to the first embodiment of the present invention from an arrow A in FIG. 2;
FIG. 4 is a front view showing the inside of the lid of the vital sign box when the lid of the vital sign box according to the first embodiment of the present invention is opened substantially vertically to a bottom face of the vital sign box and an camera provided in the vital sign box is also stood substantially vertically to the bottom face of the vital sign box;
FIG. 5 is a drawing showing a display screen on which the vital sign box according to the first embodiment of the present invention lets a user input the user's name and password in order to specify the user;
FIG. 6 is an explanatory diagram for explaining that a display 10 of the vital sign box according to the first embodiment of the present invention displays the contents shown in FIG. 5, and if a “Grandfather” portion in the display 10 is touched by a user, the “Grandfather” portion is displayed with blinking;
FIG. 7 is a diagram showing a display screen for letting a user of the vital sign box according to the first embodiment of the present invention input the user's name;
FIG. 8 is a diagram showing a display screen for letting a user of the vital sign box according to the first embodiment of the present invention input a password;
FIG. 9 is a diagram showing a display screen on which the vital sign box according to the first embodiment of the present invention lets a user select any one of the use of each vital sensor or an camera 5 , display of data stored in memory 9 , or communication with a hospital;
FIG. 10 is an explanatory diagram for explaining that a display 10 of the vital sign box according to the first embodiment of the present invention displays the contents shown in FIG. 9, and if a “Measurement/Record” portion in the display 10 is touched by a user, the “Measurement/Record” portion is displayed with blinking;
FIG. 11 is a diagram showing a display screen on which the vital sign box according to the first embodiment of the present invention lets a user select whether the user uses any one of each vital sensor and the camera 5 ;
FIG. 12 is a diagram showing an example of a chart of a measurement result of body temperature measured by an earhole clinical thermometer 3 included in the vital sign box according to the first embodiment of the present invention;
FIG. 13 is a diagram showing another example of a chart of a measurement result of body temperature measured by the earhole clinical thermometer 3 included in the vital sign box according to the first embodiment of the present invention, which is different from the example in FIG. 12;
FIG. 14 is a diagram showing an example of charts of measurement results of blood pressure measured by a blood pressure monitor 2 included in the vital sign box according to the first embodiment of the present invention;
FIG. 15 is a diagram showing another example of charts of measurement results of blood pressure measured by the blood pressure monitor 2 included in the vital sign box according to the first embodiment of the present invention, which is different from the example in FIG. 14;
FIG. 16 is a diagram showing an example of a chart of a measurement result of pulse rates measured by the blood pressure monitor 2 included in the vital sign box according to the first embodiment of the present invention;
FIG. 17 is a diagram showing another example of a chart of a measurement result of pulse rates measured by the blood pressure monitor 2 included in the vital sign box according to the first embodiment of the present invention, which is different from the example in FIG. 16;
FIG. 18 is a diagram showing an example of an electrocardiogram measured by the electrocardiograph 1 of the vital sign box according to the first embodiment of the present invention;
FIG. 19 is an explanatory diagram of a display area when objects, whose pictures are taken by an camera 5 of the vital sign box according to the first embodiment of the present invention, are displayed in a display 10 ;
FIG. 20 is an explanatory diagram of a display area when an object, whose picture is taken by an camera 5 of the vital sign box according to the first embodiment of the present invention is displayed in a display 10 with being magnified;
FIG. 21 is a diagram showing an example of a chart of a measurement result of blood glucose levels measured by a glucose meter 4 included in the vital sign box according to the first embodiment of the present invention;
FIG. 22 is a diagram showing another example of a chart of a measurement result of blood glucose levels measured by the glucose meter 4 included in the vital sign box according to the first embodiment of the present invention, which is different from the example in FIG. 21;
FIG. 23 is a diagram showing an example of a chart of a measurement result of body weight measured by a scale that can perform data transmission to the vital sign box according to the first embodiment of the present invention;
FIG. 24 is a diagram showing another example of a chart of a measurement result of body weight measured by the scale that can perform data transmission to the vital sign box according to the first embodiment of the present invention, which is different from the example in FIG. 23;
FIG. 25 is a drawing showing a display screen for letting a user input a name and a telephone number of a communication partner in order to specify the communication partner of the vital sign box according to the first embodiment of the present invention;
FIG. 26 is a drawing showing inquiry items that are displayed in the display 10 included in the vital sign box according to the first embodiment of the present invention, and about which a user is asked;
FIG. 27 is a drawing showing a display screen for letting a user of the vital sign box according to the first embodiment of the present invention input a name and a telephone number of a communication partner;
FIG. 28 is a drawing showing a display screen for letting a user of the vital sign box according to the first embodiment of the present invention input a telephone number of a communication partner;
FIG. 29 is a drawing showing a display screen first displayed in the display 10 of the vital sign box and a personal computer of a communication partner after the vital sign box according to the first embodiment of the present invention and the personal computer of the communication partner could communicate with each other;
FIG. 30 is a drawing showing a display screen where an arrow is displayed in the display 10 of the vital sign box and the personal computer of the communication partner while the vital sign box according to the first embodiment of the present invention and the personal computer of the communication partner are communicating;
FIG. 31 is a drawing showing a display screen that is displayed in the display 10 of the vital sign box according to the first embodiment of the present invention and is displayed for instructing a user to turn off the vital sign box;
FIG. 32 is a side view of an vital sign box when a lid of the vital sign box according to the first embodiment of the present invention is opened, which is different from the vital sign box shown in FIG. 2;
FIG. 33 is a side view of an vital sign box when a lid of the vital sign box according to the first embodiment of the present invention is opened, which is different from each vital sign box shown in FIGS. 2 and 32;
FIG. 34 is a configuration of a power supply section 17 supplying electric power to each vital sensor and the camera 5 of the vital sign box according to the first embodiment of the present invention with using an electromagnetic wave generated by electromagnetic induction;
FIG. 35 is a configuration of another power supply section 17 supplying electric power to each vital sensor and the camera 5 of the vital sign box according to the first embodiment of the present invention with using an electromagnetic wave generated by electromagnetic induction, which is different from the power supply section 17 in FIG. 34; and
FIG. 36 is a perspective view showing a conventional vital sign box used in Medi Data that is an online medical check system developed by SECOM Co., Ltd./SECOM home medical care system Co., Ltd.
Description of Symbols
1
Electrocardiograph
1a
Contact section for a left arm
1b
Contact section for a right arm
2
Blood Pressure Monitor
3
Earhole clinical thermometer
4
Blood glucose meter
4a
Blood-collecting needle
4b
Sensor chip
4c
Connection jack
5
Electronic camera
6
Base
6a
Connecting section
7
LED
8
Reception sensor
9
Memory
10
Display
11
Speaker
12
Microphone
13
Communication terminal
14
Housing
15
Lid
16
Shank
17
Power supply section
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, embodiments of the present invention will be described with reference to drawings.
Embodiment 1
First of all, the configuration of an vital sign box of a first embodiment of the present invention will be described.
FIG. 1 is a perspective view of the vital sign box when a lid of the vital sign box according to the first embodiment of the present invention is opened. FIG. 2 is a side view of the vital sign box when the lid of the vital sign box according to the first embodiment of the present invention is opened. FIG. 3 is a top view of the vital sign box when viewing the vital sign box, the lid of which is opened, according to the first embodiment of the present invention from an arrow A in FIG. 2 . FIG. 4 is a front view showing the inside of the lid of the vital sign box when the lid of the vital sign box according to the first embodiment of the present invention is opened substantially vertically to a bottom face of the vital sign box and an camera provided in the vital sign box is also stood substantially vertically to the bottom face of the vital sign box.
As shown in FIGS. 1 to 4 , the vital sign box according to the first embodiment of the present invention consists of an electrocardiograph 1 , a blood pressure monitor 2 , an earhole clinical thermometer 3 , a blood glucose meter 4 , an camera 5 , a base 6 , an LED 7 , a reception sensor 8 , memory 9 , a display 10 , a speaker 11 , a microphone 12 , a communication terminal 13 , and a housing 14 .
The electrocardiograph 1 is means of measuring electrocardio, and, as shown in FIG. 3, consists of a clip-like contact section for a left arm 1 a and a contact section for a right arm 1 b that contact to left and right arms of a human body respectively. Those contact section for a left arm 1 a and contact section for a right arm 1 b are connected to a main body of the vital sign box with connection cords, and are means of transmitting measurements to the LED 7 through the connection cords with using electrical signals. In addition, inside the contact section for a left arm 1 a and contact section for a right arm 1 b , a circuit for measuring electrocardio is built in, and the circuit is utilized in electrocardio measurement.
The blood pressure monitor 2 is means of measuring blood pressure and a pulse rate, and is a handy type meter. Furthermore, the blood pressure monitor 2 is means that is not connected to the main body of the vital sign box with a connection cord but transmits a measurement to the reception sensor 8 with using an infrared ray having a predetermined wavelength.
The earhole clinical thermometer 3 is means of measuring body temperature, and is a handy type meter similarly to the blood pressure monitor 2 . Furthermore, the earhole clinical thermometer 3 is means that is not connected to the main body of the vital sign box with a connection cord but transmits a measurement to the reception sensor 8 with using an infrared ray having a predetermined wavelength.
The blood glucose meter 4 is means of measuring sugar density in blood, and has a blood-collecting needle 4 a , a sensor chip 4 b , and a connection jack 4 c . Furthermore, when being housed in the housing 14 , the blood glucose meter 4 , blood-collecting needle 4 a , sensor chip 4 b , and connection jack 4 c are housed separately. Moreover, the blood glucose meter 4 is a handy type meter, and the sensor chip 4 b is mounted and used when a blood glucose level is measured. The blood glucose meter 4 measures a blood glucose level of the blood collected by the blood-collecting needle 4 a with utilizing the sensor chip 4 b . In addition, when measured data is transmitted to the main body of the vital sign box, the blood glucose meter 4 is connected to the connection jack 4 c , and furthermore, the connection jack 4 c is connected to the main body of the vital sign box. The measured data is transmitted from the blood glucose meter 4 to the LED 7 in the main body of the vital sign box through the connection jack 4 c with using an electrical signal. The blood-collecting needle 4 a is means of gathering blood from a human body, the sensor chip 4 b is means of measuring a blood glucose level of the blood collected by the blood-collecting needle 4 a , and the connection jack 4 c connects the blood glucose meter 4 to the main body of the vital sign box.
In addition, the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 are used an an example of vital sensors according to the vital sign box of the present invention.
In addition, the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 are used as an example of vital sensors according to the vital sign box of the present invention, the vital sensors which are described in claims 1 , 11 , 13 , 15 , 17 , 20 , 21 , 25 and 26 .
The camera 5 is means of taking a picture of a predetermined object, has a lighting section lighting the object, and is detachable from the base 6 .
The base 6 has a connecting section 6 a , is connected to the housing 14 through the connecting section 6 a , is rotatable with the connecting section 6 a as a fulcrum, and not only can be fixed at a predetermined angle, but also is means of containing the camera 5 .
The LED 7 is means of converting each measurement, transmitted with using electrical signals from the electrocardiograph 1 and blood glucose meter 4 , into an infrared ray having a predetermined wavelength and transmitting each measurement to the reception sensor 8 .
The reception sensor 8 is means of receiving each infrared ray having a predetermined wavelength from the blood pressure monitor 2 , earhole clinical thermometer 3 , and LED 7 .
The memory 9 is installed with being embedded in the housing 14 , and is means of not only recording each measurement on the basis of the infrared ray received by the reception sensor 8 , but also recording an image of an object recorded by the camera 5 .
The display 10 is means of displaying each measurement measured by the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 , an object, a picture of which is taken by the camera 5 , and usage of the vital sign box according to the first embodiment of the present invention. The display 10 is a touch panel type liquid crystal display, and hence changes display contents when each of predetermined portions is touched.
The speaker 11 is means of outputting each measurement measured by the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 or usage of the vital sign box according to the first embodiment of the present invention with using sound.
Microphone 12 is means of collecting sound of voice and the like of a user of the vital sign box according to the first embodiment of the present invention.
The communication terminal 13 is means of transmitting each measurement measured by the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 , and an object recorded by the camera 5 to a communications partner with using a communication line.
The housing 14 is means of having the lid 15 and containing all of the above-described sections from the electrocardiograph 1 to the terminal 13 . The lid 15 has the shank 16 that substantially becomes a shaft when the lid 15 is opened and closed, and not only is installed in the housing 14 through the shank 16 , but also can be fixed at a predetermined angle of gradient to the housing 14 . In addition, it is assumed that the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , blood glucose meter 4 , camera 5 , base 6 , LED 7 , reception sensor 8 , and memory 9 are contained in a main body of the housing 14 , that the display 10 , speaker 11 , and microphone 12 are provided inside the lid 15 , and that the communication terminal 13 is provided outside the main body of the housing 14 .
In addition, as show in FIG. 1, in the housing 14 and lid 15 each, clamps 20 a , 20 b , 21 a , and 21 b are attached for closing the lid 15 and fixing the lid 15 to the housing 14 . Furthermore, a handle 22 for easily carrying the vital sign box of the first embodiment when the lid 15 is closed and is fixed to the housing 14 is provided in the housing 14 .
Moreover, although being not shown in FIGS. 1 to 4 , a program recording medium that stores a program to let the display 10 and speaker 11 output the usage of the vital sign box is built in the vital sign box according to the first embodiment of the present invention.
In addition, it is made that the vital sign box of the first embodiment of the present invention can receive data from a scale that is different from the vital sign box and can transmit a measurement to the vital sign box with using an infrared ray having a predetermined wavelength. It is made that the LED 7 receives data from the scale at that time.
Furthermore, it is assumed that the vital sign box according to the first embodiment of the present invention is connected to a personal computer in a hospital through the communication terminal 13 .
Moreover, although having been explained once, FIG. 3 will be explained again. FIG. 3 is a top view showing the main body of the housing 14 when the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , blood glucose meter 4 , camera 5 , base 6 , LED 7 , reception sensor 8 , and memory 9 are contained in the main body of the housing 14 and the lid 15 is opened.
Next, the operation of the vital sign box according to the first embodiment of the present invention will be described.
First of all, a user switches on the vital sign box, and opens the lid 15 of the housing 14 as shown in FIGS. 1 and 2.
When the vital sign box is turned on, the display 10 provided inside the lid 15 begins displaying the usage of the vital sign box on the basis of the program stored in the program recording medium. In addition, similarly, on the basis of the program stored in the program recording medium, the speaker 11 begins outputting the usage of the vital sign box by sound.
FIG. 5 shows display contents that are first displayed in the display 10 after the vital sign box was switched on. FIG. 5 is a drawing showing a display screen on which the vital sign box lets a user input the user's name and password in order to specify the user. By the way, the reason why a user is specified is for the vial sign box to associate a measurement measured by each vital sensor and an image a picture of which is taken by the camera 5 with each user, and to manage the measurement and image every user. In addition, in connection to it, the reason is also to protect the privacy of the measurement and the shot image of each user is protected. Furthermore, when the display 10 displays contents shown in FIG. 5, the user touches a portion of any one of “Grandfather,” “Grandmother,” “Registration wait 3,” and “Registration wait 4” in the display 10 . By the way, the display of the “Grandfather” and “Grandmother” means that names and passwords of the “Grandfather” and “Grandmother” have been already registered. In addition, the display of the “Registration wait 3” and “Registration wait 4” means that names and passwords of users are not registered.
Then, if the user is the “Grandfather” or “Grandmother” and the user's name and password have been registered beforehand, the user touches an adequate portion, furthermore touches a “password” to input the user's password, and goes to the next step shown in FIG. 9 . On the other hand, if the user is not the “Grandfather” or “Grandmother” but the user's name and password are not registered, the user touches a portion of any one of the “Registration wait 3” and “Registration wait 4.” The user touches the “Registration wait 3” or “Registration wait 4” so as to use the vital sign box many times later and to let the vital sign box manage measurements measured by each vital sensor and/or images taken by the camera 5 . When the user touches the “Registration wait 3” or “Registration wait 4,” the display 10 displays the contents shown in FIG. 7, and lets the user register the user's name with letting the user utilize the touch panel. If the user touches a “Confirm” portion after registration, the display 10 displays the contents shown in FIG. 8 to let the user register, for example, four character password with letting the user use the touch panel again. In this manner, if the user is made to register the user's name and password, the name and password are managed by the vital sign box after that with being associated with the “Registration wait 3” or “Registration wait 4” that was touched before the registration of the name and password. In addition, if the name and password are registered, the display 10 displays the contents shown in FIG. 9 .
If the user operates according to the display of the display 10 as described above, the display 10 displays the contents shown in FIG. 9 .
In addition, for the convenience of explanation, it is assumed that the user of the vital sign box is a “Grandfather.” Therefore, in this case, when the display 10 displays the contents shown in FIG. 5, the user touches the “Grandfather” portion in the display 10 . When the “Grandfather” portion is touched in this manner, the display 10 displays the “Grandfather” portion with blinking as shown in FIG. 6 . In addition, in FIG. 6, it is assumed that slanted lines of the portion displaying the “Grandfather” portion denote that the portion displaying the “Grandfather” blinks. In addition, it is assumed for the convenience of the following explanation as described above that the user of the vital sign box is the “Grandfather.” Nevertheless, it is assumed that, even if the user is not the “Grandfather” but the user touches the “Grandmother,” “Registration wait 3,” or “Registration wait 4” when the display 10 displays the contents shown in FIG. 5, the display 10 displays and blinking the touched portion. Furthermore, also in the following description, it is assumed that, if a predetermined portion of the display 10 is touched by a user, the display 10 displays and blinking the touched portion.
Moreover, although the usage of the vital sign box only by the display of the display 10 is explained in the above description, it is made that the usage is explained simultaneously with using sound from the speaker 11 . Similarly, also in the following explanation, it is assumed that the usage of the vital sign box is explained not only in the display of the display 10 , but also by a sound output from the speaker 11 .
In addition, in the above description, the display 10 corresponds to a password input section of the present invention according to claim 34 .
Furthermore, as explained when the configuration of vital sign box according to the first embodiment of the present invention is described, the display 10 is a touch panel type liquid crystal display. Hence, for a user, the display 10 is convenient because it is not necessary to use a ten-key pad or a mouse when the user changes the display contents of the display 10 .
By the way, FIG. 9 is a drawing showing a display screen for letting a user select any one of using each vital sensor or the camera 5 of the vital sign box, letting the display 10 display the data that is stored as measurements and pictures in the memory 9 , and communicating with a personal computer in a hospital that is connected to the vital sign box.
In this manner, it is assumed that, when the contents shown in FIG. 9 is displayed by the display 10 , first of all, the user uses each vital sensor and the camera 5 . At this time, the user touches a “Measurement/Record” in the display 10 , and the display 10 displays the “Measurement/record” portion with blinking the “Measurement/record” portion as shown in FIG. 10 if the “Measurement/Record” portion is touched. After that, the display 10 changes the display contents to the contents shown in FIG. 11 . In addition, in FIG. 10, it is assumed that slanted lines of the portion displaying the “Measurement/Record” denote that the portion displaying the “Measurement/Record” blinks, similarly slanted lines of the portion displaying the “Grandfather” in FIG. 6 .
By the way, FIG. 11 is a diagram showing a display screen on which the vital sign box lets a user select whether the user uses any one of each vital sensor and the camera 5 . The “Temperature,” “Blood pressure,” “Electrocardio,” “Camera,” “Blood glucose level,” and “Body weight” that are shown in FIG. 11 correspond to the earhole clinical thermometer 3 , blood pressure monitor 2 , electrocardiograph 1 , camera 5 , and blood glucose meter 4 in the vital sign box respectively. They are displayed with images obtained by graphing measurements measured by respective vital sensors. In addition, because the “Pulse rate” shown in FIG. 11 is measured by the blood pressure monitor 2 , the “Pulse rate” corresponds to the blood pressure monitor 2 . Furthermore, the “Body weight” corresponds to the scale outside the vital sign box.
By the way, it is assumed that, when the contents shown in FIG. 11 are displayed by the display 10 , first of all, a user is going to measure the “Temperature.” At this time, the user touches the “Temperature” in the display 10 , takes out the earhole clinical thermometer 3 from the vital sign box, and measures body temperature by contacting the earhole clinical thermometer 3 to the user's earhole. Since being a cordless vital sensor, the earhole clinical thermometer 3 is convenient for a user to handle the thermometer 3 . Then, when finishing the measurement of the body temperature, the user presses a send switch provided in the earhole clinical thermometer 3 . When the send switch is pressed, the earhole clinical thermometer 3 transmits a measurement to the reception sensor 8 with using an infrared ray having a predetermined wavelength. In this manner, by letting a user press the send switch to transmit a measurement, it is possible to prevent the mishit or an input of a devious value that can be generated when letting the user input a measurement with using the ten-key pad. In addition, for a user, it becomes unnecessary to perform such troublesome work that the user inputs the measurement with using the ten-key pad. Next, when receiving the measurement from the earhole clinical thermometer 3 , the reception sensor 8 not only outputs information as such to the speaker 11 , but also outputs the information of the measurement to the memory 9 . Then, the speaker 11 outputs such information that the reception sensor 8 has received the measurement from the earhole clinical thermometer 3 by sound. For example, the speaker 11 outputs such a sentence that “The measurement is received.” by sound. In this manner, if the receipt information of a measurement is outputted by sound, a user can confirm that a measured measurement is received by the main body of the vital sign box. On the other hand, when receiving the measurement from the reception sensor 8 , the memory 9 not only lets the display 10 display the measurement in a number as shown in FIG. 12, but also lets the display 10 display the measurements for last five days including the measurement inputted from the reception sensor 8 . At that time, the display 10 displays a final measurement on a graph, in other words, the latest measurement with blinking the measurement. In FIG. 12, it is assumed that a measurement on November 11 is the final measurement, the final measurement is displayed as a black dot, and the black dot portion is displayed with blinking. In addition, the display 10 displays the graph with letting the final measurement be a reference and determining a predetermined range between a certain higher value and a certain lower value than the final measurement as a display range. For example, the display range is a range having the width of 3.5° C. between the final measurement +1.5° C./−2° C., and is determined so that each measurement in the display period is displayed in a substantially central part of the display screen. Thus, since fluctuations do not become clear if the display range becomes larger than the fluctuations of measurements, the display range is determined so that the fluctuations of the measurements become clear. In this manner, by letting a final measurement be a reference and determining a predetermined range between a certain higher value and a certain lower value than the final measurement as a display range, the fluctuations of daily measurements become clear. In addition, the display 10 displays with adjusting a display scale in order to make fluctuations of measurements clear. Furthermore, as show in FIG. 12, when displaying a graph of measurements for past five days including the final measurement, the display 10 displays a “30-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 30 days including the final measurement may be displayed as a graph. In addition, when the user touches the “30-day display” portion, the display 10 , as shown in FIG. 13, displays the measurements for the last 30 days, including the final measurement, in the graph. Also, in regard to the graphical representation, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, a display range is determined by making the final measurement value be a reference so that a predetermined range between a certain higher value and a certain lower value than the final measurement becomes the display range. In addition, a display scale is also determined so that fluctuations of measurements become clear. Furthermore, as show in FIG. 13, when displaying a graph of measurements for past 30 days including the final measurement, the display 10 displays a “5-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 5 days including the final measurement are redisplayed as a graph. When the user touches the “5-day display” portion, the display 10 , as shown in FIG. 12, redisplays the measurements for the last 5 days in a graph. By the way, a measurement received by the reception sensor 8 is outputted as sound from the speaker 11 . Then, if the user confirms display contents in FIG. 12 or 13 and touches a “Return” portion, the display 10 displays contents shown in FIG. 11 once again.
Next, it is assumed that, when the contents shown in FIG. 11 are displayed in the display 10 , the user is going to measure “Blood pressure” and/or “Pulse rate.” At this time, the user touches the “Blood pressure” or “Pulse rate” in the display 10 , takes out the blood pressure monitor 2 from the vital sign box, and measures the blood pressure and pulse rate by wrapping the blood pressure monitor 2 around the user's arm. In addition, the blood pressure and pulse rate are measured at the substantially same time by the blood pressure monitor 2 . Since being a cordless vital sensor, the blood pressure monitor 2 is convenient for a user to handle the blood pressure monitor 2 . Then, when finishing the measurement of the blood pressure and pulse rate, the user presses a send switch provided in the blood pressure monitor 2 . When the send switch is pressed, the blood pressure monitor 2 transmits a measurement to the reception sensor 8 with using an infrared ray having a predetermined wavelength. In this manner, by letting a user press the send switch to transmit a measurement, it is possible to prevent the mishit or an input of a devious value that can be generated when letting the user input a measurement with using the ten-key pad. Next, when receiving the measurement from the blood pressure monitor 2 , the reception sensor 8 not only outputs information as such to the speaker 11 , but also outputs the information of the measurement to the memory 9 . Then, the speaker 11 outputs by sound such information that the reception sensor 8 has received the measurement from the blood pressure monitor 2 .
On the other hand, when receiving the measurement from the reception sensor 8 , the memory 9 not only lets the display 10 display the measurement in a number as shown in FIG. 14, but also lets the display 10 display the measurements for last five days, including the measurement inputted from the reception sensor 8 , in a graph. At that time, as shown in FIG. 14, the display 10 displays highest blood pressure level values and lowest blood pressure values independently in graphs in the same screen with dividing the display area. In addition, the display 10 displays final measurements on the graphs, in other words, the latest measurements with blinking the measurements. Furthermore, when displaying the graphs, the display 10 determines display ranges with the final measurement values as respective references. For example, the display range is a range having the width of 50 mmHg between the final measurement +15 mmHg/−35 mmHg, and is determined so that each measurement in the display period is displayed in a substantially central part of the display screen. Thus, since fluctuations do not become clear if the display range becomes larger than the fluctuations of measurements, the display range is determined so that the fluctuations of the measurements become clear. In this manner, by letting each final measurement be a reference and determining a predetermined range between a certain higher value and a certain lower value than each final measurement as each display range, the fluctuations of daily measurements become clear. In addition, the display 10 displays with adjusting each display scale in order to make fluctuations of measurements clear. Furthermore, as show in FIG. 14, when displaying each graph of measurements for past five days including each final measurement, the display 10 displays each “30-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 30 days including each final measurement are displayed as each graph. In addition, when the user touches the “30-day display” portion, the display 10 , as shown in FIG. 15, displays the measurements for the last 30 days, including each final measurement, in each graph. Also, in regard to the graphical representation, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, each display range is determined by making the final measurement value be a reference so that each predetermined range between a certain higher value and a certain lower value than the final measurement becomes each display range. In addition, each display scale is also determined so that fluctuations of measurements become clear. Furthermore, as show in FIG. 15, when displaying each graph of measurements for past 30 days including each final measurement, the display 10 displays a “5-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 5 days including each final measurement are redisplayed as each graph. When the user touches the “5-day display” portion, the display 10 , as shown in FIG. 14, redisplays the measurements for the last 5 days in each graph. By the way, a measurement received by the reception sensor 8 is outputted as sound from the speaker 11 .
In this manner, if a screen showing the measurement result of blood pressure is displayed in the display 10 and display contents do not change from that status, for example, predetermined time of five seconds passes, the display 10 not only displays measurements in numbers about the measurement result of pulse rates as shown in FIG. 16, but also displays as a graph the measurements for past five days including the measurement inputted from the reception sensor 8 . At that time, the display 10 not only blinks and displays the final measurement, but also displays the graph after determining a display range with the final measurement as a reference so that each measurement in a display period is displayed in a substantially central part of the display screen. In addition, a display scale is also determined so that fluctuations of measurements become clear, and the graph is displayed. Furthermore, as show in FIG. 16, when displaying a graph of measurements of pulse rates for past five days including the final measurement, the display 10 displays a “30-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 30 days including the final measurement are displayed as a graph. In addition, when the user touches the “30-day display” portion, the display 10 , as shown in FIG. 17, displays the measurements for the last 30 days, including the final measurement, in the graph. Also, in regard to the graphical representation, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, the display range is determined. In addition, a display scale is also determined so that fluctuations of measurements become clear. Furthermore, as show in FIG. 17, when displaying a graph of measurements for past 30 days including the final measurement, the display 10 displays a “5-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 5 days including the final measurement are redisplayed as a graph. When the user touches the “5-day display” portion, the display 10 , as shown in FIG. 16, redisplays the measurements of pulse rates for the last 5 days in a graph. In addition, a measurement of a pulse rate received by the reception sensor 8 is also outputted as sound from the speaker 11 .
Now, if a screen showing the measurement result of pulse rates is displayed in the display 10 and display contents do not change from that status, for example, predetermined time of five seconds passes, the display 10 changes display contents from the measurement result of the pulse rates to the contents shown in FIG. 14 about the measurement result of blood pressure. In this manner, if not receiving the user's instruction for changing the display of the measurement period of the graph within predetermined time, the display 10 changes display contents so as to switch between the measurement result of blood pressure and measurement result of pulse rates.
In any case, if the user confirms the display contents when the display 10 displays any one of FIGS. 14 to 17 , and touches a “Return” portion, the contents shown in FIG. 11 are displayed once again in the display 10 .
It is assumed that, when contents shown in FIG. 11 are next displayed in the display 10 , the user is going to measure “Electrocardio.” At this time, the user touches the “Electrocardio” in the display 10 , takes out the electrocardiograph 1 from the vital sign box, and measures the electrocardio by contacting the contact section for a left arm 1 a , and contact section for a right arm 1 b to left and right arms respectively. The user presses a send switch provided in the electrocardiograph 1 during the electrocardio measurement, and when the send switch is pressed, the electrocardiograph 1 transmits a measurement to the LED 7 through a connection cord with using an electrical signal. In this manner, by letting a user press the send switch to transmit a measurement, it is possible to prevent the mishit or an input of a devious value that can be generated when letting the user input a measurement with using the ten-key pad. The LED 7 converts each measurement, transmitted with using electrical signals from the electrocardiograph 1 , into an infrared ray having a predetermined wavelength and transmits the measurement to the reception sensor 8 . When receiving the measurement by the electrocardiograph 1 from the LED 7 in the infrared ray, the reception sensor 8 not only outputs information as such to the speaker 11 , but also outputs the information of the measurement to the display 10 and the memory 9 . Then, the speaker 11 outputs by sound such information that the reception sensor 8 has received the measurement from the electrocardiograph 1 . The display 10 , as shown in FIG. 18, displays an electrocardiographic waveform on the basis of the measurement received by the LED 7 , in real time for a predetermined period of, for example, 10 seconds. At that time, the display 10 displays the electrocardiographic waveform so that the electrocardiographic waveform is continuously displayed. In addition, if one electrocardio measuring period is, for example, 50 seconds, at the time of finishing the measurement the display 10 displays the waveform equivalent to the last predetermined time of predetermined electrocardio measuring time of, for example, the last ten seconds. In addition, so as to make fluctuations of the electrocardio clear when displaying, an electrocardiographic waveform, the display 10 displays an electrocardiogram so that a status of the fluctuations of the electrocardio is displayed in a substantially central part of the display screen. In addition, the display 10 displays the electrocardiogram with adjusting a display scale in order to make fluctuations of measurements clear. On the other hand, the memory 9 records waveform data for the last predetermined time in a predetermined electrocardio measuring time, for example, for last ten seconds, which is displayed at the time of finishing the measurement in the display 10 . Then, if the user confirms display contents in FIG. 18 and touches a “Return” portion, the display 10 displays contents shown in FIG. 11 once again.
Next, it is assumed that, when contents shown in FIG. 11 are displayed in the display 10 , the user is going to use the camera 5 . At this time, the user touches a “Camera” portion in the display 10 .
By the way, a main body of the housing 14 of the vital sign box is put on a predetermined mount and the like so that the height of a CCD of the camera 5 becomes substantially equal to the height of a central part of the user's face when the base 6 is stood substantially vertical to the bottom face of the vital sign box with using the connecting section 6 a while, as shown in FIG. 4, the camera 5 is housed in the base 6 . When the user is going to take a picture of the user's own face with the camera 5 , the user lets the camera 5 take a picture of the user's own face with practically vertically standing and fixing the base 6 to the bottom face of the vital sign box while the camera 5 is housed in the base 6 . Then, an image shot by the camera 5 is displayed as any one of camera images 1 to 4 in the display 10 that are shown in FIG. 19 . By the way, the display 10 , as shown in FIG. 19, displays “Screen zoom” and “Screen erase” in the lower side of the screen when displaying the image of an object such as a face. When the user is going to enlarge any one of the camera images 1 to 4 , the user touches the image among the camera images 1 to 4 that the user is going to enlarge, and furthermore, touches the “Screen zoom” portion. When the “Screen zoom” portion is touched, the image among the camera images 1 to 4 that is touched by the user beforehand is enlarged and displayed in the display 10 as shown in FIG. 20 . In case of finishing the zoom, when the user touches the “Return” portion in display contents that are shown in FIG. 20 and are displayed in the display 10 , the contents shown in FIG. 19 are displayed once again in the display 10 . In addition, if the user is going to erase any one of the camera images 1 to 4 , the user touches the image among the camera images 1 to 4 that the user is going to erase, and touches the “Screen erase” portion. The image is erased if the “Screen erase” is touched. Furthermore, when a user is going to record any image among the camera images 1 to 4 in the memory 9 , the user touches the image among the camera images 1 to 4 that the user is going to record. When the image that the user is going to record in the memory 9 is displayed in a frame of the camera image touched, the user presses a switch that is used to record an image and is provided in the camera 5 . In this manner, when the switch is pressed, the image at that timing is recorded in the memory 9 as a static image. In addition, since the camera 5 is connected to the main body of the vital sign box with a connecting cord, the image that is shot is outputted through the connecting cord to the display 10 and/or memory 9 . Furthermore, it is assumed that the memory 9 can record up to four images. Moreover, different four images that are taken by the camera 5 can be displayed in the display 10 simultaneously as shown in FIG. 19 . Then, it is assumed that it is possible that, so as to display the fifth image different from the images displayed, for example, the fifth image enters into the frame of the camera image 1 , and other images are sequentially shifted and displayed as the image having been included in the frame of the camera image 1 enters into the frame of the camera image 2 and so on.
By the way, differently from the above-described status, there is a case that, for example, the main body of the housing 14 of the vital sign box is not put on the predetermined mount described above, and the height of the CCD of the camera 5 is not equal to the height of the central part of the user's face when the base 6 is stood substantially vertically to the bottom face of the vital sign box while the camera 5 is housed in the base 6 . Nevertheless, in case a user is going to take a picture of the user's own face with the camera 5 , the user takes a picture of the user's own face by rotating the base 6 with using the connecting section 6 a of the base 6 while the camera 5 is contained in the base 6 , and fixing the base 6 with inclining the base 6 at a predetermined angle to the bottom face of the vital sign box. The base 6 is rotatable and can be fixed at the predetermined angle of gradient. Hence, it is possible to take a picture of the user's own face and the like with the camera 5 without changing the user's posture by fixing the base 6 in a predetermined direction and at a predetermined angle of gradient.
In addition, the camera 5 is detachable from the base 6 . Hence, if a user is going to take a picture of, for example, the user's ankle instead of the user's face with the camera 5 , the user takes out the camera 5 from the base 6 , and can take a picture of the ankle with holding the camera 5 in user's hands and so on.
Furthermore, since having a lighting section for lighting an imaging object, the camera 5 can take a clear picture. In addition, since having a function capable of enlarging and shrinking an image, the camera 5 can take an image, which is enlarged or shrunk, and lets the display 10 display the image.
After that, if the user confirms display contents in FIG. 19 and touches a “Return” portion, the display 10 displays contents shown in FIG. 11 once again.
It is assumed that, when contents shown in FIG. 11 is next displayed in the display 10 , the user is going to measure a “Blood glucose level.” At this time, the user touches a “Blood glucoses” portion in the display 10 , and takes out the blood glucose meter 4 , blood-collecting needle 4 a , and sensor chip 4 b from the vital sign box to attach the sensor chip 4 b at a predetermined position of the blood glucosemeter 4 . Next, the user collects the user's own blood of about 5 μl (micro liter) with using the blood-collecting needle 4 b to drip the blood, which is collected, on the sensor chip 4 b . Then, the user measures sugar density in the blood with using the sensor chip 4 b attached on the blood glucose meter 4 . When finishing the measurement of the sugar density in the blood, the user connects the connection jack 4 c to the blood glucose meter 4 , and furthermore, connects the connection jack 4 c to the main body of the vital sign box to press the send switch provided in the blood glucose meter 4 . When the send switch is pressed, the blood glucose meter 4 transmits the measurement to the LED 7 , provided in the main body of the vital sign box, through the connection jack 4 c with using an electrical signal. The LED 7 converts the measurement, transmitted with using the electrical signal from the blood glucose meter 4 , into an infrared ray having a predetermined wavelength and transmits the measurement to the reception sensor 8 . When receiving the measurement by the blood glucose meter 4 from the LED 7 in the infrared ray, the reception sensor 8 not only outputs information as such to the speaker 11 , but also outputs the information of the measurement to the memory 9 . Then, the speaker 11 outputs by sound such information that the reception sensor 8 has received the measurement from the blood glucose meter 4 . On the other hand, when receiving the measurement from the reception sensor 8 , the memory 9 not only lets the display 10 display the measurement in a number as shown in FIG. 21, but also lets the display 10 display the measurements for last five days including the measurement inputted from the reception sensor 8 . At that time, the display 10 displays and blinks the final measurement. In addition, the display 10 displays the graph with letting the final measurement be a reference and defining a predetermined range between a certain higher value and a certain lower value than the final measurement as a display range. Furthermore, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, the graph is displayed. In addition, the display 10 displays the graph with adjusting a display scale in order to make fluctuations of measurements clear. Furthermore, as show in FIG. 21, when displaying each graph of measurements for past five days including each final measurement, the display 10 displays each “30-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 30 days including each final measurement are displayed as each graph. In addition, when the user touches the “30-day display” portion, the display 10 , as shown in FIG. 22, displays the measurements for the last 30 days, including the final measurement, in the graph. Also, in regard to the graphical representation, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, each display range is determined by making the final measurement value be a reference so that each predetermined range between a certain higher value and a certain lower value than the final measurement becomes each display range. In addition, a display scale is also determined so that fluctuations of measurements become clear. Furthermore, as show in FIG. 22, when displaying a graph of measurements for past 30 days including the final measurement, the display 10 displays a “5-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 5 days including the final measurement are redisplayed as a graph. When the user touches the “5-day display” portion, the display 10 , as shown in FIG. 21, redisplays the measurements for the last 5 days in a graph. By the way, a measurement received by the reception sensor 8 is outputted as sound from the speaker 11 . Then, if the user confirms display contents in FIG. 21 or 22 and touches a “Return” portion, the display 10 displays contents shown in FIG. 11 once again.
Next, it is assumed that, when contents shown in FIG. 11 are displayed in the display 10 , the user is going to measure “Body weight.” At this time, the user touches a “Body weight” portion in the display 10 . Then, the user measures the user's own body weight by mounting the scale outside the vital sign box, the scale that can transmit the measurement to the vital sign box with using an infrared ray having a predetermined wavelength. When finishing the measurement of the body weight, the scale transmits a measurement to the reception sensor 8 with using the infrared ray having the predetermined wavelength. When receiving the measurement from the scale, the reception sensor 8 not only outputs information as such to the speaker 11 , but also outputs the information of the measurement to the memory 9 . Then, the speaker 11 outputs by sound such information that the reception sensor 8 has received the measurement from the scale. On the other hand, when receiving the measurement from the reception sensor 8 , the memory 9 not only lets the display 10 display the measurement in a number as shown in FIG. 23, but also lets the display 10 display the measurements for last five days including the measurement inputted from the reception sensor 8 . At that time, the display 10 displays and blinks the final measurement. In addition, with letting the final measurement be a reference and determining a predetermined range between a certain higher value and a certain lower value than the final measurement as a display range, the display 10 displays the graph, so that each measurement in the display period can be displayed in a substantially central part of the display screen. In addition, the display 10 displays with adjusting a display scale in order to make fluctuations of measurements clear. Furthermore, as show in FIG. 23, when displaying each graph of measurements for past five days including each final measurement, the display 10 displays each “30-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 30 days including each final measurement are displayed as each graph. In addition, when the user touches the “30-day display” portion, the display 10 , as shown in FIG. 24, displays the measurements for the last 30 days, including the final measurement, in the graph. Also, in regard to the graphical representation, in order that each measurement in the display period can be displayed in a substantially central part of the display screen, each display range is determined by making the final measurement value be a reference so that each predetermined range between a certain higher value and a certain lower value than the final measurement becomes each display range. In addition, a display scale is also determined so that fluctuations of measurements become clear. Furthermore, as show in FIG. 24, when displaying a graph of measurements for past 30 days including the final measurement, the display 10 displays a “5-day display” portion for changing the display contents in the lower left corner of the display screen simultaneously so that the measurements for past 5 days including the final measurement are redisplayed as a graph. When the user touches the “5-day display” portion, the display 10 , as shown in FIG. 23, redisplays the measurements for the last 5 days in a graph. By the way, the measurement received by the reception sensor 8 is outputted as sound from the speaker 11 . Then, if the user confirms display contents in FIG. 23 or 24 and touches a “Return” portion, the display 10 displays contents shown in FIG. 11 once again.
As described above, when all or part of the respective vital sensors, camera 5 , and scale are used and the use is finished, the contents shown in FIG. 11 are displayed in the display 10 . At this time, the user touches the “Return” portion in FIG. 11, and when the “Return” is touched by the user, the display 10 displays the contents shown in FIG. 9 .
It is assumed that, when contents shown in FIG. 9 are next displayed in the display 10 , the user lets the display 10 display measurements and/or shot images stored in the memory 9 . At this time, the user touches a “Display” in the display 10 , and the display 10 displays and blinks the “Display” portion when the “Display” portion is touched, and after that, changes the display contents to the contents shown in FIG. 11 .
In addition, when the contents shown in FIG. 11 are displayed in the display 10 , the user determines which data of the “Temperature, “Blood pressure,” “Pulse rate,” “Electrocardio,” and “Blood glucose level” measured by respective vital sensors, images taken by the camera 5 , and the “Body weight” measured by the scale, that are stored in the memory 9 , is displayed in the display 10 . Then, the user touches an adequate portion among the “Temperature,” “Blood pressure,” “Pulse rate,” “Electrocardio,” “camera,” “Blood glucose level,” and “Body weight” in the display 10 that corresponds to the data determined. The display 10 reads measurements and graph(s), or data of shot images, which correspond to the portion touched by the user, from the memory 9 , and displays them. In addition, the data displayed in the display 10 is the data displayed in realtime in the display 10 at the time of measuring an object or taking a picture that are explained with using FIGS. 12 to 24 .
Furthermore, although there are two kinds of graphs of measurements relating to, for example, “Body weight” and the like as shown in FIGS. 12 and 13, first of all a 5-day graph shown in FIG. 12 is displayed in the display 10 . Then, similarly to the above description on the display method of measurements in a graph, by the user touching the “30-day display” portion displayed in the display 10 so as to let display 10 display the 30-day graph, the 30-day graph shown in FIG. 13 is displayed in the display 10 . In this manner, it is assumed that, in the case of letting the display 10 display data stored in the memory 9 and being able to display the data obtained by the respective vital sensors, camera 5 , or scale as two kinds of screens, which screen is to be displayed is determined similarly to the case of letting the display 10 display a measurement measured in realtime and a shot image.
In addition, when the user confirms the display contents of data, recorded in the memory 9 , in the display 10 , the user touches the “Return” portion of the screen to change the display contents in the display 10 to the contents shown in FIG. 11 . Furthermore, the user touches the “Return” portion shown in FIG. 11 to change the contents shown in FIG. 9 .
It is assumed that, when the contents shown in FIG. 9 are next displayed in the display 10 , the user is going to communicate with the personal computer connected to the vital sign box via a communications line. At this time, the user touches a “Telephone” portion in the display 10 , and the display 10 displays and blinks the “Telephone” portion when the “Telephone” portion is touched, and after that, changes the display contents to the contents shown in FIG. 25 . FIG. 25 is a drawing showing a display screen for letting a user input a name and a telephone number of a communication partner in order to specify the communication partner of the vital sign box. When the display 10 displays the contents shown in FIG. 25, the user touches any one of “Matsushita Hospital,” “xx clinic,” “Registration wait 3,” and “Registration wait 4,” and “Misc.” portions. By the way, the display of the “Matsushita Hospital” and “xx clinic” means that names and telephone numbers of the “Matsushita Hospital” and “xx clinic” have been already registered. Furthermore, the display of the “Registration wait 3,” “Registration wait 4” and “Misc.” means that names and telephone numbers of communication partners have not been registered yet.
Then, if a communication partner is the “Matsushita Hospital” or “xx clinic” and the name and telephone number have been registered beforehand, the user touches the concerned portion. When the concerned portion is touched, the display 10 displays inquiry items to the user as shown in FIG. 26 . The user replies to the inquiry items shown in FIG. 26, and when the answer is finished, the user touches a “Confirmed” portion. In addition, the display 10 is used as an inquiry result input unit of the present invention according to claim 27 . By the way, when the contents shown in FIG. 26 is displayed in the display 10 and the “Confirmed” portion is touched by the user, the vital sign boxs communicates with the communication partner through the communication terminal 13 , and the display in the display 10 goes to the next step shown in FIG. 29 . On the other hand, if the communication partner is not the “Matsushita Hospital” or “xx clinic” and its name and telephone number are not registered, the user touches any one of the “Registration wait 3,” “Registration wait 4,” and “Misc.” portions. If considering to contacts many times to a specific communication partner in future, the user touches the “Registration wait 3” or “Registration wait 4” portion, or if not, the user touches the “Misc.” portion. If the user touches the “Registration wait 3” or “Registration wait 4,” the display 10 displays the contents shown in FIG. 27 to let the user register a name and a telephone number of the communication partner with letting the user utilize the touch panel. If the user touches the “Confirmed” portion after the registration, the vital sign box contacts to the communication partner through the communication terminal 13 , and the display 10 displays the contents at the next step. In this manner, by letting a user register a name and a telephone number of a communication partner, thereafter, the name and telephone number are associated with the “Registration wait 3” or “Registration wait 4” that is shown in FIG. 25 and touched before the registration of the name and telephone number, and are managed by the vital sign box. On the other hand, if the user touches the “Misc.” portion when the display 10 displays the contents shown in FIG. 25, the display 10 displays the contents shown in FIG. 28 to let the user input a telephone number of a communication partner with letting the user utilize the touch panel. If the user touches the “Confirmed” portion after the input, the vital sign box contacts to the communication partner through the communication terminal 13 , and the display 10 displays the contents at the next step.
In addition, as explained at the time of describing the configuration of an vital sign box of a first embodiment of the present invention, for the convenience of the following explanation, it is assumed that the communication partner of the vital sign box is the “Matsushita Hospital.”
Moreover, although the contact method to a communication partner only by the display in the display 10 is explained in the above description, it is assumed that the contact method to the communication partner is explained simultaneously with using sound from the speaker 11 . In this manner, as described above, also in the following explanation, it is assumed that the usage of the vital sign box is explained not only with the display in the display 10 , but also with a sound output from the speaker 11 .
By the way, it is assumed that a user of the vital sign box is a “Grandfather,” a communication partner of the vital sign box is the “Matsushita Hospital,” and the vital sign box can communicate with the personal computer in the “Matsushita Hospital” on the basis of the contact from the vital sign box. In the display 10 of the vital sign box, as shown in FIG. 29, data, which relates to the “Grandfather,” is measured by each vital sensor, and is graphed, among data stored in the memory 9 , newest images taken by the camera 5 , data that is measured by the scale and graphed, and the inquiry result are displayed separately with sharing an display area. Each graph in FIG. 29 is different from each graph shown in FIG. 11, and is obtained by graphing values that are shown in FIGS. 13, 15 , 17 , 18 , 19 , 22 , and 24 and are actually measured. In addition, when displaying the contents shown in FIG. 29, the display 10 displays that the vital sign box becomes communicable with the personal computer in the “Matsushita Hospital” that is the communication partner. Furthermore, the speaker 11 also outputs by sound that the vital sign box becomes in the status of being able to communicate. In addition, at that time, the vital sign boxs inputs a face image of a doctor in the “Matsushita Hospital,” which is taken by a camera connected to the personal computer, from the personal computer of the communication partner through the communication terminal 13 . Then, the display 10 displays the doctor's image in the top right portion of the screen. In addition, the vital sign boxs transmits data displayed in the display 10 to the personal computer of the communication partner through the communication terminal 13 , and lets the contents, which are shown in FIG. 29 and displayed in the display 10 , displayed on a screen of the personal computer. Furthermore, the “Grandfather” who is a user of the vital sign box lets the camera 5 take a picture of the user's own face with fixing an angle of gradient of camera 5 at a predetermined angle. The vital sign box transmits the user's real time image, taken by the camera 5 , to the personal computer of the communication partner through the communication terminal 13 . In addition, at that time, the microphone 12 becomes in a status that the microphone 12 can collect sonic reflection of realtime voice of the “Grandfather,” and can transmit the voice to the personal computer of the communication partner through the communication terminal 13 . Furthermore, the display 10 becomes in a status that the display 10 can input information from the communication partner through the communication terminal 13 and can display the information. Moreover, the speaker 11 becomes in a status that the speaker 11 can input information such as the voice of the doctor in the communication partner through the communication terminal 13 and can output the information as sound. In this manner, by also using the vital sign box as a picture phone, the “Grandfather” that is a user of the vital sign box receives telemedicine from the doctor in the communication partner.
In addition, suppose that, when the “Grandfather” that is a user of the vital sign box receives telemedicine from the doctor in the communication partner, the doctor observes, for example, a graph of blood pressure in a screen of the personal computer and finds an abnormal indication. Then, when the doctor controls the screen to magnify only the graph in order to pay attention to the graph, not only the graph of blood pressure is magnified on the screen of the doctor's personal computer, but also the graph of blood pressure is magnified and displayed in the display 10 of the vital sign box by the zoom control being inputted into the vital sign box through the communication terminal 13 . Furthermore, when the doctor locates an arrowhead on the graph as shown in FIG. 30 in order to specify the abnormal point, coordinate information of the arrowhead is inputted into the vital sign box through the communication terminal 13 from the doctor's personal computer. Hence, also on the graph of blood glucose level in the vital sign box, an arrowhead is displayed in a location that substantially corresponds to the location that the doctor specifies. In this manner, the above-described arrowhead is utilized as, for example, an arrowhead for informed consent. By the way, since the display 10 stores shape information of an arrowhead to be displayed, it is possible to display the arrowhead by not only being based on the coordinate information of the arrowhead from the doctor's personal computer, but also utilizing the shape information of the arrowhead stored.
Up to here, for the description of communication between the vital sign box and the doctor's personal computer, an example of communication is explained with using the graphs of blood pressure shown in FIGS. 29 and 30. Nevertheless, the communication between the vital sign box and the doctor's personal computer is not limited to the application of the graph of blood pressure shown in FIG. 29 . Thus, other graphs and data shown in FIG. 29 are also used similarly to the graph of blood pressure shown in FIG. 29, and the information of images and/or sound is exchanged between both parties.
Then, when the user of the vital sign box finishes communication with the communication partner, the user touches an “End” portion displayed in the display 10 at that time when the contents shown in FIG. 29 is displayed in the display 10 , and changes the display of the display 10 to the contents shown in FIG. 9 . On the other hand, if the display contents in the display 10 at the time of finishing communication is the contents shown in FIG. 30, the user touches the “Return” portion displayed in the display 10 to let the display 10 display the contents shown in FIG. 29, and touches the “End” portion to change the display in the display 10 to the contents shown in FIG. 9 . In any case, if the contents shown in FIG. 9 are displayed in the display 10 , the user next touches the “End” portion shown in FIG. 9 . In this manner, when the “End” portion shown in FIG. 9 is touched, the display 10 , as shown in FIG. 31, displays information to instruct the user to finish the use of the vital sign box and turn off the vital sign box, and lets the user to turn off the vital sign box.
In addition, in the above-described first embodiment, the base 6 is rotatable, and not only can be fixed at a predetermined angle, but also is means of containing the camera 5 , and the camera 5 is detachable from the base 6 . Nevertheless, it can be also performed that, without providing the base 6 in the vital sign box, the camera 5 is rotatable with connecting to the housing 14 and can be fixed at a predetermined angle.
In addition, in the above-described first embodiment, the lid 15 of the vital sign box, as shown in FIG. 2, is provided through the shank 16 substantially in one edge side of an upper surface of the main body of the housing 14 . In such a structure, there is a possibility of causing such an unstable status that, as shown in FIG. 2, when the lid 15 is let to be vertical to the bottom face of the vital sign box, mainly because of the weight of the display 10 inside the lid 15 , the lid 15 falls down to the side where the shank 16 of the housing 14 is provided, and in connection with it, the main body of the housing 14 rises with one side of the bottom section of the housing 14 , which faces to the shank 16 , as a substantial shaft. Then, in order to solve such structural instability, it can be also performed in regard to the structure of the vital sign box that the shank 16 , as shown in FIG. 32, is located so that the main body of the housing 14 is divided into a front section and a rear section, the lid 15 is provided through the shank 16 , and the display 10 is provided inside the lid 15 with letting the lid 15 be fixed in a status that the lid 15 is vertical to the bottom section of the vital sign box with using the shank 16 at the time of using the vital sign box. In this manner, if the main body of the housing 14 has the front section and rear section to the shank 16 , it is possible to avoid the unstable status that the main body of the housing 14 rises when the lid 15 is let to be vertical to the bottom section of the vital sign box.
In addition, in order to solve the structural problems that are described above and depends on a mounted location of the lid 15 of the housing 14 as shown in FIG. 2, it can be also performed that the display 10 provided inside the lid 15 is thinned and lightened.
Furthermore, in order to solve the above-described structural instability depending on a mounted location of the lid 15 of the housing 14 as shown in FIG. 2, instead of providing the display 10 inside the lid 15 , it can be also performed that, as shown in FIG. 33, the display 10 is made to be movable so that the display 10 can be contained in the main body of the housing 14 in a condition that the display 10 lies in a bottom section of the main body of the housing 14 at the time of non-use, and can be fixed in a condition that the display 10 is vertical to the bottom of the main body of the housing 14 at the time of use. Moreover, it can be also performed that, so as to fix the display 10 in a condition that the display 10 is vertical to the bottom section of the housing 14 at the time of using the display 10 , a fixing section of the display 10 is provided in the main body of the housing 14 .
In addition, although each driving power supply of the respective vital sensors and camera 5 is not explained in the above-described first embodiment, it can be performed that, by mounting each battery in the respective vital sensors and camera 5 , the respective vital sensors and camera 5 are driven by electric power from the batteries respectively. Alternatively, it can be also performed that, by supplying electric power to the respective vital sensors and camera 5 with using the following method, the respective vital sensors and camera 5 are driven by the electric power. Thus, as shown in FIG. 34, for example, it is such a structure that a power supply section 17 is provided in the bottom of the housing 14 of the vital sign box, the power supply section 17 which consists of a predetermined conductive wire that is configured lest the conductive wire should contact to each vital sensor and the camera 5 and further supplies electric power from the outside of the vital sign box to each vital sensor and the camera 5 with using an electromagnetic wave by electromagnetic induction. In addition, the power supply section 17 is provided inside the main body of the housing 14 so that the power supply section 17 becomes substantially in parallel to the bottom face of the main body of the housing 14 . In this case, as shown in FIG. 34, a shape of the power supply section 17 in a position corresponding to each housing location at the time of each vital sensor and the camera 5 being housed in the housing 14 is made to be a winding wire shape. Furthermore, each electric power storage section storing the electromagnetic wave from the power supply section 17 as electric power is provided in each vital sensor and the camera 5 . Moreover, with using an electromagnetic wave by electromagnetic induction from each winding wire section by applying the current to the power supply section 17 from the outside of the vital sign box external when electric power is supplied to each vital sensor and the camera 5 , the electric power is supplied to each vital sensor and the camera 5 . In this way, it becomes not necessary to mount each battery in each vital sensor and the camera 5 . By the way, it can be also performed that, for example, instead of such a structure that each winding wire section is provided only in the specific location as shown in FIG. 34, the power supply section 17 provided in the bottom section of the housing 14 is configured by a predetermined conductive wire whose entire shape is a winding wire shape. In brief, the power supply section 17 is sufficient so long as the power supply section 17 does not contact to each vital sensor and the camera 5 , and supplies electric power from the outside of the vital sign box to each vital sensor and the camera 5 with using an electromagnetic wave by electromagnetic induction. In addition, it is not always necessary to supply electric power with using an electromagnetic wave by above-described electromagnetic induction to all of the vital sensors and camera 5 , but it is also good to supply the electric power to part of the vital sensors and camera 5 .
Furthermore, in the above-described first embodiment, it is assumed that the display 10 , as shown in FIG. 26, displays inquiry items to a user of the vital sign box just before the vital sign box and the personal computer of the “Matsushita Hospital” or “xx clinic” can communicate with each other. Nevertheless, the display of the inquiry items to a user by the display 10 is not limited to the display performed just before communication. For example, the display of the inquiry items to a user by the display 10 can be performed after the vital sign box and personal computer of the “Matsushita Hospital” or “xx Clinic” can communicate with each other. In brief, the display 10 of the vital sign box according to the first embodiment of the present invention is sufficient so long as the display 10 displays the inquiry items to a user.
Moreover, in the above-described first embodiment, although it is assumed that inquiry items to a user of the vital sign box are displayed by the display 10 , the inquiry can be also performed with using sound from the speaker 11 . The inquiry to a user of the vital sign box with using sound, similarly to the display by the display 10 , can be also performed in any timing. By the way, if the inquiry items are outputted with using sound, it becomes necessary to provide an inquiry result input section, into which the user inputs answers to the inquiry items, in the vital sign box. It is possible to use, for example, the display 10 as the inquiry result input section. In addition, it is made to provide a communication terminal for transmitting answers to inquiry items, which the inquiry result input section inputs, to a communication partner. As the communication terminal, for example, the communication terminal 13 can be also used. In addition, by also using the communication terminal to be used so as means of inputting information from a communication partner, it can be performed not only to let the display 10 display the information from the communication partner, but also to let the speaker 11 output the information from the communication partner with using sound. Nevertheless, the information from the communication partner can be also outputted with using one out of the display 10 and speaker 11 .
In addition, in the above-described first embodiment, although it is made that the usage of the vital sign box is outputted by the display performed by the display 10 and by sound from the speaker 11 , the usage of the vital sign box can be also performed by any one of the display by the display 10 and the sound from the speaker 11 . Furthermore, if the usage of the vital sign box is output only by sound from the speaker 11 , a change instruction input section for inputting an instruction from a user can be also provided in the vital sign box so that an output method of the usage is changed to the display by the display 10 .
Moreover, in the above-described first embodiment, as described at the time of describing the configuration of the vital sign box according to the first embodiment of the present invention, the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 are used as an example of vital sensors in the vital sign box of the present invention according to each of claims 1 , 11 , 13 , 15 , 17 , 20 , 21 , 25 and 26 . Nevertheless, the vital sensors that are provided in the vital sign box of the present invention according to each of the above-described claims are not limited to the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 . All of the electrocardiograph 1 , blood pressure monitor 2 , earhole clinical thermometer 3 , and blood glucose meter 4 can be provided in the vital sign box of the present invention, or only the part of them can be also provided. In addition, for example, other vital sensors such as a blood oxymeter measuring blood oxygen concentration can be also provided.
In addition, in the above-described first embodiment, as shown in FIG. 11, it is made that the usage of the vital sign box is displayed in graphic images of measurements measured by respective vital sensors, images taken by the camera 5 , a graphic image of measurements measured by the scale, and letters. Nevertheless, the usage of the vital sign box can be displayed only in graphic images of measurements measured by respective vital sensors, images taken by the camera 5 , and a graphic image of measurements measured by the scale, or can be also displayed only in letters. Furthermore, only the images, only the letters, or images combined with letters can be also used and displayed every screen. Moreover, although each graph in FIG. 11 is made to be a graphic image of measurements measured by each vital sensor, if a user's data has been already stored in the memory 9 at that time, a graph of the data stored can be also used as each graph in FIG. 11 . In addition, also as for an image to be taken by the camera 5 , if a user's image has been already stored in the memory 9 at that time, the memory can be also substituted by the image stored.
Furthermore, in the above-described first embodiment, it is made that a measurement measured by each vital sensor is displayed in the display 10 with using a number of the measurement or in a transition graph of measurements for last 5 days or 30 days including the measurement. In addition, it is made that a measurement is also outputted from the speaker 11 by sound. However, a measurement measured by each vital sensor can be also displayed only in a number in the display 10 , or can be also displayed only in a graph in the display 10 . Moreover, only sound can be also outputted from the speaker 11 . Furthermore, the display of only a number in the display 10 and an output by sound from the speaker 11 can be also performed. Alternatively, the display of only a graph in the display 10 and an output by sound from the speaker 11 can be also performed.
In addition, in the above-described first embodiment, it is made that, for example, as shown in FIGS. 12, 13 , and 14 , a measurement measured by each vital sensor is displayed in the display 10 as a transition graph of measurements for 5 days or 30 days including the measurement. However, in the display 10 , a transition graph of measurements for the last 10 days can be also displayed without displaying the transition graph showing the measurements for 5 days or 30 days. In brief, a graph displayed in the display 10 is sufficient so long as the graph shows the transition of measurements in a predetermined period. Moreover, by providing means of a user inputting, for example, an instruction for specify the period in the vital sign box, it is also possible to let the display 10 change the period according to the instruction each time a graph is displayed.
In addition, in the above-described first embodiment, for example, as shown in FIGS. 12 and 13, when measurements measured by each vital sensor are displayed on the display 10 as a graph so as to show the transition during the last 5 days or 30 days, a display range is determined with a final measurement as a reference. Nevertheless, the display range can be also determined by letting a mean value of measurements in a period to be displayed be a reference, and defining the period be a range between predetermined higher value and lower value than the value that is the reference.
Moreover, in the above-described first embodiment, as shown in FIGS. 12 and 14, it is made that the display 10 displays and blinks a final measurement in a 5-day graph of measurements when displaying the graph of measurements measured by each vital sensor. On the other hand, it can be also performed that the display 10 displays and blinks the final measurement when displaying a 30-day graph of measurements, or that the display 10 displays and does not blink the final measurement.
Furthermore, in the above-described first embodiment, a communication partner of the vital sign box is the “Matsushita Hospital.” Nevertheless, the contents, first displayed in the display 10 when the vital sign box can communicate with another communication partner, is not limited to the contents shown in FIG. 29 . It is also good to display some one except inquiry items among contents shown in FIG. 29, or to display only a message that the vital sign box becomes communicable with a communication partner. In brief, this means that, if a communication partner of the vital sign box is not the “Matsushita Hospital,” when the vital sign box becomes communicable, the contents displayed in the display 10 are not limited.
In addition, in the above-described first embodiment, it is made that, when the vital sign box becomes communicable with a personal computer of the “Matsushita Hospital” that is a communication partner of the vital sign box, a latest image taken by the camera 5 is displayed in FIG. 29 displayed in the display 10 . Nevertheless, so long as the image is an image taken by the camera 5 , it is not necessary to display the latest image in the display 10 displaying the contents shown in FIG. 29 . For example, it is also good to display an image to be selected by letting a user select beforehand the image to be displayed. Furthermore, it is also good that, if image data is not stored in the memory 9 , an image taken by the camera 5 is displayed.
Moreover, in the above-described first embodiment, although it is assumed that a communication partner of the vital sign box is “Matsushita Hospital,” it is also good that the communication partner is, for example, a personal computer of a relative who lives apart from the “Grandfather” who is a user of the vital sign box. In that case, it is also possible to use the camera 5 in the vital sign box as means of taking a realtime picture of the “Grandfather” that is a user, or as a picture phone for performing communication with the relative.
In addition, in the above-described first embodiment, although a communication partner of the vital sign box is a personal computer of the “Matsushita Hospital.” The communication partner of the vital sign box is not limited to a personal computer so long as the partner can communicate with the vital sign box via a communication line such as a telephone line. For example, by connecting two vital sign boxs with each other via a communication line, both vital sign boxs can communicate with each other, and hence it is also possible to use the partner's vital sign box as an alternative of a personal computer. Furthermore, it is also possible to use both vital sign boxs as alternatives of picture phones.
Moreover, in the above-described first embodiment, it is made that it may happen that, when the vital sign box becomes communicable with a personal computer of the “Matsushita hospital” that is a communication partner, as shown in FIG. 30, arrowhead information for displaying an arrowhead in a graph is transmitted from the personal computer to the vital sign box. In addition, in that case, it is made that the arrowhead information is coordinate information and the vital sign box displays the arrowhead on the basis of the coordinate information of the arrowhead from the personal computer by utilizing shape information of the arrowhead stored. However, it is also good that arrowhead information transmitted from the personal computer to the vital sign box is coordinate information and shape information, and the arrowhead is displayed in a predetermined position by decoding the arrowhead from the shape information by the vital sign box and further using the coordinate information. However, in this case, an amount of information of the arrowhead information from the personal computer to the vital sign box increases in comparison to a case of only the coordinate information.
Furthermore, in the above-described first embodiment, although it is described that the vital sign box is operated by a user himself/herself, a user of the vital sign box can be a person, who assists a patient who cannot operate the vital sign box by oneself, such as a family member of a bedridden home health care patient or a visiting nurse.
Moreover, in the above-described first embodiment, although it is made that the display 10 is a touch panel type liquid crystal display, the display. 10 can be a CRT display. In brief, it is good that the display 10 is a display just displaying each measurement measured by each vital sensor such as the electrocardiograph 1 and the blood pressure monitor 2 , an object taken by the camera 5 , the usage of the vital sign box, and the like. In addition, it is better that the display changes display contents when a predetermined portion is touched.
In addition, in the above-described first embodiment, it is made that, for example, as described in FIG. 6, when a predetermined portion such as the “Grandfather” in the display 10 is touched by a user, the portion touched is displayed and blinked. Nevertheless, it is also good that, when the predetermined portion in the display 10 is touched by the user, a color of the touched portion changes so that the touched portion is distinguished from other portion. In brief, it is sufficient only that, when a predetermined portion on the display 10 is touched by a user, the portion touched is displayed so that the portion is distinguished from the other portion.
Furthermore, in the above-described first embodiment, it is made that, if contents displayed in the display 10 are not change in a predetermined period, the measurement result of blood pressure and a pulse rate measured by the blood pressure monitor 2 are displayed with being mutually changed to an opponent measurement. Nevertheless, it is also good that, by providing switching means of changing the measurement result between blood pressure and a pulse rate, which is displayed in the display 10 , in the vital sign box, the display 10 changes display contents when a user instructs the switching means. Moreover, it is also good to substitute the touch panel type display 10 for the switching means.
In addition, in the above-described first embodiment, it is made that a user presses a switch, which is provided in the camera 5 , for recording an image in the memory 9 when an image taken by the camera 5 is recorded in the memory 9 . Nevertheless, recording means of recording an image in the memory 9 can be provided in the main body of the vital sign box. It is also good to substitute the touch panel type display 10 for the recording means. In brief, it is sufficient only that the recording means of recording an image taken by the camera 5 in the memory 9 is provide in the vital sign box.
In addition, if the display 10 in the above-described vital sign box is a touch panel type display and a software keyboard function shown in FIG. 7 is provided and displayed in the display 10 , a merit that a user can input characters is created without connecting a keyboard to the vital sign box. The software keyboard function can be utilized for the above-described inquiry result input, and further can be used for inputting questions to a doctor.
Furthermore, in the above-described first embodiment, although it is made that an image to be recorded in the memory 9 is a static image, an image stored in the memory 9 can be a moving image.
Moreover, in the above-described first embodiment, it is made that the vital sign box receives data from a scale that is outside the vital sign box and can transmits a measured value to the vital sign box with using an infrared ray having a predetermined wavelength. But, it is also good that it is made that the vital sign box cannot receive data from such a scale. Alternatively, it can be performed that the vital sign box receives data from equipment, which is outside the vital sign box and can transmit a measurement to the vital sign box with using an infrared ray having a predetermined wavelength, besides a scale, and records and manages the measurement with data from each vital sensor.
In addition, in the above-described first embodiment, it is made that the vital sign box is used by any user among a “Grandfather,” a “grandmother,” “Registration wait 3,” and “Registration wait 4,” that are shown in FIG. 5, that is, a user having been already registered, or a user who is going to be registered from now on. Nevertheless, it can be performed to provide, for example, a function for making it possible for a house guest to an owner of the vital sign box, a one-time user, and the like, that is, a person, whose name and password are not registered, to use the vital sign box.
Furthermore, although the camera 5 in the vital sign box according to the above-described first embodiment is used, for example, for taking a picture of an arm injury, it is necessary to adequately adjust a focus at that time. Although fixed focus adjustment and automatic focus adjustment can be listed as the focus adjustment, it can be assumed that the camera 5 in this embodiment is a fixed focus type camera. If so, it is possible to make the camera be smaller, lighter, and cheaper than an automatic focusing type camera.
In this way, if the camera 5 is a fixed focus type camera like this, it is desirable to provide range-finding means, which is used for measuring the distance between an imaging object such as an arm injury and a predetermined section such as a lens of the camera 5 , in the camera 5 . The reason is because it is necessary to condense rays of light from the camera 5 to the imaging object and to adjust the focus.
By the way, it is possible to use a string-like body or a rod-like body, which is attached in a predetermined location such as a lens of the camera 5 and has predetermined length, as the above-described range-finding means. The length of the string-like body or rod-like body may be set in such a manner that in taking a picture of the imaging object, when the tip of the string-like body or rod-like body is brought into contact with the imaging object, the focus can be adjusted. For example, it is recommended that the length is 3 cm.
In addition, instruction receiving means such as a button for receiving an imaging instruction from a user, and imaging means of taking a picture of an imaging object when the imaging instruction is received are provided in the camera 5 . It is made that the user takes a picture of the imaging object by performing the imaging instruction to the camera 5 through contacting an end of the above-described string-like body or rod-like body with the imaging object, and pressing the button at that time when the user is going to take a picture of the imaging object such as an arm injury. By performing this, it becomes possible to take a picture at a correct focus.
In addition, the range-finding means is not limited to the above-described string-like body or rod-like body, but it is possible to use means, which utilizes an electromagnetic wave such as an ultrasonic wave or an infrared ray, as the range-finding means. Concretely, means of emitting an electromagnetic wave such as an infrared ray and detecting means of detecting the electromagnetic wave such as an infrared ray reflected by an imaging object is provided in the camera 5 . Further, the distance between the imaging object and a predetermined position such as a lens of the camera is measured from the result detected by the detecting means. At that time, if comparison result output means of comparing the measured distance with the predetermined distance that the imaging object can be adequately shot, and outputting the comparison result by a sound and an image is provided in the camera 5 , a user can perform an imaging instruction by pressing a button when the imaging object is located in an appropriate focal position. For example, the result that it becomes possible to adequately take a picture of the imaging object by accessing the imaging object by 2 cm more corresponds to the comparison result. By performing so, it becomes possible to take a picture at a correct focus. In addition, it can be performed that the above-described comparison result output means outputs information as such by a sound or an image when the imaging object is located in an appropriate focal position.
Furthermore, if the distance between the imaging object and camera is measured with using an electromagnetic wave as described above, it can be performed that the imaging means automatically takes a picture of the imaging object when the detected distance is the distance that the imaging object can be shot adequately.
Moreover, it can be performed that at least part of the housing 14 of the above-described vital sign box consists of metallic material, and a connecting section that connects a heating section, which generates heat in connection with image display to a display, outputting of sound from a speaker, and information communication at a communication terminal, such as a CPU (central control processing unit) and an HDD (hard disk drive) that are housed in the housing 14 , and a metallic material section of the above-described housing 14 , and that consists of metallic material (for example, a copper wire) is provided in the vital sign box. Then, heat in the heating section can be discharged outside the vital sign box through the connecting section.
For example, if the body temperature of a human body is measured with a clinical thermometer contained in the vital sign box, it is necessary to keep the temperature of the clinical thermometer itself at about room temperature before measurement. Hence, by discharging heat in this way, the clinical thermometer is kept to be at about room temperature, and hence this has a merit that the clinical thermometer can be used effectively. In addition, even if the clinical thermometer is an actually measuring type clinical thermometer or a forecasting type clinical thermometer, the heat radiation effect is the same so long as the clinical thermometer is a device measuring body temperature electrically.
Furthermore, if heat radiation is neglected, it is conceivable that the measurement accuracy of a clinical thermometer deteriorates. Nevertheless, as described above, for example, by providing a connecting section consisting of a copper wire or the like, heat can be radiated with using heat transfer in the connecting section, and hence it becomes possible to suppress the temperature rise of the vital sign box. Moreover, in regard to an vital sign box, when sensor installation locations are designed, it is effective to arrange the vital sign box apart from a clinical thermometer.
Furthermore, a medium that bears a program and/or data for letting a computer execute all or part of functions of the above-described vital sign box, from which the computer can read the above-described program and/or data, and with which the above-described program and/or data that are read execute the above-described functions with collaborating with the above-described computer also belongs to the present invention.
Moreover, an information aggregation that is a program and/or data for letting a computer execute all or part of functions of the above-described vital sign box, from which the computer can read the above-described program and/or data, and with which the above-described program and/or data that are read execute the above-described functions with collaborating with the above-described computer also belongs to the present invention.
The data includes data structure, a data format, and a kind of data. The medium includes a recording medium such as ROM, a communication medium such as the Internet, and a transmission medium such as light, a radio wave, and a sound wave. The bearing medium includes, for example, a recording medium recording a program and/or data, a transmission medium transmitting a program and/or data, and the like.
The processability by a computer includes readability by a computer in case of, for example, a recording medium such as ROM, and processability of a program and/or data, which are objects of transmission and have been actually transmitted, by a computer in case of a transmission medium.
The information aggregation includes, for example, software such as a program and/or data.
Apparently from the above description, the present invention can provide an vital sign box that has means of being able to take a picture with flexibly changing an imaging object and/or an imaging angle.
In addition, the present invention can provide an vital sign box that has a vital sensor that can input a measurement into memory without letting a user perform a manual input.
Furthermore, the present invention can provide an vital sign box including a display to clearly display the fluctuations of measurements in a predetermined period that are measured and recorded by a vital sensor.
Moreover, the present invention can provide an vital sign box including a speaker outputting a measurement, which is measured by a vital sensor, with using sound.
In addition, the present invention can provide an vital sign box that includes imaging means of taking a picture of an object, and can transmit an image of the object that is taken by the imaging means to a communication partner. Furthermore, the present invention can provide an vital sign box that receives information from a communication partner, and can perform bi-directional communication.
Moreover, the present invention can provide an vital sign box inquiring health conditions of a user of the vital sign box. | An vital sign box has a plurality of vital sensors measuring predetermined biological, chemical, or physical conditions of a living body; an camera taking a picture of a predetermined object; and a housing containing the plurality of vital sensors and the camera. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
Not Applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
Not Applicable.
BACKGROUND OF THE INVENTION
The present invention relates in general to determining co-channel interference levels for wireless transmissions, and, more specifically, to measuring a desired/undesired ratio using portable equipment that does not require disruption of broadcasting or complicated test equipment or procedures.
In connection with obligations of licensees of wireless broadcasting services, it often becomes necessary to measure various signals at potential receiving locations in order to comply with requirements designed to minimize interference between different broadcasters. For example, in the Broadband Radio Service (BRS) authorized in a 2.5 GHz band by the Federal Communications Commission in the United States, a transition is being conducted wherein licensees of the Multipoint Distribution Service (MDS) are being reassigned to frequencies in the BRS. The BRS has been used to broadcast analog television (i.e., video) signals. Some new licensees in the BRS will operate on the same frequencies as existing licensees with the band. Licensees at the same frequencies will operate in respective service areas, but the potential for co-channel interference still exists and the FCC has specified certain interference requirements to be met. More specifically, the FCC requires that, as measured at a particular receiving site, the co-channel desired/undesired (D/U) ratio for a protected (i.e., previously existing) licensee must be at least the lesser of either 45 dB or the actual D/U ratio at the receiving site for the previously existing licensee prior to the transition minus 1.5 dB.
It is known that D/U ratio measurements can be done by first measuring the received power of a desired signal and then shutting off the desired transmitter and measuring the level of any undesired signal that may be present. This type of testing creates problems because it may be necessary to shut off the transmitter repeatedly or for noticeably long periods, resulting in interruption of programming to viewers being served by the BRS licensee (which may be a cable television provider, for example). In addition, the coordination required if multiple receive sites are being transitioned can be difficult and time consuming.
Difficulties arise when attempting to conduct measurements of desired and undesired power when both signals are present simultaneously. Typically, the undesired signal falls within a well-defined window relative to the desired signal. Considering the BRS service, the frequency difference between the two signals will be between 0 kHz and 11 kHz, and the D/U need only be measured down to 45 dB. As the frequency separation between the two transmitters approaches zero, extremely high resolving capability would be required in any measuring equipment. This situation can be improved by shifting the frequency of the desired transmitter to increase the separation, but even with frequency shifting the proximity of the desired and undesired carrier frequencies as well as the complex voltage of the active video signal makes the D/U measurement virtually impossible using standard test equipment. Relatively expensive equipment and/or highly skilled test operators have been required.
SUMMARY OF THE INVENTION
The present invention achieves an accurate and convenient system and method for determining D/U ratios without disrupting any broadcast signals and without requiring expensive test equipment or highly specialized training of test technicians.
In one aspect of the invention, a system is provided for measuring a D/U ratio for desired and undesired signals in a wireless video transmission system at a shared channel frequency based on a received signal at a geographic location in proximity to regions within respective service areas for the desired and undesired signals. A video tuner demodulates the received signal to generate a baseband video signal. A leveling circuit normalizes the baseband signal. A video processor identifies horizontal sync pulses within the baseband signal, generates a sampled signal comprising the horizontal sync pulses, and removes components of the desired signal from the sampled signal to generate an undesired signal component. A D/U analyzer determines a Fourier transform having a plurality of bins in response to the undesired signal component, identifies at least one of the bins having a spectral peak corresponding to an undesired signal, and calculates the D/U ratio in response to a magnitude of the identified peak.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the spatial relationship between a receiving site and desired and undesired transmitters.
FIG. 2 is a waveform diagram showing an NTSC baseband television signal.
FIG. 3 shows horizontal sync pulses in the presence of an undesired signal.
FIG. 4 shows a sync-amplitude signal obtained by sampling and holding a sync level signal.
FIG. 5 is a flowchart showing one preferred method of the present invention.
FIG. 6 is a frequency-power spectrum of a sampled sync signal showing the presence of interfering undesired signals.
FIG. 7 is a block diagram showing main functionality of a test system of the present invention.
FIG. 8 is a block diagram showing one preferred hardware embodiment of the system of FIG. 7 .
FIG. 9 is a schematic diagram of a level detector.
FIG. 10 is a schematic diagram of an RF attenuator for working together with the level detector in order to sustain an RF level at a predetermined magnitude.
FIG. 11 is a schematic diagram showing a video processor of the invention.
FIG. 12 is a flowchart showing operation of the testing system in greater detail.
FIG. 13 is a block diagram showing the main software components of the test system.
FIG. 14 is a screen shot of a user interface for initiating a test measurement of the present invention.
FIG. 15 is a screen shot from the user interface during capture of reception data.
FIG. 16 is a screen shot showing test results.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings, FIG. 1 shows a transmitter 10 with a corresponding service area 11 having a receive site 12 . RF broadcast signals 13 propagate from transmitter 10 to receiving site 12 . Undesired transmitters 14 and 15 in other service areas radiate broadcast signals 16 and 17 , respectively, that also reach receiving site 12 . The present invention measures the D/U ratio corresponding to the various broadcasts to ensure compliance with FCC regulatory levels and to facilitate adjustments by the operators of the transmitters to achieve compliance.
A receiver 20 located at receiving site 12 is connected to a video distribution system 24 , such as a cable headend. Receiver 20 includes an antenna 21 , a downconverter 22 , and a demodulator 23 . A test system 25 of the present invention is connected to the output of downconverter 22 .
In order to be able to measure the much lower level undesired signals in the presence of the strong desired signals, the present invention takes measurements at a time during which the voltage of the desired video signal is substantially constant so that the measured variation in voltage is caused by the presence of undesired signals. In particular, measurements are made during horizontal sync pulses. During the horizontal sync pulses, the signal carrier is at its highest level. In addition, the sync pulses are evenly distributed over time, making them well suited for use as a measurement time because it is easier to detect variations in the horizontal sync pulses resulting from an interfering undesired signal. As shown in FIG. 2 , regular horizontal blanking intervals 27 include respective horizontal sync pulses 28 . Each horizontal sync pulse lasts 4.7 μS, and consecutive horizontal sync pulses repeat at a period of 63.5 μS (i.e., they repeat at a frequency of 15.734 kHz).
As broadcast, each horizontal sync pulse is a square pulse having a predetermined, constant voltage level. As shown in FIG. 3 , the received horizontal sync pulses deviate from the ideal pulse shape due to interfering transmissions from undesired transmitters. Thus, the amplitude or received signal strength corresponding to each horizontal sync pulse has deviations 29 superimposed on the ideal pulse shape as a result of energy from interfering sources having an overlapping frequency spectra.
The horizontal sync pulses contain no program material, occur every 63.5 μS at the highest RF signal level, and as seen at the receiver have a substantially constant received signal strength. Variations in signal strength seen at the times of the horizontal sync pulse are thus due to contributions by undesired signals. By limiting the measurement to coincide with the horizontal sync pulses, the invention can remove the active video portion of the signal so that the measured variations are due to undesired signals which are automatically separated from the desired sync pulses. By constructing a sampled waveform containing only data from horizontal sync pulses, a frequency analysis can be employed to distinguish between desired and undesired signal contributions. Since the expected signal strength of the desired signal alone is substantially constant, the desired signal contribution shows up as the portion of the frequency spectra at around 0 Hz (i.e., DC). Other signal contributions correspond either to undesired broadcasts on the same shared channel frequency or noise.
FIG. 4 shows a preferred embodiment for constructing a sampled sync signal containing only signal components present during the horizontal sync pulses. Thus, a sampled sync signal 30 has a magnitude determined by sampling an average signal strength level of an individual horizontal sync pulse at 31 and holding that sample value at 32 until the occurrence of the next horizontal sync pulse. The sample interval 31 may last for about 3 μS during a center portion of a horizontal sync pulse, for example. Hold period 32 then comprises the remaining 60.5 μS. Thus, sampled sync signal 30 represents the varying energy content derived from the undesired signals.
FIG. 5 shows an overall method of the present invention wherein test equipment is set up at a test location in step 35 . Typically, the test system equipment is installed in association with a fixed receiver within the area being served by the desired signal and outside the service area for the undesired signal. In step 36 , the carrier frequency of the desired transmitter is offset by a predetermined offset frequency from the shared channel frequency assigned by the FCC. As explained below, the use of a frequency offset allows energy contributions from undesired signals to be distinguished from noise or other non-video sources.
In step 37 , the test equipment is tuned in order to receive the desired broadcast signal. The predetermined offset frequency introduced for the desired transmitter is sufficiently small (e.g., about 2-3 kHz) that tuning to and receiving the desired broadcast signal is not significantly affected.
In order to reliably compare the desired signal level to an undesired signal level, the received signal seen by the reception antenna is normalized to a predetermined level in step 38 . The tuner demodulates the desired signal and samples of the normalized demodulated signal are collected during the horizontal sync pulses in step 39 .
In step 40 , a fast Fourier transform (FFT) is calculated for each sampled sync signal derived from a respective one of a plurality of measuring periods. A measuring period lasting about 200 mS, for example, is input to a spectrum analyzer to calculate all the frequency components of each FFT. In step 41 , peaks are identified in any particular FFT that correspond to an undesired broadcast signal. Once the frequency of an undesired signal is identified according to the peaks, then the maximum level of the FFT at the identified peak frequencies is determined over the plurality of measuring periods. Due to the phase relationship between the horizontal sync pulses of the desired signal and the frequency content of the interfering portion of an undesired signal, the energy of the interfering signal oscillates between constructive interference and destructive interference. By identifying a maximum FFT level, the maximum constructive interference can be found which corresponds to the true D/U ratio. Typically, the plurality of measuring periods covers a time span of about 35 seconds to ensure that the appropriate maximum has occurred. In step 43 , the D/U ratio is calculated for each undesired signal's carrier frequency identified by a corresponding peak. If the worst D/U ratio is below the regulatory limit, then calculation of D/U ratios for other interfering undesired signals would be unnecessary.
FIG. 6 shows a calculated Fourier transform corresponding to the frequency spectra for the sampled sync signal over one measuring period. The carrier frequency of the desired transmitter is offset so that the carrier frequency of any undesired transmitters on the shared channel frequency will be seen in this frequency spectrum as being offset from zero Hz. Due to variations in the precision of the frequency reference used by various transmitters, some small offset may normally be seen between the desired and any undesired frequency signals. By deliberately adding an additional offset of around 5 kHz, the undesired frequencies are easier to identify and can be positively identified as an interfering signal in the following manner.
Due to the presence of the desired signal, a frequency peak is seen at 15.734 kHz corresponding to the repetition frequency of the horizontal sync pulses in the desired signal. If an undesired signal is present, then the energy of the horizontal sync pulses contained in the undesired signals are likewise shown as spectral peaks in the Fourier transform. As a result of folding during demodulation, however, spectral peaks corresponding to the horizontal sync pulses of any particular undesired signals are shown at the corresponding frequency offset both above and below the spectral peak at 15.7 kHz. Thus, a frequency-power peak 45 appearing at a difference frequency equal to DELTA 1 corresponds with a symmetrical peak 46 at a difference frequency equal to negative DELTA 1 from 15.734 kHz. Since spectral peaks 45 and 46 are symmetrically spaced above and below the frequency of the horizontal sync pulses, it can be concluded that frequency DELTA 1 identifies the frequency of a spectral peak 47 of the corresponding undesired signal carrier. Likewise, a second undesired signal appears at a frequency DELTA 2 as confirmed by symmetrical placed spectral peaks corresponding to the horizontal sync pulses of the second undesired signal. Another spectral peak 48 in the vicinity of the peak at 15.7 kHz is found not to correspond to an undesired signal because it has no matching spectral peak symmetrically placed on the opposite side of 15.7 kHz. Therefore, it can be concluded that spectral peak 48 is due to noise or some other radiated admission source which does not need to be considered in order to determine the D/U ratio.
FIG. 7 shows a portable test system based on a laptop PC 50 . An auxiliary battery 51 and charger 52 are provided for allowing prolonged periods of use without continuous connection to an active power source. A DC power distribution and USB hub 53 is coupled to laptop 50 , a DDU measurement block 54 , and an RF measurement block 55 . RF measurement block 55 receives the VHF/UHF RF input also seen by the receiver installed at the test site. Digital attenuation, logarithmic detection, and level measurement of horizontal sync pulses are performed in RF measurement block 55 . DDU measurement block 54 performs tuning, demodulation, and signal processing and sampling.
FIG. 8 shows a preferred embodiment of the test system in greater detail. A USB video tuner and capture card 57 is controlled by laptop 50 and provides a demodulated video/audio signal to laptop 50 through a USB hub 58 . The demodulated signal may also be stored by the capture feature in card 57 under control of laptop 50 . The demodulated signal is also provided along with an intermediate frequency signal to a custom circuit block 60 which generates a sampled sync signal as will be described below. The sampled sync signal may be stored in a D/U waveform capture card 61 . A USB A/D converter 62 is coupled to custom circuit block 60 and to USB hub 58 for providing conversion of a level detection signal as will be described below. Custom circuit block 60 receives an RF signal from the downconverter which is part of the normal installation at the receive site.
In order to automatically calibrate the sampled sync signal according to the level of the desired signal, the IF signal generated in USB video tuner and capture card 57 is provided to a level detector circuit 65 within custom circuit block 60 as shown in FIG. 9 . A lowpass filter 66 receives the IF signal from an input connector 67 and couples the filtered IF signal to an input of a logarithmic amplifier 68 which comprises an integrated circuit AD8310 available from Analog Devices, Inc. of Norwood, Mass. Logarithmic amplifier 68 is connected to perform a signal level determination in accordance with published configurations of the AD8310. When a switch 69 is configured to supply a high DC voltage level to an enable input of the AD8310, an output voltage level is provided at an output terminal 70 which is proportional to the received signal strength of the input IF signal. The received signal strength signal is provided to A/D converter 62 and the digitized IF level is provided to an attenuator circuit 72 which is part of the custom circuit block 60 as shown in FIG. 10 . In the embodiment of FIG. 9 , level detector circuit 65 is implemented using an evaluation board with support components as recommended by Analog Devices.
Attenuator circuit 72 in FIG. 10 can provide two-step attenuation using an analog fixed attenuator 73 , and a digitally controlled variable attenuator 74 . In particular, variable attenuator 74 is comprised of a digital step attenuator integrated circuit DAT-3175-PP available from Mini-Circuits Laboratory of Brooklyn, N.Y. Fixed attenuator 73 is a known commercial device. The digitized IF level from A/D converter 62 is provided at a connector 75 . When a most significant bit 76 of the digitized IF signal is a 1, then fixed analog attenuator 73 is switched on in order to introduce a predetermined attenuation such as 20 dB. Other bits of the parallel control word from the A/D converter 62 are coupled to respective inputs of variable attenuator 74 through respective buffer circuits. The support circuits for integrated circuit DAT-3175-PP are as shown for evaluation board TB-337 also available from Mini-Circuits. An attenuated RF signal is provided at output connector 79 such that the RF signal has been attenuated by the amount necessary to maintain the level of the IF signal at a predetermined level.
The properly attenuated RF signal is passed to the USB video tuner and capture card 57 which provides a baseband video signal after demodulation to a video processing circuit 80 as shown in FIG. 11 . Video processing circuit 80 is included in custom circuit block 60 and is built around a Sync Separator integrated circuit EL4583 available from Intersil Americas Inc. of Milpitas, Calif. The baseband video signal is applied to pin 4 of the EL4583 and after filtering is applied to a sample and hold circuit 81 . Pin 9 is a level output which is an analog voltage equal to twice the horizontal sync pulse amplitude of the video input signal applied to pin 4. In a normal video receiver, the level output of pin 9 would be used to provide an indication of signal strength. In the present invention, variations in the level output signal are instead used to characterize signal contributions from undesired signals. Thus, the level output signal from pin 9 is applied to D/U waveform capture card 61 for storage and also for use in an analysis performed by software programs loaded on laptop PC 50 . More particularly, the level output at pin 9 provides the sampled sync signal.
A preferred method for identifying carrier frequencies of undesired broadcast signals and for characterizing the D/U ratio is shown in FIG. 12 . In step 84 , the software components within laptop PC 50 and the states of the hardware elements are all initialized. In step 85 , a control program in laptop PC 50 sets the video tuner to the desired shared channel frequency to be tested and then activates the level detecting circuit to measure the IF level. In step 86 , the measured IF level is used to set the attenuation of the RF signal in order to obtain a predetermined target IF level which results in calibration of the sampled sync signal so that the D/U ratio can be directly determined from the sampled sync signal level.
In step 87 , horizontal sync pulses of the desired signal are detected using the sync separator in the video processing circuit. The amplitude of each horizontal sync pulse is sampled and held until the occurrence of the next horizontal sync pulse in order to construct a sampled sync signal that varies in accordance with the amplitude of each horizontal sync pulse. An FFT of the horizontal sync pulse level from the sampled sync signal is computed in step 89 . Based on this first FFT, a search is conducted for the spectral peaks within the FFT in order to identify the presence of undesired broadcast signals that may interfere with the desired signal. A spectral peak may be defined as a frequency bin or bins in the Fourier transform have an amplitude greater than surrounding bins as is known in the art.
In step 90 , a search is conducted for peaks within the FFT between 15.734 kHz (the peak corresponding to the horizontal sync frequency of the desired signal) and an upper limit corresponding to a worse case separation of the desired signal and other undesired broadcast signals. The worst case frequency is determined according to the largest frequency error that may be inadvertently present in the transmission of an undesired signal from its assigned frequency plus the predetermined offset frequency deliberately introduced in the transmission of the desired signal for purposes of this test. A typical upper bound may be about 22 kHz, for example.
For each spectral peak found in the search, a check is made to determine whether there is a symmetrical peak at the negative DELTA frequency of such peak in step 91 . If no such corresponding symmetrical peaks are found for any peak about 15.7 kHz, then no undesired signals are detected and the test system indicates a failure at step 92 .
In step 93 , for each peak wherein a corresponding peak is found at the negative DELTA frequency, such DELTA frequency is added as a detected undesired frequency in a table. With the carrier frequencies of the undesired signals having been identified, a complete data collection is performed in step 94 sufficient to allow characterization of the D/U ratio. Thus, the method collects and stores additional sample and hold data for a plurality of measuring periods. In a preferred embodiment, each measuring period lasts about 200 mS and the sum of measuring period spans about 35 seconds (i.e., including about 175 measuring periods). In step 95 , Fourier transforms are computed for each respective measuring period. FFT values at the undesired signal carrier frequencies shown in the table are stored. Due to the shifting phase relationship between the desired and undesired broadcast RF signals, interference between the desired and undesired signals varies between constructive interference and destructive interference. It is necessary to identify the occurrence of constructive interference in order to accurately determine the D/U ratio. First, however, the data from the plurality of measuring periods is filtered for spurious data and checked for validity in step 96 . Then the maximum level for each table frequency is found in step 97 . Based on the maximum levels, the D/U ratio is calculated in step 98 and the results are displayed.
The software for the laptop PC of the present invention is comprised of two main blocks, namely a user interface and automation block and a D/U processing block. The user interface is designed to lead a test technician through each of the steps required to make D/U signal level measurements. In connection with transitioning transmitters getting reassigned channel allocations in the BRS service, the user interface may be adapted to collecting both pre-transition and post-transition measurements. The user interface deals with channel selection, recording and storing of video samples, acquiring and storing data from the D/U module, evaluation of pre- and post-transition measurements for conformity with FCC requirements, and other miscellaneous tasks.
The D/U processing software operates as previously described in connection with the flowcharts. All of the applications for the laptop PC are based on ActiveX and DLL, taking advantage of the .Net framework and DirectX. FIG. 13 shows main software blocks based within the .Net framework together with various standard libraries of functions 101 - 103 . An RF module 104 is a customized software module for supervising operation of the hardware components as previously described. The tuning/recording module 105 provides the user interface and supervision for selecting the appropriate channel to be characterized. An FFT and display module 106 controls the processing of sampled sync signal data as described in the previous flowcharts. Preferably, a spectrum analyzer within block 106 is comprised of an audio spectrum analyzer of a type that comprises commercially available software.
FIG. 14 shows a screen shot during set up and initialization of the test equipment after connection to a downconverter at a site being tested. An instruction window 110 assists a technician in conducting the necessary operations to obtain a D/U measurement. A window 111 allows the technician to enter identifying information of a particular site and to select a channel frequency for testing, as well as identifying pre- and post-transition measurements. A window 112 is used to indicate a path for storing test data and captured video on the laptop PC.
FIG. 15 shows a screen shot during data capture of the present invention. A message window 113 informs the technician of parameters and events during the testing. A video window 114 displays the current desired signal being detected in order to allow the technician to confirm the identity of the desired signal being measured and to show the overall video quality at the time of testing.
FIG. 16 is a screen shot showing a results screen. The screen layout is similar to that shown by a conventional audio spectrum analyzer which may be conveniently used in the present invention since the frequency spectrum of the sampled sync signal falls within the audio frequency range. An FFT frequency-power spectrum 120 is plotted as confirmation to the technician that acceptable data has been gathered. For example, visual inspection can confirm the presence of a spectral peak at 15.734 kHz corresponding to the horizontal sync frequency of the desired signal. Based on the data represented in FIG. 16 , a DELTA frequency of 2.5 kHz has been identified wherein a D/U ratio of −32 DB is calculated, as shown in window 121 . As seen in plot 120 , the spectral peak at 2.5 kHz is best identified by the DELTA frequency method rather than by simple visual inspection of spectral peaks. The method of the present invention is sufficiently simple and repeatable to be implemented by software that does not require significant expertise of the test technician in order to operate successfully. | A D/U ratio is measured for desired and undesired signals in a wireless video transmission system at a shared channel frequency based on a received signal at a geographic location in proximity to regions within respective service areas for the desired and undesired signals. A video tuner demodulates the received signal to generate a baseband video signal. A leveling circuit normalizes the baseband signal. A video processor identifies horizontal sync pulses within the baseband signal, generates a sampled signal comprising the horizontal sync pulses, and removes components of the desired signal from the sampled signal to generate an undesired signal component. A D/U analyzer determines a Fourier transform having a plurality of bins in response to the undesired signal component, identifies at least one of the bins having a spectral peak corresponding to an undesired signal, and calculates the D/U ratio in response to a magnitude of the identified peak. | 7 |
BACKGROUND OF THE INVENTION
This invention pertains to the packaging and material handlng arts and more specifically to a new and useful container for the packaging of fragile items.
Those skilled in the packaging and material handling arts having long recognized a need for a simple container which is useful for packaging fragile items by suspending and thereby mechanically isolating the items from the exterior of the container so that shock and vibration which is suffered by the external container is not also suffered by the fragile item packaged therein.
Various solutions have been proposed for such a problem which range from packing the fragile items in layers of resilient material to providing complicated suspension systems within the package. Providing layers of resilient material has the disadvantage that it adds weight to the package and is wasteful of material. The J. E. Clenny and W. H. Fairchild patent, U.S. Pat. No. 987,958, shows one manner in which cardboard buffers are used to fill in the space between the inner and outer carton and thus shock mount the inner carton.
The Hoover patent, U.S. Pat. No. 2,700,460, and the two Ryno patents, U.S. Pat. Nos. 2,700,518 and No. 2,785,795, show complex systems in which the fragile item is suspended in a flexible tubing which is then twisted at the ends and thereby providing a suspension system. Such systems are too complex to be economical for large volume packaging.
SUMMARY OF THE INVENTION
The primary objective of this invention is to provide a container for packaging fragile items which overcomes the difficulties of the prior art devices. The unique construction of the present invention, which incorporates a carton suspended within a carton by tabs that are integral to the inner carton, provides several advantages.
First, the inner carton is securely suspended and attached to the outer carton by means of a slot and tab thereby requiring only a minimum amount of material for the actual suspension function.
The use of integral tabs allows the suspension system to be formed out of the same blank as the inner carton thereby simplifying assembly of the container.
Also, the unique construction allows the suspension system to be completely assembled at the same time that the package is assembled, i.e., the package requires no further manipulations in order to engage the suspension system aside from the assembly of the cartons themselves.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of the blank from which the inner carton is formed.
FIG. 2 is a plan view of the blank from which the outer carton is formed.
FIG. 3 is an exploded perspective view of a container showing the component parts thereof.
FIG. 4 is a perspective view of a partially formed container showing the upper end with the tab of the inner container protruding through a slot in the outer container.
FIG. 5 is a perspective view of a container showing the container with the upper tabs bent over to engage the end portion of the outer container.
FIG. 6 is a sectional view taken along line 6--6 of FIG. 5.
FIG. 7 is a sectional view taken along line 7--7 of FIG. 5.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIG. 3, in accordance with the instant invention, a container which is suitable for packaging a fragile item 1 comprises an inner carton 5 and outer carton 13. The inner carton 5 is assembled from a blank which is shown in FIG. 1. The blank 4 consists of side wall panels 8a, 8b, 8c and 8d hingedly connected to each other at fold lines 88a, 88b and 88c. A sealing tab 7 is hingedly connected to side wall panel 8d at fold line 88d. The blank 4 also has top wall panels 10a, 10b, 10c and 10d which are respectively hinged to side wall panels 8a, 8b, 8c and 8d at hinge lines 110a, 110b, 110c and 110d. The blank 4 also has bottom wall panels 12a, 12b, 12c and 12d which are respectively hinged to side wall panels 8a, 8b, 8c and 8d at hinge lines 112a, 112b, 112c and 112d. Also, the top panels 10a and 10c have tabs 14a and 14c hingedly connected at hinge lines 114a and 114c. The tabs 14a and 14c include fold lines 214a and 214c, the purpose of which will presently appear. The bottom panels 12a and 12c have tabs 16a and 16c respectively attached at hinge lines 116a and 116c. The tabs 16a and 16c include hinge lines 216a and 216c, the purpose of which will presently appear.
In reference to FIG. 2, the outer carton 13 is constructed from a blank 6 which has side wall panels 9a, 9b, 9c and 9d hingedly connected at fold lines 99a, 99b and 99c. A sealing tab 11 is hingedly connected to side wall panel 9d at fold line 99d. The blank 6 also has top wall panels 20a, 20b, 20c and 20d respectively hinged to side wall panels 9a, 9b, 9c and 9d at hinge lines 120a, 120b, 120c and 120d. The blank 6 also has bottom wall panels 22a, 22b, 22c and 22d which are respectively hinged to side wall panels 9a, 9b, 9c and 9d at hinge lines 122a, 122b, 122c and 122d. The top wall panels 20b and 20d and the bottom wall panels 22b and 22d each respectively have flat shallow slots 24b, 24d, 26b and 26d cut therein. Top and bottom wall panels 20a, 20c, 22a and 22c each respectively have elongated slots 28a, 28c, 30a and 30c cut therein. The purpose of these slots will presently be made apparent.
With reference to FIG. 3, the cartons 5 and 13 are assembled from the two blanks 4 and 6. When the sealing tab 7 of blank 4 is attached by gluing or other suitable means to the inside of side wall 8a, the resulting carton 5 takes on a rectangular shape such that the side walls 8a, 8b, 8c and 8d are folded to be perpendicular to each other. The same is true with respect to blank 6 when its sealing tab 11 is attached to the inside of side wall 9a to form carton 13.
The top flaps 10b and 10d of carton 5 are folded toward the center of the carton 5 along lines 110b and 110d. Then, top flaps 10a and 10c of carton 5 are folded along lines 110a and 110c respectively so that top flaps 10a and 10c overlap top flaps 10b and 10d and are glued thereto. In the process of folding top flaps 10a and 10c, tabs 14a and 14c are folded outwardly so that tabs 14a and 14c are abutting and are congruent to each other. The same operation is repeated in folding the bottom flaps of carton 5.
With respect to carton 13, top flaps 20c and 20a are initially folded along lines 120a and 120c so that slots 24a and 24c are adjacent thereby forming a single slot. Next, top flap 20b is folded along fold line 120b so as to overlap flaps 20a and 20c, and flap 20b is glued to flaps 20a and 20c. Top flap 20d is then folded along fold line 120d to overlap top flaps 20b, 20a and 20c and is glued to flap 20b. The inner carton 5 is then inserted through the open bottom end of the outer carton 13 and the congruent tabs 14c and 14a extend through the slot formed by overlying slots 24a, 24c, 26a and 26c in the top end of the carton 13 as shown in FIG. 4. The flaps 14a and 14c are then bent outwardly along fold lines 214a and 214c respectively and can be glued to the surface of flap 20d as indicated in FIG. 5. The bottom end of outer carton 13 is then folded so that the tabs 16c and 16a are congruent and similarly protrude through the slot formed by 26b, 26d, 30a and 30c. The tabs 16a and 16c are then folded back along fold lines 216a and 216c so that they lay flat and can be glued to the bottom flap 22b.
With reference to FIGS. 6 and 7, it can be seen that the fragile item 1 is completely sealed within the inner carton 5, and the carton 5 is completely isolated from carton 13 by an air space around the top and sides and bottom except for those portions of tabs 14a and 14c which lie between fold lines 214a and 114a and 214c and 114c respectively. In this manner, the carton 5 is suspended from both the top and the bottom of the outer carton 13 and is, therefore, mechanically shock mounted. | A container for packaging fragile items. The container provides an inner carton suspended within an outer carton. The suspension is achieved by means of integral end flaps on the inner carton which interlock the end flaps of the outer carton. | 8 |
BACKGROUND OF THE DISCLOSURE
This invention relates to an improvement in the process of making 1:1 zinc and 1:1 manganese complexes with alpha amino acids, particularly methionine. In that sense, it represents an improvement over the processes disclosed in commonly owned U.S. Pat. Nos. 3,941,818 issued Mar. 2, 1976, entitled "1:1 ZINC METHIONINE COMPLEXES" and 3,950,372 issued Apr. 13, 1976, and entitled "1:1 MANGANESE ALPHA AMINO ACID COMPLEXES".
Both of the previously issued patents relate to the 1:1 complexed salts per se, and to general processes for preparing the same. The novel salts have as expressed in the earlier issued patents, the useful feature of being highly body absorbable nutritional supplements for both animals and humans to provide readily available sources of zinc ions on the one hand, and manganese ions on the other hand.
In the commercial preparation of these 1:1 metal amino acid complexes, there have been from time to time certain problems in solubilizing the precursor salts and the alpha amino acid, both of which exist in solid powdered form. As a result, even though the salts are theoretically highly soluble in water, the amount of necessary mixing to assure substantial dissolving (even at elevated temperatures) in order to provide the necessary intimate contact for adequate reacting between the two to form 1:1 complexes of the zinc and/or manganese and the alpha amino acid is quite excessive. Thus, there has been an inherent problem in the preparation technique, both from the standpoint of the very practical problem of adequate dissolving even in hot water, and also the problem of assuring that the product is substantially all the desired 1:1 complexes.
Accordingly, there has been a real and a continuing need for the discovery of process improvements which allows the ready dissolving of the initial precursor reactants or ingredients, and which will simultaneously assure product yield in high amounts of the desired 1:1 complexes of the metal ions and the alpha amino salts.
This invention has as its primary objective the fulfillment of this need in order that the 1:1 manganese alpha amino acid complexes of U.S. Pat. No. 3,950,372 and the 1:1 zinc alpha amino acid complexes of U.S. Pat. No. 3,941,818, may be prepared easily without long process delays and in high yield of the desired 1:1 complexes.
For details of desirability and utility of 1:1 manganese alpha amino acid complexes, see the previously referred to U.S. Pat. No. 3,950,372 which is incorporated herein by reference. For details of desirability and utility of 1:1 zinc alpha amino acid complexes, see U.S. Pat. No. 3,941,818 which is incorporated herein by reference.
The method of accomplishing each of the objectives of this invention will become apparent from the detailed decription of the invention which follows hereinafter.
SUMMARY OF THE INVENTION
This invention relates to a process improvement which allows increased ease of preparation in high yields of 1:1 complexes of zinc and manganese with alpha amino acids to provide in high yield the desired 1:1 complexes in a form which can be readily absorbed biochemically after ingestion by animals and humans to provide adequate and proper dietary levels of zinc and methionine as necessary for proper health, weight gain and dietary balance. The reaction is a straightforward reaction between the respective zinc salt and the respective manganese salt and the alpha amino acid, which are both at least partially dissolved in water. It is significantly catalyzed, both from the standpoint of solubilization of the respective salts and from the standpoint of producing the desired 1:1 complexes between the respective zinc ion and manganese ion and the desired alpha amino acid, preferably methionine, by conducting the reaction in the presence of catalytically effective amount of ferric ion, preferably in the form of ferric sulfate.
DETAILED DESCRIPTION OF THE INVENTION
It is important to note that the respective zinc and manganese compounds which are prepared in accordance with this invention are referred to as complexed salts. These salts are to be carefully distinguished from conventional salts such as, for example, zinc chloride or manganese chloride. Such conventional salts such as zinc chloride or manganese chloride contain only an electrostatic attraction between the cation and the anion. The 1:1 complexed salts prepared by this invention differ from conventional salts in that while they have an electrostatic attraction between the cation and the anion, there is also a coordination bond between the cation and the amino moiety of the alpha amino acid.
The preferred alpha amino acid for use in this invention is methionine. From the standpoint of both zinc complex salts and the manganese complex salts, however, it should be understood that other alpha amino acids may be employed as well. Preferably those are essential alpha amino acids. Those essential alpha amino acids which are preferred for utilization in forming the 1:1 complex salts of this invention are arginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophane, and valine. Glycine, while not an essential amino acid, is also a preferred alpha amino acid in that it is readily available and can be utilized for synthesis of the complex salts of this invention. The two most preferred natural alpha amino acids are methionine and glycine.
With regard to the preferred zinc methionine complexed salts which are prepared in accordance with the improved process of this invention, they have the general formula: ##STR1## wherein X is an anion and w is an integer equal to the anionic charge of X. The cation of these complexed salts is represented by the bracketed material in the above formula and represents a 1:1 complex of zinc and methionine.
With regard to the manganese alpha amino acid complex salts of the present invention, they have the formula: ##STR2## wherein R is an alpha moiety of alpha amino acid, preferably methionine or glycine, X is an anion, and W is an integer equal to the anion charge of X. The cation of these complexed salts is represented by the bracketed material in the above formula and represents a 1:1 complex of manganese and alpha amino acid.
The process of preparing the desired zinc and methionine 1:1 complex salts of the alpha amino acids referred to herein, in each instance as the earlier patents mention, is straightforward and direct. Commonly it begins with the use of a water soluble zinc salt and/or a water soluble manganese salt, respectively. Suitable zinc salts which can be employed are the halides, the sulfates, and the phosphates. The desired weight ratio of zinc salt to methionine is within the range of 1:1 to 2:1, preferably 3:2. Suitable manganese salts which can be employed are likewise halides, sulfates and phosphates. The desired weight ratio of manganese to methionine is 1:1 to 2:1, preferably 4:3. In each instance, the sulfate salts are preferred from the standpoint of availability and, at least currently, cost.
In the general process, these salts are at least partially water dissolved, preferably at elevated temperatures. Temperatures within the range of from about 180° F. to about 205° F. have been found desirable, most preferably temperatures with the range of 190° F. to about 205° F. In actual practice, one common technique is to stir the salt into a water solution while simultaneously injecting steam to elevate the temperature within the desired range.
In the most preferred embodiment of the present invention the catalytic ferric ion is next added. It should be understood, however, that the catalytic amount of ferric ion can be added both before the addition of the alpha amino acid or after, with before being modestly preferred.
As previously mentioned, it has been discovered that when the reaction between the water soluble metal salt and the alpha amino acid is conducted in the presence of a catalytically effective amount of ferric ion, two desirable things occur. In the first instance, the dissolving of the salt and the amino acid in the water appears to be significantly enhanced from the standpoint of rapidity and in the second instance, there is an increased yield of the desirable 1:1 complexes formed.
It is not known precisely why the ferric ion catalyzes the process, but it nevertheless does. The ferric ion may be added in the form of any water soluble salt such as ferric chloride, ferric sulfate, ferric phosphate, ferric acetate or any other suitable water soluble ferric salt. The most preferred are ferric chloride and ferric sulfate. The amount added can be from about 2% to about 10% based upon the dry weight of alpha amino acid, preferably from about 4% to about 8% based upon the dry weight of alpha amino acid employed. For the most preferred alpha amino acid of this invention, methionine, 4% by weight has been found best in experimentation to date. However, it should be understood that any amount within the range from about 2% up to about 10% by weight of the alpha amino acid will work. The lower limit expressed herein, i.e., 2%, is about the minimum quantity needed for any significant improvement. The upper level is a practical and economic level, since amounts in excess do not seem to add anything except expense. After the preferred catalytic amount of ferric ion is added to the water soluble salt of either zinc or manganese, and mixed therein, the desired alpha amino acid is then stirred into the reaction mixture along with increased injection of steam in order to elevate the temperature again to within the desired temperature range.
It is noted in the reaction process that where the ferric ion is used, almost immediately the solution becomes clear, lumping does not occur, and in the case of zinc methionine complexes, it immediately turns to a clear reddish brown solution. In the case of manganese methionine complexes, the reaction immediately turns to a distinct clear solution of similar color. In both instances, there is no problem of "lumping" and the reaction becomes straightforward and direct to the desired 1:1 complexes.
After the reaction is completed, which is ordinarily a matter of minutes, but may be up to an hour or longer if desired, the product is ready for finishing.
If product concentrate is desired, it may be spray dried in each instance. On the other hand, if the product is to be mixed with a carrier, such as a cereal product, it may be mixed together at varying ratios, put into drying drums, and dry coated on the cereal product.
The following examples are offered to further illustrate the improved process of this invention.
EXAMPLE 1
(Preparation of 1:1 Zinc Methionine Complexes)
This process prepares in batch form a 1,010 pound batch of product.
Five hundred pounds of water are heated to within the range of from 200° F. to 205° F. by injecting steam into a batch holding stainless steel vessel. Three hundred pounds of reagent grade zinc sulfate are added to the vessel, while continually stirring the same. Simultaneously 10 pounds of ferric sulfate are added and steam is continuously injected in order to maintain the temperature within the range of 200° F. to 205° F. Thereafter, 200 pounds of methionine is added, while continuously stirring.
Immediately, the reaction product turns clear, all lumping is elminated, and the product appears to be a true solution, reddish brown in color. When it is readily apparent that everything is dissolved and nothing is in suspension, the product is then passed to a spray dryer and spray dried to provide a 1:1 zinc methionine complex.
The formation of the 1:1 complex is confirmed by infrared analysis, titration curve analysis, and quantitative analysis. Such was found to be present in excess of a 90% yield of the desired product.
EXAMPLE 2
(Formation of 1:1 Manganese Alpha Amino Acid Complexes)
A substantially similar process as used in Example 1 is done with the following changes. In this instance again the amount of the batch was 1,010 pounds, 500 pounds of water, and 500 pounds of solids. In the solids, the manganese salt employed was manganese sulfate, and the ferric catalyst employed was again ferric sulfate. The amount of manganese sulfate employed was 286 pounds, and the amount of methionine employed was 214 pounds. The ratio of these was 4:3. The amount of catalyst employed was 10 pounds.
Again, it was evident that no lumping occurred, that there was a true solution formed, and that the reaction was nearly instantaneously complete upon stirring with the reactants present. Again, the desired 1:1 manganese methionine complex was formed in a yield in excess of 90%.
It therefore can be seen that the invention accomplishes at least all of its stated objectives. | A method of making 1:1 complex salts of alpha amino acids and a metal ion which is either zinc or manganese, the method comprising reacting a water soluble zinc salt or manganese salt with an alpha amino acid in the presence of catalytically effective amount of ferric ion which aids in solubilizing the metal salt while simultaneously enhancing the formation of 1:1 complexes between the selected zinc or manganese salt and the desired alpha amino acid, particularly methionine. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to controls and, more specifically, to a touchless water control system having at least one sensor capable of determining hand movement from point A to point B in a first direction, from point C to point D in a second direction and from point E to point F in a third direction thereby establishing a spatial field spaced away from a faucet through which a user's hand can be moved to initiate or terminate water flow, vary and set water temperature and water pressure.
2. Description of the Prior Art
There are other control devices designed for fluid flow. Typical of these is U.S. Pat. No. 3,556,146 issued to Groen on Jan. 19, 1971.
Another patent was issued to Pepper on Sep. 6, 1983 as U.S. Pat. No. 4,402,095. Yet another U.S. Pat. No. 4,788,998 was issued to Pepper, deceased et al. on Dec. 6, 1988 and still yet another was issued on Feb. 4, 1992 to Tsutsui et al. as U.S. Pat. No. 5,085,399.
Another patent was issued to Aharon on Aug. 27, 1996 as U.S. Pat. No. 5,549,273. Yet another U.S. Pat. No. 5,875,257 was issued to Marrin et al. on Feb. 23, 1999. Another was issued to Jeromson et al. on Feb. 4, 2003 as U.S. Pat. No. 6,513,787 and still yet another was published on May 8, 1991 to Mitsutoshi as Japan Patent No. JP3107682.
Another patent was published to Tadao, et al. on Nov. 26, 1996 as Japan Patent No. JP8311945. Yet another Japan Patent No. JP2003293411 was published to Takeshi on Oct. 15, 2003. Another was published to Yoichi et al. on Jul. 27, 2006 as Japan Patent No. JP2006193954 and still yet another was published on May 15, 2008 to Boey as International Patent Publication No. WO 2008/057630.
U.S. Pat. No. 3,556,146
Inventor: Johannes Groen
Issued: Jan. 19, 1971
A liquid dispensing device, in particular for hospitals and clinics, whereby the supply of hot or cold water to a wash bowl or the like may be controlled without touching any valves by hand. The water supply is regulated by an electromagnetic valve controlled by a proximity detector operating as a variable voltage divider. The proximity detector is fed with a high frequency signal and delivers an output voltage which may be influenced by putting the hand near the proximity detector. Separate proximity detectors for controlling the supply of hot and cold water, respectively, are mounted on the outlet pipe of the wash bowl in such manner that they may be actuated either separately or simultaneously, so that hot, cold or tepid water may be supplied as desired.
U.S. Pat. No. 4,402,095
Inventor: Robert B. Pepper
Issued: Sep. 6, 1983
A water faucet is disclosed that is automatically turned on and off in response to the proximity of the user's hand or other object to the faucet. An ultrasonic transducer is located in the faucet near the water outlet and transmits bursts of ultrasonic waves. When a wave reflects off a user's hand and creates an echo signal, the echo is detected by the ultrasonic transducer. Circuitry connected to the ultrasonic transducer determines when an object is within a predetermined distance of the faucet by measuring the time elapsed between the transmission of the burst and the reception of the echo. Once an object is within this predetermined distance, the circuitry causes a valve to open and water is supplied by the faucet.
U.S. Pat. No. 4,788,998
Inventor: Robert B. Pepper, deceased
Issued: Dec. 6, 1988
A water faucet is disclosed that is automatically turned on and off in response to the proximity of the user's hand or other object to the faucet. An ultrasonic transducer is located in the faucet near the water outlet and transmits bursts of ultrasonic waves. When a wave reflects off a user's hand and creates an echo signal, the echo is detected by the ultrasonic transducer. Circuitry connected to the ultrasonic transducer determines when an object is within a predetermined distance of the faucet by measuring the time elapsed between the transmission of the burst and the reception of the echo. Once an object is within this predetermined distance, the circuitry causes a valve to open and water is supplied by the faucet. Additionally, there is an embodiment wherein the level to which the receptacle is to be filled can be selected by the user and the fill system automatically fills the receptacle to that level. Further, there is a drain control system disclosed that causes fluid to be removed from the receptacle if the user selects an empty level or a fluid level that is lower than the fluid level of the fluid currently within the receptacle. Still further, there is a receptacle having a pilot well in communication with the main portion of the receptacle. The distance measuring sensor can be placed within the pilot well so that the rim of the receptacle exposed to the user is unencumbered.
U.S. Pat. No. 5,085,399
Inventor: Osamu Tsutsui et al.
Issued: Feb. 4, 1992
An automatically operating valve for regulating water flow, especially a mixing valve for automatically mixing hot water and cold water to obtain a mixed water of a desired temperature is characterized by employing piezoelectric actuators for operating valve bodies thereof. Due to such a construction, the valve can not only fully close or open but also carries out the fine flow amount control by regulating the opening rate or angle of the valve body. Especially in case the automatically operating valve is a mixing valve, the mixing ratio of hot water and cold water can be accurately regulated so that the mixed water of a desired temperature can be always automatically obtained.
U.S. Pat. No. 5,549,273
Inventor: Carmel Aharon
Issued: Aug. 27, 1996
An electronically operated assembly to be used in conjunction with water faucets is provided with a sensor that senses the presence of objects such as human hands and automatically starts the flow of water. The water flow automatically stops when the object is removed from the faucet vicinity. An electronically automated assembly for water faucets comprises a water flow control valve and a small size electric motor adapted to operate the water flow control valve via a transmission gear and an infrared sensing device connected to a source of electric power adapted to activate or disconnect the electric motor.
U.S. Pat. No. 5,875,257
Inventor: Teresa Marrin et al.
Issued: Feb. 23, 1999
Apparatus for continuous sensing of hand and arm gestures comprises hand-held means for continuously sensing at least tempo and emphasis. These sensed parameters are represented quantitatively, and transduced by appropriate circuitry into electrical signals indicative of the parameter quantities. The signals may be used to control the performance of a musical composition (or the evolution of some other dynamic system), or may instead convey information. The signals may, for example, be provided to an interpreter that dynamically infers control commands from the gestures on a real-time basis in accordance with the generally accepted canon of musical conducting, directing the controlled system in accordance therewith. The invention may also sense one or more additional conducting parameters such as the speed and/or velocity, direction (i.e., trajectory) in three dimensions, absolute three-dimensional position, the “size” of a gesture in terms of the spatial distance between successive beats, and the “placement” of a beat pattern in space.
U.S. Pat. No. 6,513,787
Inventor: Peter James Jeromson et al.
Issued: Feb. 4, 2003
The fluid supply apparatus supplies and controls one or more fluids while adjusting/controlling one or more continuously parameters; and includes an outlet, at least one control valve and a touchless user control interface. For example a faucet has sensors mounted thereon to control water flow (6) and temperature (16, 17). For example a user hand in field (16) will increase temperature over time and decrease in field (17). The on/off sensor field may include the water stream, a bi-colour light emitting diode indicates temperature, temperature feedback means maintains the desired temperature, a battery or super capacitor allows operation or fluid shut off if power fails, an anti-tamper feature requires the fluid to be shut off if more than one sensor is covered and a time prevents waster wastage. The hygienic touchless interface may be in a tile or flat plate. Other applications may include panel mounted fluid control systems for controlling a plurality of fluid types and associated parameters.
Japan Patent Number JP3107682
Inventor: Kimura Mitsutoshi
Published: May 8, 1991
PURPOSE: To regularly and certainly operate a device without a possibility of improper operation by a foreign material by providing first to third opening and closing means for opening and closing a solenoid valve, depending on the distance detected by a distance sensor in a valve control means. CONSTITUTION: When a user goes in front of a sink 14 and reaches out his hand just before a distance sensor 21 (a position closer to the sensor 21 than a first distance), a first opening and closing means 1 operates to open a solenoid valve 13, so that water or hot water is released from a faucet 12. When the user again reaches out the hand just before the sensor 21, a second opening and closing means 2 operates to close the valve 13. The valve 13 is alternately opened and closed every time when the hand is consciously reached out just before the sensor 21, and the release and stop of water from the faucet 12 are repeated. When the user leaves the sink 14 during release of water, a third opening and closing means 3 operates to close the valve 13, so that the release of water is stopped. When a foreign material passes just before the sensor 21 in the absence of the user, the means 1 detects this to open the valve 13, but after the foreign material passed, the means 3 operates to close the valve 13.
Japan Patent Number JP8311945
Inventor: Soma Tadao et al.
Published: Nov. 26, 1996
PURPOSE: To make it possible to inject water at the position of a hand with accuracy by laying out a sensor which detects light at the tip of an arm member which follows a rotary movement of a faucet and bringing a hand near a water outlet so as to pass water and separating the hand from the outlet so as to stop the flow of water. CONSTITUTION: The length dimensions of a faucet 12 and an optical detection sensor 20 are arranged with an optical detection member 19 by expanding and contracting the arm. The arm member 19 is turned, centering on a mounting shaft 22 of the arm member 19. The positional arrangement of the sensor 20 is made so as to set that the sensor come to the tip of the faucet 12. As descried above, fingers are held out to the tip of the faucet 12 on a washstand. When the sensor 20 detects this, a faucet drive mechanism 15 makes a closing motion so that tap water may flow out from a water outlet 13. Then, the fingers are pulled in after cleaning and the faucet drive mechanism 15 makes a closing motion by way of the sensor 20, thereby halting the flow of water. When the faucet 12 is interrupting, the faucet 12 is turned to a corner, thereby securing an upper space. The faucet 12 and the optical detection sensor 20 are turned in one piece motion by mounting a connection member 2 and both members 12 and 20 may be independently turnable respectively.
Japan Patent Number JP2003293411
Inventor: Sugimoto Takeshi
Published: Oct. 15, 2003
PROBLEM TO BE SOLVED: To provide a water supply control device, enabling reduction of wrong sensing due to detection of others than the hand and detection of the hand during washing work during the operation of a rotary handle or a lever handle of a water faucet and to provide a water supply control device, preventing an increase in size of a top part of a spout, not impairing the appearance of the spout, and having good design. SOLUTION: This water supply control device has a capacitance detecting type sensor used as a detecting part having a human body detecting means, and includes an opening and closing valve unit for opening and closing a passage according to the input from the detecting part, a controller for controlling the opening and closing valve unit, and a discharge part for discharging liquid supplied by the opening and closing valve unit. As a detecting means of the capacitance detecting type sensor, a detecting electrode is exposed on the detecting surface.
Japan Patent Number JP2006193954
Inventor: Murase Yoichi et al.
Published: Jul. 27, 2006
PROBLEM TO BE SOLVED: To provide an automatic water-discharge controller capable of making precise water-discharge control by corresponding to the movement such as a forward movement of a hand to the water-discharge controller, a hand washing and a backward movement of the hand or the like of a user in the water discharge controller making use of an object sensor. SOLUTION: When water is not discharged, the first electromagnetic wave beam 23 is emitted to the first direction facilitating the detection of the forward movement of the hand 10 from a microwave motion-body sensor 22. When the forward movement of the hand 10 is detected by the first electromagnetic wave 23, the water discharge starts and, at the same time, the second electromagnetic wave beam 31 is emitted to the second direction facilitating the detection of the movement of scattering water 34 during the hand washing and having difficulty in making detection of a stream 30 naturally flowing out from a faucet 21. When the movement of the scattering water 34 can't be detected by the second electromagnetic wave beam 31, the water discharge stops.
International Patent Publication Number WO 2008/057630
Inventor: Kum Foong Boey
Published: May 15, 2008
A faucet control system comprises a valve apparatus, sensors or a touch panel to be activated by a user, and a controller that controls the valve apparatus. A first sensor may start fluid flow and a second sensor may alter the proportion of fluids delivered from two fluid sources. The sensors may be activated without being touched and may include infrared sensing elements. The touch panel may be activated with hand pressure and may include electrically conductive sheets. The touch panel may have a first portion for allowing fluid flow from a first fluid source, a second portion for allowing fluid flow from the first fluid source and a second fluid source, and a third portion for allowing fluid flow from the second fluid source. The controller may include an adjustable timer so that fluid flow can be stopped automatically after a selected period of time.
While these controls may be suitable for the purposes for which they were designed, they would not be as suitable for the purposes of the present invention, as hereinafter described.
SUMMARY OF THE PRESENT INVENTION
A primary object of the present invention is to provide a touchless water control system.
Another object of the present invention is to provide a touchless water control system for starting water flow from a faucet.
Yet another object of the present invention is to provide a touchless water control system for stopping water flow from a faucet.
Still yet another object of the present invention is to provide a touchless water control system for varying water temperature from a faucet.
An additional object of the present invention is to provide a touchless water control system for varying water pressure from a faucet.
A further object of the present invention is to provide a touchless water control system having at least one sensor spaced away from said faucet.
A yet further object of the present invention is to provide a touchless water control system wherein hand articulation relative to said one sensor enables control over the temperature and pressure dispensed from a faucet.
A still yet further object of the present invention is to provide a touchless water control system having at least two sensors spaced away from said faucet.
Another object of the present invention is to provide a touchless water control system wherein hand articulation relative to said two sensors enables control over the temperature and pressure of the water dispensed from a faucet.
Yet another object of the present invention is to provide a touchless water control system having at least two sensors spaced away from said faucet and angularly disposed to each other.
Still yet another object of the present invention is to provide a touchless water control system wherein hand articulation in both direction and time may control on and off of the water, temperature of the water and pressure of the water.
An additional object of the present invention is to provide a touchless water control system wherein tapping proximate the sensor turns the water on or off.
A further object of the present invention is to provide a touchless water control system wherein stationary objects within the sensor field does not affect the sensor(s).
A yet further object of the present invention is to provide a touchless water control system having sensors selected from the group of infrared, sonic and capacitance.
A still further object of the present invention is to provide a touchless water control system that is programmable to a desired set of functions.
Another object of the present invention is to provide a touchless water control system that can be selectively programmed wirelessly.
Additional objects of the present invention will appear as the description proceeds.
The present invention overcomes the shortcomings of the prior art by providing a touchless water control system having at least one sensor capable of determining hand movement and time in a first direction, hand movement and time in a second direction and hand movement and time in a third direction thereby establishing a spatial field spaced away from a faucet through which a user=s hand can be moved to initiate or terminate water flow, water temperature and water pressure.
The foregoing and other objects and advantages will appear from the description to follow. In the description reference is made to the accompanying drawings, which forms a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments will be described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. In the accompanying drawings, like reference characters designate the same or similar parts throughout the several views.
The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
In order that the invention may be more fully understood, it will now be described, by way of example, with reference to the accompanying drawing in which:
FIG. 1 is an illustrative perspective view of the present invention.
FIG. 2 is an illustrative view of the present invention.
FIG. 3 is a top view of the present invention.
FIG. 4 is a front view of the present invention.
FIG. 5 is a side view of the present invention.
FIG. 6 is a perspective illustrative view of the present invention in use.
FIG. 7 is a side view of the present invention in use.
FIG. 8 is a side view of the present invention in use.
FIG. 9 is a perspective illustrative view of the present invention.
FIG. 10 is a perspective illustrative view of the present invention in use.
FIG. 11 is a perspective illustrative view of the present invention.
FIG. 12 is a perspective illustrative view of the present invention in use.
FIG. 13 is an illustrative view of an additional element of the present invention.
DESCRIPTION OF THE REFERENCED NUMERALS
Turning now descriptively to the drawings, in which similar reference characters denote similar elements throughout the several views, the Figures illustrate the Spatially Reactive Water System of the present invention. With regard to the reference numerals used, the following numbering is used throughout the various drawing figures.
10 Spatially Reactive Fluid Control System of the present invention 12 faucet 14 sink 16 horizontal sensor 18 vertical sensor 20 moisture sensor 22 CPU 24 hot water 26 cold water 28 regulatory valves 30 back splash 32 water amount (pressure) 34 hot/cold (temperature) 36 user's hand 38 “X” displacement 40 “Y” displacement 42 “Z” displacement 44 lower pressure 46 raise pressure 48 decrease temperature 50 increase temperature 52 sweeping side motion 54 coplanar spaced apart sensors 56 left/right mixes hot and cold temperature 58 to solenoids and water supply 60 hand passing in any direction 62 single sensor 64 tap movement 66 height level 68 fluid source 70 to fluid outlet 72 programmable microprocessor 74 visual indicators
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following discussion describes in detail one embodiment of the invention (and several variations of that embodiment). This discussion should not be construed, however, as limiting the invention to those particular embodiments, practitioners skilled in the art will recognize numerous other embodiments as well. For definition of the complete scope of the invention, the reader is directed to appended claims.
Referring to FIG. 1 , shown is an illustrative perspective view of the present invention 10 . Typically when using a sink 14 there is provided at least one valve for initiating water flow, intensity of water flow, temperature of water being dispensed and water shut-off. All of which are controllable through use of the touchless control system of the present invention, which incorporates a pair of sensors 16 , 18 in electrical communication with actuators creating a three dimensional zone through which an operator moves their hand to control selection of the aforementioned functions typically controlled through proportion valves. The present invention's 10 control over a sink's 14 faucet 12 is determined by locational interpretation of the user's hand relative to a pair of perpendicularly disposed sensors 16 , 18 having associated regulatory valves 28 for hot 24 and cold 26 lines that work in unison to determine the user's relative position to the sensors 16 , 18 thereby controlling the turning on and off of water, setting of temperature and the amount of water pressure desired by the user.
Referring to FIG. 2 , shown is an illustrative view of the present invention 10 . The present invention 10 is a fluid dispensing control system for varying temperature and pressure at an outlet, such as a faucet 12 . Illustrated is one example of the present invention 10 where temperature and pressure are programmable regulated through locational interpretation of the user's hand relative to a pair of perpendicularly disposed motion sensors 16 , 18 . When installed the present invention's sensors 16 , 18 are visible or invisible to the human eye and utilize wave inference as a sensing medium. Utilizing this embodiment of the touchless system creates a more hygienic environment.
Referring to FIG. 3 , shown is a top view of the present invention 10 . Shown is a top view of the present invention 10 depicting how an area is set aside in the sink's 14 counter and back splash 30 for placement of both the vertical 18 and horizontal 16 sensing panels.
Referring to FIG. 4 , shown is a front view of the present invention 10 . Shown is a front view of the present invention 10 depicting an area set aside in the sink's 14 back splash and counter top for placement of both the vertical 18 and horizontal 16 sensing panels on either side or both sides of the dispensing faucet 12 . In which case left or right (sensor set) can be activated by entering the field at that point the other side will become inactive for that use.
Referring to FIG. 5 , shown is a side view of the present invention 10 . Shown is a side view of the present invention 10 depicting the arrangement of the vertical 18 and horizontal 16 sensors in relation to each other. The vertical sensor 18 senses up and down movement while the horizontal sensor 16 senses forward and backward motion. The sensors are depicted in a specific configuration for illustrative purposes to control water amount (pressure) 32 and hot or cold (temperature) 34 with their actual location more of a desired design aesthetics.
Referring to FIG. 6 , shown is a perspective illustrative view of the present invention 10 in use. Shown is the user's hand held over the sensing area of the present invention, movement of the user's hand 36 about the three axis of a three dimensional plane each determine a different function for the sink 14 to perform. Movement up and down the “Y” plane 40 controls the sinks 14 pressure, movement in forward and back on the “Z” plane 42 determines a hotter or colder temperature and movement in the “X” direction 38 enters a setting or command to turn off the faucet 12 .
Referring to FIG. 7 , shown is a side view of the present invention 10 in use. Shown is how when the user raises or lowers their hand 36 the water pressure is changed respectively 44 , 46 . In order to lower the water pressure 44 the user raises their hand, in order to raise the pressure 46 the user lowers their hand. To turn off the water the user pulls their hand away, sweeps hand through field or taps counter top. However different off methods can be changed depending on user specification.
Referring to FIG. 8 , shown is a side view of the present invention 10 in use. Shown is how when the user advances or retracts their hand 36 the water temperature is changed respectively 48 , 50 . In order to increase the water temperature 50 the user advances their hand, in order to lower the temperature 48 the user retracts their hand. When a desired setting is met the user sweeps their hand away to the side.
Referring to FIG. 9 , shown is a perspective illustrative view of the present invention 10 . Shown is the manner by which the user can decide on a preferred setting. After a preferred setting is reached the user can maintain said setting by simply sweeping their hand 36 horizontally 52 to either side. Turning off the device is achieved by touching the bottom sensor or sweeping hand across field 52 or pulling hand away from sensors.
Referring to FIG. 10 , shown is a perspective illustrative view of the present invention 10 in use. Shown is the user's hand held 36 over a pair of coplanar spaced apart sensors 54 comprising the sensing area, each sensor sensing movement in one direction causes a pressure change independent from the other while movement through another direction 56 causes mixing of the hot and cold water to a desired temperature.
Referring to FIG. 11 , shown is a perspective illustrative view of the present invention 10 . Shown is at least one sensor for controlling a fluid flow through a faucet by passing a hand through a sensor defined field through any direction 60 that may also include time duration for initiating and terminating fluid flow and for controlling temperature and pressure of the flow. Also shown is a moisture sensor 20 which allows the system to compensate for moisture levels in air and surfaces.
Referring to FIG. 12 , shown is a perspective illustrative view of the present invention 10 in use. Shown is the user's hand 36 held over the single sensor 62 that will control temperature and pressure through the number of taps 64 upon the sensor 62 and the duration between the taps 64 . Additional adjustment for pressure or hot and cold water can be made utilizing a combination of taps 64 for one setting and height adjustment for the other.
Referring to FIG. 13 , shown is an illustrative view of an additional element of the present invention 10 . Shown is the present invention 10 having a plurality of optional visual indicator displays 74 whereby the temperature or pressure of the water may be presented to the user visually by either graphics, bars, charts or numerically.
It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of devices differing from the type described above.
While certain novel features of this invention have been shown and described and are pointed out in the annexed claims, it is not intended to be limited to the details above, since it will be understood that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | A touchless water control system having at least one sensor capable of determining hand movement from point A to point B in a first direction, from point C to point D in a second direction and from point E to point F in a third direction thereby establishing a spatial field spaced away from a faucet through which a user's hand can be moved to initiate or terminate water flow, water temperature and water pressure. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to pulsed laser diodes. More specifically, but without limitation thereto, the present invention relates to driving a laser diode with a resonant electrical circuit formed by an impedance mismatch at each end of a transmission line connecting an impulse generator to the laser diode.
High energy optical pulses are widely used in applications such as optical fiber communications, optoelectronic sampling, optical clocking of logic circuits, and photonic switching. The generation of picosecond optical pulses at high pulse repetition frequencies from laser diodes has received much interest in recent years because the laser diodes are much smaller, less expensive, more reliable, and more efficient than gas lasers, and because of the variety of applications in optical signal processing and optical fiber communication systems. The majority of research in this area has centered on using active optical mode locking schemes. These schemes employ electrical modulation and utilize an optical resonant cavity, generally an external resonant cavity, although more sophisticated setups utilize a monolithic cavity structure. Passive optical mode locking schemes have also been studied. These schemes typically use a saturable absorber which results in a device that self resonates. Some of the drawbacks of these optical mode locking schemes are their complexity, and their sensitivity to mechanical vibration. Methods utilizing gain switching have also been studied. These methods have the advantage of being simple, but with the drawbacks of longer pulse width, less optical pulse power, and smaller on-off ratio than mode locking schemes.
Both mode-locking and gain-switching are commonly used to generate pulses having pulse widths in the picosecond range. The limitation on mode-locking of conventional laser diodes having a typical cavity length in the 300 μm range is low pulse energy. The pulse energy of these laser diodes is approximately 1 pJ, although high energy pulses of about 50 pJ before compression were reported recently by A. Azouz et al from mode-locking a laser diode having a 2000 μm cavity (A. Azouz, N. Stelmakh, P. Langlois, J-M Lourtioz, and P. Gavrilovic, "Nonlinear Chirp Compensation in High-power Broad-spectrum Pulses from Single-stripe Mode-locked Laser Diodes", IEEE Journal of Selected Topics in Quantum Electronics, vol. 1, pp. 577-582, 1995). However, mode-locking suffers from the complexity of an external cavity. Compared to mode-locking, gain-switching is simpler, more compact, and more reliable for generating high energy pulses having a duration in the range of about 10 picoseconds. Current gain-switching techniques, however, suffer the disadvantages of longer pulse widths, lower optical power, and a smaller on-off ratio than mode-locking provides. A need thus continues to exist for a circuit for driving laser diodes that combines the advantages of gain-switching and mode-locking in an inexpensive, compact, reliable laser diode circuit to produce optical pulses having a narrow pulse width, high energy, low jitter, and high extinction ratio.
SUMMARY OF THE INVENTION
A resonant driving circuit for a laser diode of the present invention is directed to overcoming the problems described above, and may provide further related advantages. No embodiment of the present invention described herein shall preclude other embodiments or advantages that may exist or become obvious to those skilled in the art.
A resonant driving circuit for a laser diode of the present invention comprises an impulse generator for generating narrow output pulses, a delay line for generating a composite output of reflections of the output pulses from terminations of the transmission line, a laser diode for generating an optical output from the composite output, and a forward bias network to bias the laser diode.
Two advantages of the resonant driving circuit of the present invention are that optical pulses may be generated having high power and narrow pulse width.
Another advantage is that optical pulses may be generated that have low phase jitter.
Yet another advantage is that a higher on-off ratio may be obtained than with presently available gain-switched circuits.
Other advantages are that the resonant driving circuit of the present invention is simple, reliable, and inexpensive.
The features and advantages summarized above in addition to other aspects of the present invention will become more apparent from the description, presented in conjunction with the following drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an electrical schematic of a gain-switched laser diode circuit of the present invention.
FIG. 2A is an oscilloscope trace of the drive signal pulses measured at the output of the step recovery diode.
FIG. 2B is an oscilloscope trace of the response of a Schottky photodiode to the optical output of the laser diode.
DESCRIPTION OF THE INVENTION
The following description is presented solely for the purpose of disclosing how the present invention may be made and used. The scope of the invention is defined by the claims.
In FIG. 1 a resonant driving circuit 10 comprises a laser diode 102, a forward bias network 104, a delay line 106, and an impulse generator 110. Impulse generator 110 comprises a drive signal source 190, a step recovery diode 108, and a reverse bias network 112 to bias step recovery diode 108. Laser diode 102 may be, for example, a GaAlAs gain-guided, tapered stripe laser available commercially as Sony part no. 202V-3. The Sony 202V-3 has a typical threshold current of 80 mA, a length of about 250 μm, and supports stable single-mode near field and single-lobe far field patterns at 50 mw of cw optical power output.
Forward bias network 104 may be, for example, a DC blocking capacitor 124, an RF choke 120 and an RF bypass capacitor 122. A forward bias current 150 of, by way of example, 118 mA may be introduced into bias network 104 at forward bias input 126 by a current source 194 to bias laser diode 102 well above the laser threshold current, thereby minimizing the power required from drive signal 195. DC blocking capacitor 124 isolates step recovery diode 108 from forward bias current 150. RF choke 120 and RF bypass capacitor 122 isolate forward bias input 126 from drive signal 180.
Reverse bias network 112 may be, for example, a DC blocking capacitor 134, an RF choke 130, and an RF bypass capacitor 132. A reverse bias voltage 170 of, for example, 1.1 V may be applied to step recovery diode 108 at reverse bias input 136 by a voltage source 192. DC blocking capacitor 134 isolates drive signal input 138 from reverse bias voltage 170. RF choke 130 and RF bypass capacitor 132 isolate reverse bias input 136 from drive signal 195.
Drive signal 195 may be, for example, a sine wave having a frequency of about 1.2 GHz and a power level of about 1.1W generated by a drive signal source 190. Impulse generator 110 may be implemented, for example, by a Hewlett-Packard 2645A drive signal source 190, a Hewlett-Packard 33005C step recovery diode 108, and a biasing network 112 providing an appropriate DC voltage 170 to present an output impedance of about 30 ohms.
Delay line 106 may be, for example, a variable length of 50 ohm transmission line. If laser diode 102 is biased to present an input impedance of about 4 ohms, the circuit between step recovery diode output 180 and laser diode 102 may be approximated as a 50-ohm transmission line terminated by a short circuit at each end. According to basic transmission line theory, the reflection of a pulse traveling down a transmission line will be inverted if the transmission line is terminated by a short circuit. This principle may be used to create a resonant cavity as follows. If a pulse output from impulse generator 110 is inverted upon reflection at laser diode 102 and inverted again upon reflection at impulse generator 110, the time delay of delay line 106 may be adjusted to cause the reflected pulses to constructively interfere with pulses in step recovery diode output 180, thereby increasing the peak power and minimizing pulse spreading. The time delay of delay line 106 may be adjusted according to the formula fp=V/2L, where fp is the desired pulse repetition frequency, v is the velocity of the pulse in delay line 106, and L is the length of delay line 106. The pulse width may be varied by adjusting the DC bias current to the HP 33005C impulse generator.
FIG. 2A is an oscilloscope trace of a typical drive signal pulse measured at the output of step recovery diode 108. FIG. 2B is an oscilloscope trace of the response of a Schottky photodiode to the optical output of laser diode 102. Typical circuit performance results are an optical energy pulse of 59 pJ, an extinction (on-off) ratio of 800, a phase jitter of 250 fs, and a Full Width at Half Maximum (FWHM) of 14.5 ps. This is believed to be the highest energy reported for a short (250 μm) single stripe laser diode and is comparable to that of a 2000 μm laser diode. These unusual results are believed to be attributable to the stable single-mode near field pattern, single-lobe far field pattern, and multi-longitudinal modes associated with the tapered stripe laser diode under high driving current pulses. The current pulses are believed to be enhanced by electrical resonance resulting from the reflection at the impedance mismatch between laser diode 102 in FIG. 1 and delay line 106, and the reflection at the impedance mismatch between delay line 106 and impulse generator 110. The resonance may be optimized by adjusting the length of delay line 106.
Light output 142 emitted by laser diode 102 may be coupled into an optical device 152 for use in other applications. Examples of optical devices 152 are optical focusing systems, optical communications systems, optoelectronic sampling circuits, optoelectronic logic clocking circuits, optoelectronic multiplexers, and photonic switches, which may include optical fibers, photodiodes and other optoelectronic coupling devices.
Other modifications, variations, and applications of the present invention may be made in accordance with the above teachings other than as specifically described to practice the invention within the scope of the following claims. | A resonant driving circuit for a laser diode comprises an impulse generator for generating narrow output pulses, a delay line for generating a composite output of reflections of the output pulses from terminations of the transmission line, a laser diode for generating an optical output from the composite output, and a forward bias network to bias the laser diode. | 7 |
TECHNICAL FIELD
[0001] The present invention relates to a method and arrangement for controlling speed of a media played on a device having a touch-screen.
BACKGROUND
[0002] Hand held devices, such as mobile phones, digital cameras, and pocket computers with graphical user interfaces have become increasingly popular in recent years. The most common example of a pocket computer is a smart phone, which may be embodied in various different forms.
[0003] Commonly hand held devices are also provided with play functionality for playing recorded video and audio. The graphical display is typically touch-sensitive and may be operated by way of a pointing tool such as a stylus, pen or a user's finger. Other devices rely more on a touch-sensitive display as the main input device and may thus have dispensed with a hardware keyboard.
[0004] The hand held device used as mobile terminals, i.e. in addition to providing typical pocket computer services such as calendar, word processing and games, they may also be used in conjunction with a mobile telecommunications system for services like voice calls, fax transmissions, electronic messaging, Internet browsing, etc. It is well known in the field that because of the noticeably limited resources of pocket computers, in terms of physical size, display size, data processing power and input device, compared to laptop or desktop computers, user interface solutions known from laptop or desktop computers are generally not applicable or relevant for pocket computers. One example is controlling play functionality, e.g. fast forward play/rewind of a content using a point device.
[0005] In devices having touch-sensitive screen, a so-called “progress bar” is used to visually indicate the progress of a lengthy operation or browsing media. The progress bar may be one of a number of styles, for example:
Segmented blocks that increase in steps from left to right. A continuous bar that fills in from left to right. A block that scrolls across a progress bar in a marquee fashion
[0009] In short, a progress bar is a component in a graphical user interface used to convey a degree of progress of a (e.g., computing) task, such as a download or file transfer, audio, or video play progress. The graphic may be accompanied by a textual representation of the progress in a percent format.
[0010] When a user watches or listens to a relatively lengthy media file and wants to move to another location on the media, the progress bar may be used. In a touch-screen interface the user can often press the active progress-bar position and then move to a new position, which effects the media corresponding to the new position. The problem is that the length of the progress bar is usually scaled to correspond to the total length of the media file (1:1 relation). If the user is watching or listening to a relatively lengthy media file, e.g., audio files or movies, a small position change of the finger, on the progress bar, results in big change in the corresponding time position in the media. Thus, it is problematic to make precise changes, within the media content, using a progress bar that is “to scale.”
SUMMARY
[0011] One embodiment of the present invention provides means for controlling media with more accuracy and ability to fine tune fast forward and/or rewind of the media file.
[0012] For these and other reasons, a method of controlling reproduction speed of a media on a device, which comprises a touch sensitive screen. In a first operative mode a reproduction speed control signal is generated by displacing a pointing means on said touch sensitive screen, said displacement of said pointing means being responsive of a changing of said reproduction speed of the media with a first ratio relative said displacement. The method comprises setting a second mode in which, said displacement of said pointing means is responsive of a changing of said reproduction speed of the media with a second ratio relative said displacement. The second mode is initiated by a user, media or automatically.
[0013] The ratio may be Δt=n×Δd, wherein Δd is the displacement distance of the pointing means on the touch sensitive screen, Δt is the change of time in the media corresponding to said speed and n is a factor for changing the ratio between pointing means movement and rate of speed of the media. The displacement is applied on an active area, which is configured as a progress bar and related to a media length and used to control media reproduction. The reproduction speed of the media with a second ratio relative said displacement is set when moving said pointing means in direction deviating from said movement of the pointing means on said touch sensitive screen. According to one embodiment, the active area is a progress bar related to a media length and used to control media reproduction and the second rate of speed is set when moving a pointing means in a direction deviating from said movement of the pointing means on said touch sensitive screen and a distance between said progress bar and a point of contact between said pointing means and the touch sensitive screen changes said second ratio. The reproduction speed may be one of fast forwarding or rewinding of said media.
[0014] The invention also relates to a device including a touch sensitive screen, a memory for storing a media, and a first control unit for controlling said screen, a second control unit for reproducing said media on said touch sensitive screen. The second control unit is configured to in a first operative mode to set a reproduction speed control signal generated due to displacement of a pointing means on said touch sensitive screen, said displacement of said pointing means being responsive of a changing of said reproduction speed of the media with a first ratio relative said displacement, and to set a second mode in which, said displacement of said pointing means is responsive of a changing of said reproduction speed of the media with a second ratio relative said displacement. The device may be one of a mobile terminal, telephone, a digital media player, a camera, a personal digital assistant (PDA), a computer or a device with content displaying and touch screen capability. The media may be audio and/or video media. The reproduction speed is fast forwarding or rewinding of said media. The media may represent content accessed from an external device. The second mode is initiated by a user, the media, or automatically.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Reference is made to the attached drawings, in which elements having the same reference number designation may represent like elements throughout.
[0016] FIG. 1 is a diagram of an exemplary system in which methods and systems described herein may be implemented;
[0017] FIG. 2 illustrates a schematic view of a user interface according to an embodiment of the invention,
[0018] FIG. 3 is a flow diagram illustrating exemplary processing by the system of FIG. 1 ,
[0019] FIGS. 4 a to 4 e illustrate the operation of a user interface according to an embodiment of the present invention,
[0020] FIGS. 4 a to 4 c illustrate schematically technical aspects according to an embodiment of the present invention, and
[0021] FIG. 6 illustrates schematically a communication device according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0022] The following detailed description refers to the accompanying drawings. The same reference numbers in different drawings may identify the same or similar elements.
[0023] The term “image,” as used herein, may refer to a digital or an analog representation of visual information (e.g., a picture, a video, a photograph, animations, etc).
[0024] The term “audio” as used herein, may include may refer to a digital or an analog representation of audio information (e.g., a recorded voice, a song, an audio book, etc).
[0025] Also, the following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims and equivalents.
[0026] FIG. 1 is a diagram of an exemplary system 100 in which methods and systems described herein may be implemented. System 100 may include a bus 110 , a processor 120 , a memory 130 , a read only memory (ROM) 140 , a storage device 150 , an input device 160 , an output device 170 , and a communication interface 180 . Bus 110 permits communication among the components of system 100 . System 100 may also include one or more power supplies (not shown). One skilled in the art would recognize that system 100 may be configured in a number of other ways and may include other or different elements.
[0027] Processor 120 may include any type of processor or microprocessor that interprets and executes instructions. Processor 120 may also include logic that is able to decode media files, such as audio files, video files, multimedia files, image files, video games, etc., and generate output to, for example, a speaker, a display, etc. Memory 130 may include a random access memory (RAM) or another dynamic storage device that stores information and instructions for execution by processor 120 . Memory 130 may also be used to store temporary variables or other intermediate information during execution of instructions by processor 120 .
[0028] ROM 140 may include a conventional ROM device and/or another static storage device that stores static information and instructions for processor 120 . Storage device 150 may include a magnetic disk or optical disk and its corresponding drive and/or some other type of magnetic or optical recording medium and its corresponding drive for storing information and instructions. Storage device 150 may also include a flash memory (e.g., an electrically erasable programmable read only memory (EEPROM)) device for storing information and instructions.
[0029] Input device 160 may include one or more conventional mechanisms that permit a user to input information to the system 100 , such as a keyboard, a keypad, a directional pad, a mouse, a pen, voice recognition, a touch-screen and/or biometric mechanisms, etc. Output device 170 may include one or more conventional mechanisms that output information to the user, including a display, a printer, one or more speakers, etc. Communication interface 180 may include any transceiver-like mechanism that enables system 100 to communicate with other devices and/or systems. For example, communication interface 180 may include a modem or an Ethernet interface to a LAN. Alternatively, or additionally, communication interface 180 may include other mechanisms for communicating via a network, such as a wireless network. For example, communication interface may include a radio frequency (RF) transmitter and receiver and one or more antennas for transmitting and receiving RF data.
[0030] System 100 , consistent with the invention, provides a platform through which a user may play and/or view various media, such as music files, video files, image files, games, multimedia files, etc. System 100 may also display information associated with the media played and/or viewed by a user of system 100 in a graphical format, as described in detail below. According to an exemplary implementation, system 100 may perform various processes in response to processor 120 executing sequences of instructions contained in memory 130 . Such instructions may be read into memory 130 from another computer-readable medium, such as storage device 150 , or from a separate device via communication interface 180 . It should be understood that a computer-readable medium may include one or more memory devices or carrier waves. Execution of the sequences of instructions contained in memory 130 causes processor 120 to perform the acts that will be described hereafter. In alternative embodiments, hard-wired circuitry may be used in place of or in combination with software instructions to implement aspects consistent with the invention. Thus, the invention is not limited to any specific combination of hardware circuitry and software.
[0031] FIG. 2 illustrates a graphical touch-sensitive display 160 . Display 160 may include a general purpose display and may be programmed to display content stored in a memory (not shown) associated with the display. Display 160 , according to this example, may be configured to show a video, and thus comprises a screen such as video area 161 for rendering or reproducing the video. In an application for playing an audio content, video area 161 may be used for displaying, for example, one or more still images, a slide show, and/or other graphic images, for example, associated with the playing of the audio content.
[0032] Information about the content displayed (or played) may be displayed in an information area 162 and/or video area 161 , for example, comprising a title of the video and scene no. or any other relevant information. In case of audio media, e.g., name of artist, album, song etc. may be displayed, for example, in an information area 162 and/or video area 161 .
[0033] Display 160 may further include a visual progress bar 163 , in this case configured as an oblong slide bar in the base portion of display 160 . Bar 163 may also be arranged in side portions or upper portion (also in mid-portion if not obstructing the content play) of display 160 . Bar 163 may be provided with a displaceable indicator, such as a slidable knob 164 which may have at least two functions: showing the progress of the media played and/or initiating fast forward/rewind play of the displayed media.
[0034] Field 165 may be functionally connected to knob 164 and move together with knob 164 in one or more directions. Screen field 165 may be configured to provide information about, for example, the elapsed time and/or remaining time of the displayed media. Further control buttons 166 may be arranged for media play control, such as rewinds, play/pause, fast forward, scene selection, etc. Display 160 may also include additional control buttons 167 .
[0035] Display 160 may be controlled with a driver circuit (not shown) or processor 120 . All buttons and bars may be programmed to be visualized via display 160 and the input in form of screen touch is input to the driver (or a special dedicated circuit) and processor 120 .
[0036] Thus, display 160 , using preprogrammed control buttons controls the media play. For example, if play/pause button 166 is touched (i.e., activated), a selected media (stopped or paused) begins playing. Information about the media, such as title, may be displayed in the information area 162 . While the media is playing, a user may fast forward, rewind, and/or otherwise change the current play position of the media by means of slidable knob 164 .
[0037] According to the invention a play position point resolution (precision) increasing/decreasing function is introduced, for example, when the progress bar movement mode has been activated. When a user uses a pointing means (e.g., finger or a pointing device, such as stylus) to manipulate progress bar knob 164 , bar knob 164 can be moved in a horizontal direction (along a length of progress bar 163 ) with a (substantially) 1:1 relation with respect to progress bar 163 , but if the user moves the pointing means, alternatively, to move bar knob 164 upwards or a direction other than horizontal (with respect to the length of progress bar 163 ), the area that the horizontal movement is mapped towards decreases (<1:1 relation). The user may thus fine tune (e.g., search a particular play point in the media with greater precision), for example, a current play point of the media, by moving the pointing means upwards (or other direction than horizontal). If the user moves the pointing means towards the bottom (or an opposite direction of the non horizontal direction) the progress bar resolution (precision) increases towards (i.e., returns to) 1:1 relation.
[0038] Of course, the horizontal and other directions mentioned above are given as examples and the directions depend on the position of the progress bar. If the progress bar is arranged on the side portion of the screen, the (normal speed) forward and rewind may be controlled by moving the knob up and down (vertical movement along a length of the progress bar) and the fine tuning will be achieved by a non-vertical, e.g. horizontal, movement. The progress bar may be circular or have another regular or irregular shape.
[0039] Thus, according to an embodiment of the invention and with reference to FIG. 3 , processor may receive information from the touch-screen or the driver circuit that is actuated ( 301 ). The positioning of the touched point is assumed to be well known to a skilled person and not described in here in more detail. If it is determined that progress bar 163 is touched the direction is determined ( 302 ) and based on the determined direction the speed resolution is set ( 303 ).
[0040] FIGS. 4 a to 4 e illustrate the display of FIG. 2 in operation. In FIG. 4 a , play of a particular media is initiated. The information area shows the elapsed time of the media, i.e., 43:50. Box 168 to the right of the drawing illustrates a corresponding 1:1 (media content search) relation. When the user moves a pointing device (finger, stylus, or the like) in progress bar 163 horizontally, the length of progress bar 163 corresponds to the media that is being played. For example, if the media is 88 minutes long, the user moves the pointing device to be positioned in the middle of progress bar 163 area, the time elapsed should indicate just above 40 min. If accurate, it should be (approximately) 44 minutes.
[0041] In FIG. 4 b , the media content is fast forwarded to (a time) 66:50. The encircled area 169 illustrates the screen touch by a pointing device, not shown. Box 168 , to the right, is still in 1:1 (media content search) relation. When the user positions the pointing device on progress bar 163 , the time information increases to indicate that by moving the pointing device the user will alter the position of the media that is being played. The device may be configured to have an altering or active mode, in which the non-horizontal movement is sensed and affects the media play. This mode may be started automatically or initiated by the user or may be media dependent. When the user stops influencing progress bar 163 , progress bar 163 may return to a passive mode, for example, indicating playing of the media content corresponding to a current play point. The active or passive modes may also be initiated by the user, for example, by tapping on the screen or chosen in a property setting menu, etc.
[0042] In FIG. 4 c the pointing means is displaced vertically, in this case perpendicular to progress bar 163 . Time played is still indicated as (time) 66:50. The processor now is informed that the fine tuning procedure is activated and sets the fast forwarding function to a relation other than 1:1 illustrated by an area 167 . For example, if 10 pixels movement of the pointing means on the screen corresponded to 10 minutes of fast forwarding, the relation is changed, e.g., such that the displacement in vertical direction will reduce the fast forwarding to 5 minutes (corresponding to 10 pixels movement of the pointing means), depending on the vertical distance.
[0043] In FIG. 4 d , the pointing means is moved horizontally and due to the changed relation a slower fast forward is achieved, which may be shown in information area 162 .
[0044] In FIG. 4 e the pointing means is again displaced vertically and the fast forwarding relation is reduced further, corresponding to more precise (i.e., slower) fast forwarding.
[0045] In FIGS. 4 a - 4 e, if the resolution direction is changed, i.e. the pointing means is moved downwards, the resolution (media content search precision) will decrease. With resolution direction is meant the predetermined direction to increase or decrease the fast forwarding/rewinding resolution of the presented media.
[0046] FIGS. 5 a - 5 c illustrates schematically one technical aspect of the present invention. The touch sensitive screen may be, for example one of a resistive, capacitive, surface acoustic wave, infrared, optical imaging, strain gauge, optical imaging, dispersive signal technology, acoustic pulse recognition or any other suitable type of touch screen. The operation of a touch screen is assumed well known by a skilled person and not disclosed in detail herein.
[0047] In FIGS. 5 a - 5 c, a touch sensing element is denoted with 590 . A touch screen may include a huge number of sensing elements in rows and columns. Here, only a small number of elements in a row are illustrated. To simplify the description, irrespective of the type of the touch screen, the touch screen is simplified comprising touch sensing elements.
[0048] In operation, with respect to operation of a progress bar, when a pointing device is displaced on the touch sensitive screen, such that a certain displacement Δd, corresponding to displacement of the knob 164 , is sensed, it is interpreted to a fast forward or rewind of the media stream. The fast forward or rewind is with respect to a play time. Thus, Δd displacement of the knob corresponds to Δt fast forward/rewind of the media stream. For example, in FIG. 5 a , one Δd may correspond to Δt (e.g. 1 sec), i.e. ratio of 1:1.
[0049] Applying the present invention on the examples of FIGS. 5 a - 5 c, when the time resolution change mode (active mode) is activated, e.g., by moving the pointing device vertically, a horizontal Δd′(=2×Δd) according to FIG. 5 b corresponds to one Δt, i.e., a ratio of 2:1. In this case the pointing device must move twice the distance, according to FIG. 5 a , to move one (1) time unit (e.g., 1 sec.) within the media content. Thus, a parameter n may be set to control the ratio between the movement and the time, i.e., Δd=n×Δt or n×Δd=Δt, where n is a number.
[0050] In FIG. 5 c , another ratio is used: a horizontal Δd according to FIG. 5 c corresponds to one Δt′, where Δt′ is e.g., 2 Δt, i.e., ratio of 2:1. In this case the movement of the pointing device corresponds to a two (2) time unit movement within the media content.
[0051] Of course, all ratios and directions are given as examples; others may be selected, for example, by a user of the device. The terms “fast forward (play)” and “rewind” as used in this specification refer to “playing” (e.g., advancing) within the media content in a speed (e.g., at a rate) other than a normal play (e.g., viewing) speed.
[0052] FIG. 6 illustrates a communication device 650 incorporating the present invention. Device 650 may include processor 120 , memory 130 , read only memory (ROM) 140 , storage device 150 , input device 160 , an output device 170 , communication interface 180 , and antenna 181 . The function of varying parts has been described in conjunction with FIG. 1 . Antenna 181 may receive and/or transmit radio signals. Device 650 may also include an ear piece/loudspeaker 651 , a microphone 652 , and physical control keys 653 .
[0053] Device 650 may further include graphical touch-sensitive display 160 , including screen area 161 , information area 162 , visual progress bar 163 provided with slidable knob 164 and control buttons 167 . The function of display 160 is described in conjunction with FIG. 2 .
[0054] Further, while series of acts have been described with respect to FIG. 3 , the order of the acts may be varied in other implementations consistent with the invention. Moreover, non-dependent acts may be performed in parallel.
[0055] It will also be apparent to one of ordinary skill in the art that aspects of the invention, as described above, may be implemented in any device/system capable of displaying a content using a touch sensitive screen.
[0056] The graphical representations provided to a user may represent content retrieved locally from system 100 . In some implementations, the content may represent content accessed from an external device, such as a server accessible to system 100 via, for example, a network, and streamed to the device, for example, such that the program bar corresponds to a buffered segment or portion of the streamed content. Embodiments of the invention provide for a selected precision with respect to queuing media content to a particular presentation point corresponding to a time parameter associated with a length of the media content. Embodiments of the invention provide an effectively expanded progress bar to the user to allow the user to make incremental movements, on the progress bar (thus within the media content) to a greater degree (i.e., with more precision) than with a progress bar presented in a 1:1 scale. Thus, a user can “jump” to particular points within the media content by scrolling along a locally-expanded progress bar that is presented to the user, a magnitude of which may be selected by the user based on a particular distance from the primary progress bar. The secondary bar can be a selected distance from and substantially parallel to the primary progress bar. In one embodiment, the original indicator may continue to be shown on the primary bar and another indicator may be presented in connection with the secondary progress bar, and movements of the two progress bars may track together and be shown, to the extent that the movement can be discerned on the primary progress bar.
[0057] For example, in the implementation described above with respect to FIGS. 1-6 , aspects of the invention may be implemented in a mobile terminal/telephone, such as a cellular telephone. In addition, aspects of the invention may be implemented in a digital media player, a camera, a personal digital assistant (PDA), a computer, or any other device with content displaying and touch screen capability. Aspects of the invention may also be implemented in methods and/or computer program products. Accordingly, the invention may be embodied in hardware and/or in software (including firmware, resident software, micro-code, etc.). Furthermore, the invention may take the form of a computer program product on a computer-usable or computer-readable storage medium having computer-usable or computer-readable program code embodied in the medium for use by or in connection with an instruction execution system. The actual software code or specialized control hardware used to implement aspects consistent with the principles of the invention is not limiting of the invention. Thus, the operation and behavior of the aspects were described without reference to the specific software code—it being understood that one of ordinary skill in the art would be able to design software and control hardware to implement the aspects based on the description herein.
[0058] Further, certain portions of the invention may be implemented as “logic” that performs one or more functions. This logic may include hardware, such as a processor, a microprocessor, an application specific integrated circuit or a field programmable gate array, software, or a combination of hardware and software.
[0059] It should be emphasized that the terms “includes/including” and “comprises/comprising” when used in this specification, are taken to specify the presence of stated features, integers, steps, or components, but does not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.
[0060] No element, act, or instruction used in the description of the present application should be construed as critical or essential to the invention unless explicitly described as such. Also, as used herein, the article “a” is intended to include one or more items. Where only one item is intended, the term “one” or similar language is used. Further, the phrase “based on,” as used herein is intended to mean “based, at least in part, on” unless explicitly stated otherwise.
[0061] The scope of the invention is defined by the appended claims and their equivalents. | A method and arrangement for controlling reproduction speed of media on a device is provided. A touch sensitive screen, wherein in a first operative mode a reproduction speed control signal is generated by displacing a pointing means on the touch sensitive screen, the displacement of the pointing means being responsive to a change in the reproduction speed of the media with a first ratio relative the displacement, the method including setting a second mode in which, the displacement of the pointing means is responsive to a change in the reproduction speed of the media with a second ratio relative the displacement. | 6 |
FIELD OF THE INVENTION
The field of the invention is subterranean tools that deploy by swelling and more particularly construction details and techniques that accelerate the swelling rate for faster deployment.
BACKGROUND OF THE INVENTION
Packers made of an element that swells in oil or water have been in use for some time as evidenced by U.S. Pat. Nos. 7,997,338; 7,562,704; 7,441,596; 7,552,768; 7,681,653; 7,730,940 and 7,597,152. These designs focus on construction techniques for faster deployment, mechanical compression assists to the swelling or enhancing the performance of an inflatable using an internal swelling material to enhance the seal, elimination of leak paths along the mandrel after swelling and running conduits through the swelling sealing element and still having a good seal.
Shape conforming screens that take the shape of open hole and act as screens have been disclosed using shape memory foam that is taken above its transition temperature so that the shape reverts to an original shape which is bigger than the surrounding open hole. This allows the foam to take the borehole shape and act effectively as a subterranean screen. Some examples of this are U.S. Pat. Nos. 7,013,979; 7,318,481 and 7,644,773. The foam used heat from surrounding wellbore fluids to cross its transition temperature and revert to a shape that let it conform to the borehole shape.
One problem with swelling materials is that the swelling rate can be very slow and that effective deployment requires the swelling to complete to a particular degree before subsequent tasks can commence at the subterranean location. What is known is that if there is more heat that the swelling to the desired configuration, so that subsequent operations can commence, can happen sooner rather than later. Since time has an associated cost, it has been an object to accelerate the swelling or reverting to a former shape process, depending on the material involved.
Various techniques have added heat with heaters run in on wireline or embedded in the packer itself and triggered from a surface location, or have used the heat from well fluid at the deployment location, or heat from a reaction to chemicals pumped to the deployment location, or induction heating of shape memory metals. Some examples are: U.S. Publication 2010/0181080; U.S. Pat. No. 7,703,539; U.S. Publication 2008/0264647; U.S. Publication 2009/0151957; U.S. Pat. No. 7,703,539; U.S. Pat. No. 7,152,657; U.S. Publication 2009/0159278; U.S. Pat. No. 4,515,213; U.S. Pat. No. 3,716,101; U.S. Publication 2007/0137826; CN2,078,793 U (steam injection to accelerate swelling); and U.S. Publication 2009/0223678. Other references have isolated reactants and a catalyst in composite tubulars that have not been polymerized so they are soft so that they can be coiled for deployment and upon deployment expansion of the tubular allows the reaction to take place to make the tubular string rigid. This is illustrated in U.S. Pat. No. 7,104,317.
Bringing together discrete materials downhole for a reaction between them is illustrated in U.S. Pat. No. 5,582,251.
The present invention seeks to accelerate swelling in packers and screens made of swelling material by a variety of techniques. One way is to embed reactants and, if necessary, a catalyst in the swelling material and allow the reaction to take place at the desired location to speed the swelling to conclusion. This generally involves a removal of a barrier between or among the reactants in a variety of ways to get the exothermic reaction going. Various techniques of barrier removal are described. The heat is given off internally to the swelling member where it can have the most direct effect at a lower installed cost.
Another heat addition alternative involves addition of metallic, preferably ferromagnetic particles or electrically conductive resins or polymers in the swelling material. Induction heating is used to generate heat at the particles or resin or polymer to again apply the heat within the element while taking up no space that is of any consequence to affect the ability of the packer to seal when swelling or the screen to exclude particles when the screen is against the borehole wall in an open hole, for example. Optionally the mandrel can be dielectric such as a composite material so that the bulk of the heating is the particles alone. Otherwise the mandrel itself can also be heated and transfer heat to the surrounding element. Induction heating of pipe is known for transfer of heat to surrounding cement as discussed in U.S. Pat. No. 6,926,083 but the rate of heat transfer is very much dependent on a temperature gradient from the pipe into the cement and is less effective than inductively heating the object that needs the heat directly as proposed by the present invention. Also relevant is U.S. Pat. No. 6,285,014 which heats casing with an induction heater lowered into the casing with the idea that the heated casing will transfer heat to the surrounding viscous oil and reduce its viscosity so that it can flow.
Those skilled in the art will better appreciate additional aspects of the invention by a review of the detailed description of the preferred embodiments and the associated drawings while recognizing that the full scope of the invention is to be determined by the appended claims.
SUMMARY OF THE INVENTION
The swelling rate of a swelling packer element or a conforming foam screen material is accelerated with heat. In one variation reactants that create an exothermic reaction plus a catalyst, if needed, are allowed to come into contact upon placement at the desired location. In another technique metallic, preferably ferromagnetic, particles or electrically conductive resins or polymers are interspersed in the swelling material and heat is generated at the particles by an inductive heater. A dielectric mandrel or base pipe can be used to focus the heating effect on the ferromagnetic particles or the electrically conductive resins or polymers in the sealing element or swelling foam screen element to focus the heating there without heating the base pipe. The heat accelerates the swelling process and cuts the time to when the next operation can commence downhole.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of the embodiment where the reactants are held apart until they are allowed to mix and react to cause a release of heat to accelerate the swelling of the element; and
FIG. 2 is a schematic illustration of an alternative embodiment using ferromagnetic particles or the electrically conductive resins or polymers in the element and induction heating to accelerate swelling in the element;
FIG. 3 shows the barrier between reactants broken with a shifting sleeve extending a knife;
FIG. 4 illustrates the use of a sliding sleeve to move a protective anode out of contact with a barrier and bring a cathode into barrier contact to accelerate barrier degradation and the onset of the exothermic reaction;
FIG. 5 illustrates the use of a corrodible conductive barrier whose failure is accelerated with inductive heating.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 , the mandrel 1 supports an element 2 that can be a swelling packer element or a porous screen material that swells. In either case the objective is to speed up the swelling process with the addition of heat so that the next operation at the subterranean location can take place without having to wait a long time for the swelling to have progressed to an acceptable level. FIG. 1 illustrates heat added directly into the element 2 as opposed to indirect ways that depend on thermal gradients for heat transfer such as using the temperature in the surrounding well fluids in the annulus 8 of the wellbore 10 , which is preferably open hole but can also be cased or lined. Compartments 3 and 5 are separated by a barrier 4 . The individual reactants and a catalyst, if needed, are stored in compartments 3 and 5 . At the desired location or even on the way to the desired location the objective is to make the barrier fail or become porous or otherwise get out of the way of separating the reactants in the compartments 3 and 5 so that such reactants with a catalyst, if any, can come together for an exothermic reaction that will enhance the swelling rate of the element 2 .
Arrow 12 schematically illustrates the variety of ways the barrier 4 can be compromised. One option is a depth actuation where one side of the barrier is sensitive to hydrostatic pressure in the annulus 8 and the other compartment is isolated from hydrostatic pressure in the annulus 8 . Exposure to pressure in annulus 8 to say compartment 3 can be through a flexible membrane or bellows that keeps well fluid separate from a reactant in compartment 3 . At a given depth the annulus pressure communicating through compartment 3 and into the barrier 4 puts a differential pressure on the barrier to cause it to fail allowing compartments 3 and 5 to communicate and the exothermic reaction to start. Another variation on this if the annulus pressure is too low is to pressurize the annulus 8 when it is desired to start the reaction and the rest takes place as explained above when relying on hydrostatic in the annulus 8 .
Another way is to use a timer connected to a valve actuator that when opened allows well fluid to get to the barrier 4 and either melt, dissolve or otherwise fail the barrier 4 . The power for the timer and the actuator can be a battery located in the element 2 .
Another way is to rely on the expected temperature of well fluid to permeate the element 2 and cause the barrier 4 to melt or otherwise degrade from heat from the well fluids.
FIG. 3 illustrates the compartments 3 and 5 separated by the barrier 4 located within the element 2 that is mounted to the mandrel or base pipe 1 . A sleeve 20 has a ball seat 22 that accepts a ball 24 . Pressure from above on the ball shifts the sleeve 20 and force knife 26 to move radially to penetrate the barrier 4 . Note that the knife 26 moves through a wall opening 28 . Alternatively the knife 26 can be induced to move axially to slice through the barrier 4 using a physical force as described above or equivalent physical force or by using an indirect force such as a magnetic field. If the operator finds the use of a wall opening 28 unacceptable in a swelling packer application then the knife can be magnetized and located within compartment 3 and a magnet can be delivered to the location of the element 2 so that the repulsion of the two magnets can advance the knife 26 axially or radially through the barrier 4 . If the element 2 is a porous screen the tubular 1 will be perforated under the element 2 so that an opening 28 for the knife 26 should be of no consequence for the operator.
Another variation is to use galvanic corrosion using one or more electrodes associated with the barrier 4 . In run in mode an electrode can be energized to prevent the onset of corrosion and ultimate failure of barrier 4 , while in another mode the corrosion can be initiated using the same electrode or another electrode associated with the barrier 4 . The process can be actuated from the surface or in other ways such as by time, pressure or temperature triggers to initiate the corrosion process. Alternatively, the barrier 4 , itself can be the sacrificial member of a galvanic pair and just corrode over time. Alternatively a corrosive material can be stored in a pressurized chamber with a valve controlled by a processor to operate a valve actuator to allow the corrosive material to reach the barrier 4 and degrade the barrier to start the exothermic reaction.
Another alternative is to use at least one reactant that over time will attack the barrier 4 and undermine it.
In another variation, one compartment contains a reactant corrosive to the barrier 4 , for example NaCl aqueous solution or seawater. The second compartment contains dry super-corroding Mg alloy powder or sintered powder (see U.S. Pat. No. 4,264,362), or powder or sintered powder prepared by grinding Mg and Fe powder (see U.S. Pat. No. 4,017,414). NaCl or KCl, for example, may be added to the second compartment. The barrier 4 is preferably made of a Mg alloy. Its corrosion rate depends on the temperature. Since the barrier 4 is electrically conductive, its temperature can be increased using the induction heater 32 as shown in FIG. 5 . This will accelerate the barrier corrosion and, thus, will initiate the exothermic reaction between the chemicals in two compartments.
In another variation, the compartment containing NaCl solution also contains a Mg electrode with a corrosion potential lower than that of the Mg alloy barrier. This Mg electrode is in mechanical and electrical contact with the barrier 4 , so it acts as a sacrificial anode immersed into the same electrolyte and preserves the barrier from corrosion. A dielectric “knife” 26 actuated by a sleeve as described above, separates the sacrificial anode from the Mg alloy barrier and, thus, the barrier corrosion rate increases.
In another variation, “knife” is composed of anodic and cathodic portions, which are separated by a dielectric. Initially, anodic part of the knife is in electrical and mechanical contact with the corrodible barrier. In this configuration, the barrier is preserved by the sacrificial anode. As the knife moves, cathodic part of the knife starts contacting the barrier while the anodic part is disconnected from the barrier. This will accelerate the corrosion of the barrier since it is now a sacrificial anode, as shown in FIG. 4 .
In another version, the “knife” is cathodic with respect to the barrier. Initially it does not contact the barrier. Motion of the sleeve places the knife in contact with the barrier and the electrolyte. Now the barrier serves as a sacrificial anode.
Thus for a swelling material that acts as a packer the compartments 3 and 5 and the barrier 4 between them can be embedded in the element 2 . The same goes for the use of swelling foam that acts as a self-conforming screen with the difference being that the foam is deliberately porous and the mandrel or pipe 1 is perforated.
Another alternative technique is schematically illustrated in FIG. 2 . Here the swelling material 2 is impregnated or infused or otherwise produced to have a distribution of metal particles and preferably ferromagnetic particles, or particles made of electrically conductive resins or polymers, 30 . The particles can be positioned in swelling foam by forcing the particles through the material 2 during the fabrication process. This can be done with flow through the foam and can be coordinated with compressing the foam to get its profile reduced for run in. An induction heater 32 is preferably run in on wireline 34 for a power source although local power and a slickline can also be used. The heater 32 can be radially articulated once in position so that its coils extend into close proximity of the tubular inside wall. While electromagnetic induction heating can also be used to locally increase the temperature of a ferromagnetic pipe 1 on which a packer or a totally conformable screen 2 is mounted, the preferred method is to use a dielectric mandrel 1 and, thus, to generate heat in the electrically conductive particles 30 distributed within the swelling element 2 directly. If the pipe 1 is metallic, it will increase the temperature of the packer or the screen 2 mounted on it and, thus, will stimulate deployment. Induction heating is the process of heating an electrically conducting object (usually a metal) by electromagnetic induction, where eddy currents are generated within the metal and resistance leads to Joule heating of the metal. In an induction downhole heater 32 , a coil of insulated copper wire is placed inside the production pipe 1 opposing the packer or the conformable screen 2 . An alternating electric current from the power source on the ground level delivered for example through wireline 34 , is made to flow through the coil, which produces an oscillating magnetic field which creates heat in the base pipe in two different ways. Principally, it induces an electric current in the base pipe, which produces resistive heating proportional to the square of the current and to the electrical resistance of the pipe. Secondly, it also creates magnetic hysteresis losses in the base pipe due to its ferromagnetic nature. The first effect dominates as hysteresis losses typically account for less than ten percent of the total heat generated. Induction heaters are faster and more energy-efficient than other electrical heating devices. Moreover, they allow for instant control of heating energy. Since the induction heaters are more efficient when in the close proximity to the base pipe, it is suggested that the copper wire coils are mounted on an expandable, toward the pipe wall, wire line tool activated when it reaches the level of the packer or the screen.
If the mandrel 1 is dielectric, then the full effect of the heater 32 will go into the ferromagnetic particles 30 that are embedded in the element 2 and locally heat the element 2 from within. Preferably the particles will be randomly distributed throughout the element 2 so that the swelling process can be accelerated. Alternatively the mandrel 1 can be electrically conductive and the heating effect will take place from the mandrel 1 and from the ferromagnetic particles 30 , if the field is not completely shielded by the pipe 1 .
The ferromagnetic particles 30 are most simply incorporated into the element 2 at the time the element 2 is manufactured. In the case of a foam element 2 the ferromagnetic particles 30 can be in a solution that is pumped through the foam under pressure so as to embed the particles in the foam from a circulating process. The particles can also be incorporated into the manufacturing process for the element 2 rather than being added thereafter. Another more complex alternative is to add the particles to the element 2 after the element is at the desired subterranean location but monitoring the effectiveness of this mode of ferromagnetic particle addition can be an issue.
As an alternative to the metal or ferromagnetic particles the element 2 can be impregnated with electrically conductive resins or polymers also shown schematically as 30 and with induction heater 32 the result is the same as the heating effect described above using ferromagnetic particles.
The heater 32 can be moved in a single trip to accelerate swelling at a series of packers or screen sections. In the case of packers pressure can be applied to see if there is leakage or not past the packer after a predetermined time of heat application.
The above description is illustrative of the preferred embodiment and many modifications may be made by those skilled in the art without departing from the invention whose scope is to be determined from the literal and equivalent scope of the claims below. | The swelling rate of a swelling packer element or a conforming foam screen material is accelerated with heat. In one variation reactants that create an exothermic reaction plus a catalyst, if needed, are allowed to come into contact upon placement at the desired location. The heat accelerates the swelling process and cuts the time to when the next operation can commence downhole. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION(S)
This application is the 35 U.S.C. §371 national stage of PCT application PCT/US2012/042880, filed Jun. 18, 2012, which claims priority to and the benefit of U.S. Provisional Application Ser. No. 61/498,531, filed Jun. 18, 2011, both of which are hereby incorporated by reference herein in their entirety.
TECHNICAL FIELD
The present disclosure is generally related to photocatalytically active titanium dioxide and polylactic acid combined in a porous microparticle and to methods of synthesis thereof. The present disclosure further relates to methods of using the microparticles for the photodegradation of organic compounds in aqueous environments.
BACKGROUND
Poly(lactic acid) (PLA) is a widely used polymer derived from natural sources. PLA is a hydrophobic polymer that is completely insoluble in water. The hydrophobicity of PLA can be attenuated by copolymerization with other hydroxycarboxylic acids such as glycolic acid and 4-hydroxybutyric acid (Amy et al., (2004) J. Biomater. Sci. Polym. Edn. 15: 1281-1304; Lu et al., (2000) Biomater 21: 1837-1845; Biomaterials and Bioengineering Handbook , ed. W. DL, Marcel Dekker, New York, pp. 141-155). The tunable hydrophobicity has previously been exploited in drug delivery applications, but it is also desirable for the absorption of organic pollutants (Wang et al., (2010) J. Biomed. Mat. Res., Part B, Appl. Biomater. 93, 84-92; Liu et al., (2006) J. Biomed. Mat. Res., 78A: 798-807; Liu et al., (2005) Nanotechnology 16: S601-S608; Liu et al., (2006) Int. J. Nanomed. 1: 541-545). PLA has been considered suitable for these purposes because of its biocompatibility, tunable biodegradation and controlled hydrophobicity (Yanling et al., (2005) J Macromol Sci C Polym Rev. 45: 325-349; Hiltunen & Harkonen, (1997) Macromol. 30: 373-379), and make PLA ideal as an environmentally-acceptable sorbent material.
Titania (titanium dioxide, TiO 2 ) is a biocompatible metal oxide commonly used for anti-fouling, anti-microbial, and UV-absorbing properties. Titania has well known photocatalytic properties. It can be used to degrade most organic chemicals to CO 2 and water. The photocatalytic properties of titania have thus far only been observed in the anatase and rutile crystalline forms but not the amorphous phase (Zhang, (2009) Coord. Chem. Rev. 253: 315-3041; C. C. Sorrell, (2011) J. Mater. Sci. 46: 855-874). There have been many methods developed to form anatase phase or rutile phase titania. All of these methods require harsh conditions such as strong acids or bases or high temperatures which are not compatible with polymeric systems, precluding combining photocatalytically active TiO2 and heat-sensitive organic polymers in a single structure (Ismagilov et al., (2009) Rus. Chem. Rev. 78: 873-885; Wu et al., (2009) Eur. J. Inorg. Chem. 2009: 2789-2795; Xin, (2010) Appl. Mater. Inter. 2: 3479-3485; Kalita (2006) Mater. Sci. and Eng. A. 435-436: 327-332). Recently, however, methanol has been shown to induce the mineralization of titania into a photocatalytically active mixture of anatase and amorphous phases at low temperature and without the use of acids or bases.
There have been efforts to incorporate titania into polymer systems to utilize the desirable properties of both constituents. Such combination materials are multifunctional, being able to absorb and degrade organics, be biodegradable, and are biocompatible (environmentally benign). Because of these uses, PLA based composites have mostly been used as protective coatings.
There been few reports on PLA/titania systems prepared in situ under relatively mild conditions. All previous studies have been focused on incorporating pre-prepared titania into a polymer matrix. A variety of different approaches have been used to create mixed-hybrid PLA/titania systems such as mixed composites (Zhu et al., (2011) Polym Composite 32: 519-528), grafted to polymers (Luo et al., (2009) Acta Materials 57: 3182-3191), and by modifying TiO 2 for dispersal in composite systems (Norio Nakayama, (2007) Polym Deg Stab 92: 1255-1264).
Most of the work on developing PLA/TiO 2 composite systems has been for the purpose of bioengineering bone grafts. The PLA/TiO 2 systems have better performance than the previously studied PLA/hydroxyapatite systems. The TiO 2 reduces the acidity of the bone graft as the PLA degrades into lactic acid, and also increases the overall degradation rate. Thin films, microspheres and microfoams have been employed for this purpose. The only studies on PLA/TiO 2 's photocatalytic properties have focused on thin films for applications such as antifouling coatings. All of these systems were also composite systems and had issues related to inconsistent mixing, while most also exhibited a lag time associated with mass transfer limitations of hydroxyl radicals out of the PLA matrix. This lag time was eliminated by exposing the films to UV irradiation before exposing the films to a test dye solution.
SUMMARY
The disclosure provides a multifunctional microparticle based on incorporation of titania nanoparticles combined into a porous polylactic acid (PLA) matrix. One aspect of the present disclosure, therefore, provides embodiments of a hybrid microparticle comprising photocatalytically active titanium dioxide and a poly-(D,L-lactic acid) polymer, where the microparticle comprises a plurality of pores.
In embodiments of this aspect of the disclosure, the titanium dioxide can be embedded in a polymer comprising poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the titanium dioxide can comprise anatase titanium dioxide nanoparticles coated in a polymer comprising poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the hybrid micro particle has at least one dimension in the range of about 50 μm to about 400 μm.
In embodiments of this aspect of the disclosure, the hybrid microparticle can have at least one dimension in the range of about 100 μm to about 300 μm.
In embodiments of this aspect of the disclosure, the microparticle on contacting an organic compound and irradiated with light energy can degrade the organic compound.
In embodiments of this aspect of the disclosure, the microparticle can be degradable on prolonged irradiation by light energy.
Another aspect of the present disclosure encompasses embodiments of a method of photocatalytically degrading an organic compound in an aqueous liquid comprising: (i) adding hybrid microparticles according to the disclosure to an aqueous liquid having an organic compound desired to be degraded; and (ii) irradiating the hybrid microparticles with light energy, thereby photocatalytically degrading an organic compound in contact with the titanium dioxide of the hybrid microparticles.
In embodiments of this aspect of the disclosure, the organic compound can be, but is not limited to, a hydrocarbon, a biomolecule, an industrial waste product, or an agricultural waste product.
In embodiments of this aspect of the disclosure, the method can further comprise the step of allowing the hybrid microparticles to degrade.
Another aspect of the present disclosure encompasses embodiments of a method for generating photocatalytically capable porous hybrid microparticles comprising the steps of: combining in an organic solvent a poly-(D,L-lactic acid) or a poly-(lactic-co-glycolic acid), and a titanium oxide; (ii) adding 2-methylpentane to form a polylactide:titanium oxide: 2-methylpentane mixture; (iii) adding the polylactide:titanium oxide: 2-methylpentane mixture to a solution of polyvinyl alcohol (PVA) thereby forming an emulsion; (iv) allowing the organic solvents to evaporate, thereby forming microparticles; (v) isolating the microparticles; (vi) contacting the isolated microparticles with methanol, thereby generating porous photocatalytically capable microparticles; and (vii) isolating the photocatalytically capable porous hybrid microparticles from the methanol.
In embodiments of this aspect of the titanium oxide is combined with poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the titanium oxide can be titanium tetraisopropoxide (TTIP) or anatase titanium dioxide.
In embodiments of this aspect of the disclosure, the titanium oxide can be titanium tetraisopropoxide and forms covalent bonds with the poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the organic solvent can be chloroform or dichloromethane.
In embodiments of this aspect of the disclosure, the organic sol vent can be dichloromethane and the ratio of dichloromethane to the poly-(D,L-lactic acid):titanium oxide: 2-methylpentane mixture can be between about 13:1 to about 18:1.
In embodiments of this aspect of the disclosure, the ratio of poly-(D,L-lactic acid)+titanium oxide: 2-methylpentane can be from about 10:0 to about 3:2.
In embodiments of this aspect of the disclosure, the ratio of poly-(D,L-lactic acid)+titanium oxide: 2-methylpentane can be about 3:2.
In embodiments of this aspect of the disclosure, the photocatalytically capable microparticle can have between about 10% titanium dioxide to about 30% titanium dioxide.
In embodiments of this aspect of the disclosure, the photocatalytically capable microparticle can have about 10% titanium dioxide or about 20% titanium dioxide.
BRIEF DESCRIPTION OF THE DRAWINGS
Further aspects of the present disclosure will be more readily appreciated upon review of the detailed description of its various embodiments, described below, when taken in conjunction with the accompanying drawings.
FIGS. 1A and 1B schematically illustrate the formation of titania/PLA hybrid microparticles and the methanol mineralization steps to generate the photocatalytically active TiO 2 of the disclosure.
FIGS. 2A and 2B illustrate digital SEM images of an intact porous in situ hybrid microparticle ( FIG. 2A ) and a cross sectional view thereof ( FIG. 2B ).
FIG. 3 illustrates a digital SEM image of a titania nanoparticle obtained after dissolution of porous in situ hybrid microparticles.
FIG. 4 is a graph illustrating an XPS spectrum of in situ hybrid microparticles.
FIG. 5 is a graph illustrating an EDS spectrum of in situ hybrid microparticles.
FIG. 6 is a graph illustrating a Raman spectrum of microparticles with methanol treatment
FIG. 7 is a graph illustrating a Raman spectrum of microparticles without methanol treatment
FIG. 8 is a graph illustrating an XRD pattern of in situ hybrid TiO 2 /PLA microparticles after PLA digestion.
FIG. 9A is a graph illustrating the degradation of the dye Rhodamine 6G by mixed composition microparticles according to the present disclosure.
FIG. 9B is a graph illustrating the degradation of the dye Rhodamine 6G by in situ hybrid microparticles according to the present disclosure.
FIG. 10A is a graph illustrating the degradation of the dye Rhodamine 6G by in situ hybrid microparticles having 10% TiO 2 content according to the present disclosure.
FIG. 10B is a graph illustrating the degradation of the dye Rhodamine 6G by in situ hybrid microparticles having 10% TiO 2 content according to the present disclosure.
FIG. 11 is a graph illustrating the biodegradation of mixed composite and in situ hybrid
FIG. 12 is a pair of digital SEM images of directly mixed particles. On the left, the particles contained 10% TiO 2 mixed with PLA; on the right, the particles contained 20% TiO 2 mixed with PLA. 2MP was added to form porous particles.
FIG. 13 is a graph illustrating the dye rhodamine 6G degradation results. The dye degradation was analyzed by exposing the microparticles to a rhodamine 6G solution for 2 hours under UV irradiation and then the amount of rhodamine 6G removal was quantified.
FIG. 14 is a graph illustrating dye degradation of in situ microparticles with differing amounts of titania.
FIG. 15A is a graph illustrating biodegradation of in situ microparticles with differing amounts of titania. The biodegradation of particles was analyzed by exposing the microparticles to UV irradiation. 2 weeks data is shown. The percentage of biodegradable product loss was determined.
FIG. 15B is a graph illustrating mass loss due to biodegradation of in situ microparticles with differing amounts of titania. The biodegradation of particles was analyzed by exposing the microparticles to UV irradiation. 2 weeks data is shown. The percentage of biodegradable mass loss was determined.
The drawings are described in greater detail in the description and examples below.
The details of some exemplary embodiments of the methods and systems of the present disclosure are set forth in the description below. Other features, objects, and advantages of the disclosure will be apparent to one of skill in the art upon examination of the following description, drawings, examples and claims. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims.
DETAILED DESCRIPTION
Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.
All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed.
As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.
Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of medicine, organic chemistry, biochemistry, molecular biology, pharmacology, and the like, which are within the skill of the art. Such techniques are explained fully in the literature.
It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a support” includes a plurality of supports. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent.
As used herein, the following terms have the meanings ascribed to them unless specified otherwise. In this disclosure, “comprises,” “comprising,” “containing” and “having” and the like can have the meaning ascribed to them in U.S. Patent law and can mean “includes,” “including,” and the like; “consisting essentially of” or “consists essentially” or the like, when applied to methods and compositions encompassed by the present disclosure refers to compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps (or analogs or derivatives thereof as discussed above). Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein. “Consisting essentially of” or “consists essentially” or the like, when applied to methods and compositions encompassed by the present disclosure have the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments.
Abbreviations
TIPP: titanium tetraisopropoxide; DCM: dichloromethane; PVA: polyvinyl alcohol (MW=72,000), 2MP: 2-methylpentane; PLA: poly-(D,L-lactic acid) (PLA M n =136,000); EDX: Energy-dispersive X-ray spectroscopy; XPS: X-ray photoelectron spectroscopy.
Definitions
The term ‘mixed composite’ as used herein refers to PLA/TiO 2 microparticles obtained by direct mixing of titania nanoparticles with PLA matrix
The term ‘in situ hybrid macroparticle’ as used herein refers to PLA/TiO 2 microparticles obtained by in situ mineralization of titania nanoparticles (using titania precursor such as TIPP) within PLA matrix.
The term “hybrid microparticle” as used herein refers to a particle between about 50 μm and about 400 μm, preferably between about 10 μm and about 300 μm and comprising a titanium dioxide and a polymer formed from poly-(D,L-lactic acid).
The term “photocatalytically active” as used herein refers to a substance that shows catalytic activity when irradiated with light such as ultraviolet rays, and preferably, to a substance that, when irradiated with light, can decompose and eliminate various organic and inorganic compounds and perform sterilization.
The term “anatase” as used herein refers to one of the three mineral forms of titanium dioxide. Crystals of anatase can be prepared in laboratories by chemical methods such as sol-gel method. Examples include controlled hydrolysis of titanium tetrachloride (TiCl 4 ) or titanium alkoxides.
The term “sol-gel” as used herein refers to a wet-chemical technique used primarily for the fabrication of metal oxides) starting from a colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers. Typical precursors are metal alkoxides and metal salts (such as chlorides, nitrates and acetates), which undergo various forms of hydrolysis and polycondensation reactions.
The term “organic compound” as used herein refers to any organic molecule that can pass through the pores of the hybrid microparticles of the disclosure. Such compounds include, but are not limited to, such as hydrocarbons, alkyl and aromatic that are derived from or found in crude oil, antibiotics, pharmaceuticals, hormones, the products of industrial and agricultural processes, and the like that are suspended or dissolved in an aqueous fluid, including naturally occurring bodies of water, marine and freshwater, lakes, rivers, estuaries, lagoons, and the like. Accordingly, the microparticles of the present disclosure are advantageous for the degradation of organic compounds considered to be pollutants of aqueous bodies. The microparticles of the disclosure are suitable for degrading organic compounds photocatalytically and may then be degraded themselves to leave a residual titanium dioxide that is environmentally benign.
The term “coated” as used herein refers to an encapsulating layer of a polymer surrounding partially or entirely a core body.
The term “titanium oxide” as used herein refers to any form titanium oxide that can function as a photocatalyst for the degradation of organic molecules. The term also refers to any precursor oxide that can be converted to a photocatalytically capable form thereof by the methods of the present disclosure. For example, but not intended to be limiting, titanium tetraisopropoxide (TTIP), an alkyloxide, may be used to generate a titanium dioxide form cross-linked to a polymer formed from poly-(D,L-lactic acid). In the methods of the disclosure, displacement of the isopropionyl groups during the formation of titanium dioxide (titania) leads to the formation of isopropanol, thereby giving rise to the “sponge-like” porous structure of the hybrid microparticles of the disclosure.
The term “poly-(D,L-lactic acid)” (PLA) as used herein refers to (C 3 H 4 O 2 ) n Poly(lactic acid) or polylactide (PLA), a thermoplastic aliphatic polyester. PLA is not a polyacid (polyelectrolyte), but rather a polyester. Two lactic acid molecules undergo a single esterification and then catalytically cyclize to form a cyclic lactide ester. PLA of high molecular weight is produced from the dilactate ester by ring-opening polymerization using stannous catalyst. It is understood that several distinct forms of polylactide may be used in the compositions of the disclosure including, but not limited to, poly-L-lactide (PLLA) resulting from polymerization of L,L-lattice (also known as L-lactide), PDLA (poly-D-lactide), and poly(L-lactide-co-D,L-lactide) (PLDLLA).
Also contemplated to be useful in the formation of the microparticles of the disclosure is a poly(lactic-co-glycolic acid) copolymers (PLGA) alone or in combination with a PLA-derivative. PLGA or poly(lactic-co-glycolic acid) is a copolymer synthesized by means of random ring-opening co-polymerization of two different monomers, the cyclic dimers (1,4-dioxane-2,5-diones) of glycolic acid and lactic acid. Common catalysts used in the preparation of this polymer include tin(II) 2-ethylhexanoate, tin(II) alkoxides, or aluminum isopropoxide. During polymerization, successive monomeric units (of glycolic or lactic acid) are linked together in PLGA by ester linkages, thus yielding a linear, aliphatic polyester as a product. Depending on the ratio of lactide to glycolide used for the polymerization, different forms of PLGA can be obtained, such as, but not limited to PLGA 75:25, a copolymer whose composition is 75% lactic acid and 25% glycolic acid). Unlike the homopolymer of lactic acid (polylactide) (PLA) which has poor solubility, PLGA can be dissolved by a wide range of common solvents, including chlorinated solvents, tetrahydrofuran, acetone or ethyl acetate.
Description
The present disclosure provides for novel multi-functional hybrid titania/PLA microparticles. Two methods were found to be suitable for the generation of the multifunctional hybrid particles of the disclosure. In the first approach, the organic and inorganic materials can be combined and cast into microspheres using an oil-water emulsion. In the second approach there is covalent attachment of the inorganic component to the organic fraction of the material in situ via an acid-catalyzed sol-gel condensation. The in situ PLA/TiO 2 can then cast into microspheres. The TiO 2 formed by these procedures is amorphous so methanol mineralization was applied to produce the photocatalytically active materials.
The microparticles of the present disclosure, because of their porous structure have the ability to absorb organic compounds that can then contact the photocatalytically active titania. Upon exposure to light, and in particular solar ultraviolet irradiation, the titania photoactivated reactions to convert the organic molecules into such as carbon dioxide and other small organic moieties that can be less environmentally disadvantageous compared to the organic compounds in their original state before contact with the microparticles.
Accordingly, the microparticles of the present disclosure are particularly suitable for depositing into bodies of water that contain organic compound pollutants such as antibiotics, estrogens and derivatives thereof, crude oil-derived hydrocarbons, chemical and agricultural waste, and the like. Both during and after the microparticles have absorbed the organic compounds and subjected them to photocatalyzed degradation, the microparticles themselves are degraded so that ultimately all that remains is the insoluble form of the titania that can settle out of the water body. Titania itself is environmentally benign.
Titania Mineralization: Titania can be formed by various methods. One of the most common methods for titania formation is the solvo-thermal method. This method utilizes an acid catalyzed sol-gel condensation of the titanium tetraalkoxide precursor followed by a thermal crystallization with temperatures above 300° C. The sol-gel reaction alone produces amorphous titania that is photocatalytically inactive. The thermal crystallization step is necessary to obtain both the anatase and rutile crystalline forms of titania, both of which are photocatalytically active. The temperature used for crystallization determines the crystalline form of titania. In situ titania formation using the sol-gel method with TiO2 and PLA combined generated microparticles that were photocatalytically inactive and no crystalline titania could be detected. Significantly, using the heating conditions typically employed for the solvo-thermal method resulted in degradation of the polymer microparticles. This in situ formation followed by thermal treatment had been used previously to form titania nano and microparticles, but in all cases the polymer matrix was also destroyed by the thermal treatment (Cui et al., (2010) J. Phys. Chem. 114: 2434-2439; S. Wongnawa (2010) J. Nanopart. Res. 12: 2895-2906; Khalil et al., (2010) J. Vinyl Addit. Tech. 16: 272-276). The solvo-thermal method, therefore, was not suitable for the in situ formation of titania that is intended to remain in a polymer matrix. PLA degrades more quickly in the presence of acids or bases as well as being pyrolyzed at the temperatures required for titania mineralization.
Accordingly, a facile method to mineralize titania below 60° C. and without using concentrated strong acids or bases was developed for the preparation of the microparticles of the present disclosure. This method has previously been used for the preparation of titania in peptide and silafin networks, but not when in a polyester matrix. In the previously described methods, the peptide was designed to biomineralize titania, and the effects of methanol on the mineralization were not explored.
To explore the use of methanol as a mineralization agent, we performed a sol-gel synthesis of titania was explored by dissolving titania in isopropanol and then adding water dropwise until the formation of the white titania precipitate. The solution was then filtered, the white precipitate placed in a reaction vial, and covered with methanol. The titania was mineralized for varying amounts of time and at elevated temperatures. Anatase titania formed when exposed to methanol for 24 hrs at room temperature. Under all elevated temperatures and at shorter time periods, the titania remained amorphous.
In situ PLA/TiO 2 : The in situ formation of titania was achieved using the carboxylic acid end group of the PLA polymer as a sol-gel catalyst for the solvolysis of titanium tetraisopropoxide in chloroform. The PLA/TiO2 in chloroform mixture was cast into microparticles in the same manner as has been described in Kim et al., (2010) Chem. Commun. 46: 7433-7435, incorporated herein by reference in its entirety). Isopropanol formed during the sol-gel reaction acts as a non-solvent for PLA and also decreases the emulsion solution polarity. The decreased polarity results in an increase in PLA solubility and thus a decrease in recovered microparticle material over longer evaporation times. The isopropanol acts as a non-solvent causing increased porosity in all samples. We also used 2-methyl pentane as a non-solvent to increase porosity over that produced by isopropanol alone. After collection and drying of the microparticles, the microparticles were then exposed to methanol for 24 hrs to induce the mineralization of the titania. In situ Sol-Gel Reaction Optimization: The sol-gel reactions conditions were examined to optimize the formation of TiO 2 by testing the photocatalytic activity versus sol-gel reaction time for 15, 30, 45, and 60 minutes at both 10% titania and 20% titania. It was found for both the 10% and 20% titania samples that the 15 and 30 minute samples degraded the most dye and dye degradation decreased over increasing sol-gel reaction time periods.
Both the 10% and 20% TiO 2 samples showed almost the same activity for the 15 min sol-gel reaction time. The 20% TiO 2 samples exhibited a much sharper decrease in photocatalytic degradation as the sol-gel reaction time was increased from 15 minutes compared to the 10% TiO 2 The longer reaction times may produce inferior titania nanoparticles while also producing microparticles that have higher porosity. As the reaction time was increased, the size of the titania formed increased. Furthermore, methanol mineralization may be less efficient on larger particles. With a larger number of smaller titania nanoparticles, there is a much higher reactive surface area. The increased amount of isopropanol produced over extended reaction times also helped to increase the porosity.
In situ PLA/TiO 2 Microparticle Morphology: The in situ hybrid microparticles generated by the methods of the present disclosure were observed under optical microscope at 40× magnification. The hybrid microparticles appeared as porous sponges of irregular shapes and ranged in size from about 100 μm to about 300 μm. The visible surface roughness increased from the 10:0 microparticles to the 6:4 microparticles for both the 10% and 20 titania. It was noted that there was more visible roughness of all of the hybrid microparticles than for the most porous composite microparticles due to the presence or isopropanol.
The optimized hybrid microparticles (6:4, 15 min. sol-gel, both 10% and 20% titania) were selected for imaging by SEM, as shown in FIGS. 2A, 2B , and 12. The hybrid particles were observed in the form of many irregular shapes but there were also many spherical microparticles. The dimensions of the particles were ranged in size from about 50 μm to about 300 μm. The particles were very porous and many of the particles appeared to be combinations of many smaller microparticles fused together.
In situ PLA/TiO 2 Microparticle Photocatalytic Activity: Microparticles were tested for photocatalytic activity using a model dye, rhodamine 6G. The results of the dye degradation experiments over a two hour time period ( FIGS. 9A and 9B ) showed that the in situ microparticles both absorbed and degraded the model dye. The microparticles with 10% TiO 2 exhibited an increase in absorption capacity as the porosity increased but also exhibited a decrease in degradation. The microparticles with 20% TiO 2 showed less degradation than the microparticles with 10% TiO 2 but had a similar absorption capacity. Overall these microparticles had reduced photocatalytic activity as the anatase standard, which had an equivalent amount of titania as the 10% TiO 2 microparticles. Titania content of PLA/TiO 2 Microparticles: To test the microparticles to determine the presence of titania, EDS and XPS spectra of the particles were taken. Both the EDS and XPS spectra ( FIGS. 4 and 5 ) showed the presence of the titanium and oxygen of titania, but the presence of crystalline allotropes could not be confirmed by this method. In situ prepared titania microparticles that had been prepared with and without methanol treatment were compared. Both samples prepared with and without methanol treatment showed the presence of titanium.
Raman spectroscopy, as shown in FIGS. 6 and 7 , was performed to determine the crystalline nature of the titania. To do this, the polymer matrix was removed by a one molar NaOH aqueous solution (an SEM image of such a treated microparticle is shown in FIG. 3 ). The residue was then used for Raman analysis. The Raman analysis of the samples showed that there was crystalline structure present. The observed peaks were very broad and did not correspond to any previously reported values for either anatase or rutile titania. This result corresponds to other previous work where silafin was used as a platform for titania formation.
These results show that there are very small crystalline domains as well as areas of amorphous titania present. The broadness of the peaks indicates that the crystalline areas are small and isolated.
The Raman spectra of prepared microparticles that had not been treated with methanol ( FIG. 6 ) were also obtained. These microparticles did not exhibit any peaks characteristic of crystalline structure indicating that the titania present was completely amorphous.
Mixed Composite PLA/TiO 2 Microparticles: This study was initially focused on forming biodegradable PLA composite microparticles that have preformed titania incorporated. This approach has been performed to process many different forms of materials but it had not been used to make microspheres (Liu et al., (2006) J. Biomed. Mat. Res., 78A: 798-807; Liu et al., (2005) Nanotechnology 16: S601-S608; Liu et al., (2006) Int. J. Nanomed. 1: 541-545; Mazzocchetti & Scandola (2009) Appl. Mater. Inter. 1: 726-734; Buzarovska et al., (2009) J. Appl. Polym. Sci. 114: 3118-3124). The formation of the composite TiO 2 /PLA microparticles was met with limited success because the TiO 2 powder readily precipitates so it must be continually stirred during the casting process. Although the solution was continually mixed there was still inefficient and non-uniform incorporation of titania in the microparticles. These hybrid microparticles did degrade the model dye but there was not an increase in dye degradation when the concentration of titania in the microparticles was increased. These particles also exhibited poor absorption capacity which can slow down the dye degradation for high dye loading. Mixed Composite PLA/TiO 2 Microparticle Morphology: The composite microparticles were observed under optical microscope at 40× magnification. The composite particle appeared to be similar in shape and size to PLA microparticles that were prepared under the same conditions. The particles were spherical and ranged in size from about 100 μm to about 300 μm. The visible surface roughness increased from the 10:0 microparticles to the 6:4 microparticles for both the 10% and 20% titania.
Due to the limitations for composite particles we then focused on forming titania in situ. Previously it was reported that methanol can be used as a mineralization agent for titania (Kroger et al., (2006) Angew. Chem. Int. Ed. 45: 7239-7243).
The present disclosure provides, therefore, multifunctional hybrid polymer microparticles with in situ formed anatase. These microparticles can both absorb a model organic dye as well as degrade the dye under UV irradiation. We have also demonstrated an additional mixed hybrid composite system. The mixed hybrid microparticles have the same multifunctionality as the in situ hybrid microparticles but exhibited some limitations in the formation of the microparticles.
Degradation of PLA/TiO2 particles: The degradation behavior of PLA depends on factors such as molecular weight and higher order structures. Other important factors such as temperature, pH, light and catalytic species also alter can the biodegradation behavior. In addition, the TiO 2 in the hybrid particles can also affect the degradation of PLA/TiO 2 particles because a desired property of TiO 2 is to degrade organic compound.
The microparticles were exposed to UV irradiation for 2 weeks to observe the degradation behavior. After 2 weeks, there was very little weight loss of pure PLA microparticles. For all PLA/TiO 2 particles there was observed weight loss. FIG. 15 shows that all particles biodegraded over the two week experimental time. For directly mixed composite particles, less porous particles had less weight loss after 2 weeks UV irradiation than the more porous particles. Particles which contained 20% TiO 2 exhibited higher degradation ability than the particles with 10% TiO 2 . The in situ hybrid particles showed a slightly lower degradation for the 10% TiO 2 than the mixed composite particles. Additionally, the in situ hybrid particles with 20% TiO 2 showed much higher degradation than the mixed composite particles.
Thus, the in situ hybrid particles have both absorptive and degradative properties in addition to increased biodegradation over PLA. These materials can be useful for a variety of remediation needs, and can be integrated in many current systems for environmental restoration, water purification and the like.
One aspect of the present disclosure, therefore, provides embodiments of a hybrid microparticle comprising photocatalytically active titanium dioxide and a poly-(D,L-lactic acid) polymer, where the microparticle comprises a plurality of pores.
In embodiments of this aspect of the disclosure, the titanium dioxide can be embedded in a polymer comprising poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the titanium dioxide can comprise anatase titanium dioxide nanoparticles coated in a polymer comprising poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the hybrid microparticle has at least one dimension in the range of about 50 μm to about 400 μm.
In embodiments of this aspect of the disclosure, the hybrid microparticle can have at least one dimension in the range of about 100 μm to about 300 μm.
In embodiments of this aspect of the disclosure, the microparticle on contacting an organic compound and irradiated with light energy can degrade the organic compound.
In embodiments of this aspect of the disclosure, the microparticle can be degradable on prolonged irradiation by light energy.
Another aspect of the present disclosure encompasses embodiments of a method of photocatalytically degrading an organic compound in an aqueous liquid comprising: (i) adding hybrid microparticles according to the disclosure to an aqueous liquid having an organic compound desired to be degraded; and (ii) irradiating the hybrid microparticles with light energy, thereby photocatalytically degrading an organic compound in contact with the titanium dioxide of the hybrid microparticles.
In embodiments of this aspect of the disclosure, the organic compound can be, but is not limited to, a hydrocarbon, a biomolecule, an industrial waste product, or an agricultural waste product.
In embodiments of this aspect of the disclosure, the method can further comprise the step of allowing the hybrid microparticles to degrade.
Another aspect of the present disclosure encompasses embodiments of a method for generating photocatalytically capable porous hybrid microparticles comprising the steps of: combining in an organic solvent a poly-(D,L-lactic acid) or a poly-(lactic-co-glycolic acid), and a titanium oxide; (ii) adding 2-methylpentane to form a polylactide:titanium oxide: 2-methylpentane mixture; (iii) adding the polylactide:titanium oxide: 2-methylpentane mixture to a solution of polyvinyl alcohol (PVA) thereby forming an emulsion; (iv) allowing the organic solvents to evaporate, thereby forming microparticles; (v) isolating the microparticles; (vi) contacting the isolated microparticles with methanol, thereby generating porous photocatalytically capable microparticles; and (vii) isolating the photocatalytically capable porous hybrid microparticles from the methanol.
In embodiments of this aspect of the titanium oxide is combined with poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the titanium oxide can be titanium tetraisopropoxide (TTIP) or anatase titanium dioxide.
In embodiments of this aspect of the disclosure, the titanium oxide can be titanium tetraisopropoxide and forms covalent bonds with the poly-(D,L-lactic acid).
In embodiments of this aspect of the disclosure, the organic solvent can be chloroform or dichloromethane.
In embodiments of this aspect of the disclosure, the organic sol vent can be dichloro methane and the ratio of dichloromethane to the poly-(D,L-lactic acid):titanium oxide: 2-methylpentane mixture can be between about 13:1 to about 18:1.
In embodiments of this aspect of the disclosure, the ratio of poly-(D,L-lactic acid)+titanium oxide: 2-methylpentane can be from about 10:0 to about 3:2.
In embodiments of this aspect of the disclosure, the ratio of poly-(D,L-lactic acid)+titanium oxide: 2-methylpentane can be about 3:2.
In embodiments of this aspect of the disclosure, the photocatalytically capable microparticle can have between about 10% titanium dioxide to about 30% titanium dioxide.
In embodiments of this aspect of the disclosure, the photocatalytically capable microparticle can have about 10% titanium dioxide or about 20% titanium dioxide.
The specific examples below are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present disclosure to its fullest extent. All publications recited herein are hereby incorporated by reference in their entirety.
It should be emphasized that the embodiments of the present disclosure, particularly, any “preferred” embodiments, are merely possible examples of the implementations, merely set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) of the disclosure without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure, and the present disclosure and protected by the following claims.
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C., and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20° C. and 1 atmosphere.
EXAMPLES
Example 1
Materials: Anatase TiO 2 powder (Acros), titanium tetraisopropoxide (TTIP, Acros), dichloromethane (DCM, Acros), methanol (Acros), polyvinyl alcohol (MW=72,000, MP Biomedicals), Polysorbate 20 (MP Biomedicals), sodium azide (MP Biomedicals), and 2-methylpentane (2MP, Aldrich) were used without further purification. The poly-(D,L-lactic acid) (PLA M n =136,000) was injection grade.
Example 2
Formation of Hybrid Microparticles: In situ hybrid microparticles were formed using the ratios of 10:0, 8:2, and 6:4 PLA+TTIP:2MP. For all in situ hybrid microparticles, a ratio of 13.5:1 DCM to PLA+TTIP+2MP was used. The table below summarizes the amount of each component used in the formation of the microparticles.
TABLE 1
Sample ID
PLA
TTIP
2MP
DCM
10% 10:0 10 min
0.4690
0.1854
0.0000
8.8
10% 8:2 10 min
0.4852
0.1918
0.1693
11.4
10% 6:4 10 min
0.4700
0.1872
0.3481
11.7
20% 10:0 10 min
0.5138
0.4571
0.0000
13.1
20% 8:2 10 min
0.4525
0.4025
0.2138
14.4
20% 6:4 10 min
0.4505
0.4008
0.5674
19.2
10% 6:4 15 min
0.4011
0.1586
0.3731
12.6
10% 6:4 30 min
0.3971
0.1570
0.3694
12.5
10% 6:4 45 min
0.4288
0.1695
0.3989
13.5
10% 6:4 60 min
0.4268
0.1688
0.3971
13.4
20% 6:4 15 min
0.4273
0.3801
0.5383
18.2
20% 6:4 30 min
0.4258
0.3788
0.5364
18.1
20% 6:4 45 min
0.4019
0.3575
0.5063
17.1
20% 6:4 60 min
0.4138
0.3682
0.5213
17.6
A sample procedure for the formation of porous hybrid Titania/PLA microparticles is as follows: PLA (0.4258 g) was dissolved into 16.1 mL DCM (2.58% w/v). 0.3788 g TTIP (estimated 10% w/w TiO 2 in final product PLA microspheres) was dissolved into 1 mL DCM (0.952 M). The TTIP and PLA solutions were mixed together, vortexed for 30 seconds, and allowed to react, in the dark, for 30 minutes. 0.5364 g 2MP (6:4 ratio by weight; PLA+TTIP:2MP) was dissolved in 1 mL DCM (4.14 M). 1 mL DCM was used for both the TTIP and 2MP, the volume used to dissolve PLA was enough DCM so that the total ratio of DCM to PLA+TTIP+2MP was 13.5:1. The 2MP solution was added to the PLA+TTIP solution after 30 minute reaction time was completed. The mixture was vortexed for 30 seconds. The solution was immediately drawn into a syringe equipped with a 20 G needle and added dropwise to a PVA solution (300 mL; 1% PVA, 0.2% polysorbate 20, and 0.1% NaN 3 ) that was stirred at 300 rpm. The emulsion was stirred for 1 hour after complete addition to allow the organic solvents to evaporate. The emulsion was then filtered through course filter paper. The microparticles were collected and exposed to methanol for 24 hrs to induce mineralization. After 24 hrs the methanol was removed by rotary evaporation under vacuum at 180 RPM and 50° C.
Example 3
Formation of Composite Microparticles: Mix composite microparticles were formed using the ratios of 10:0, 8:2, and 6:4 PLA+TiO 2 :2MP. For all 10% TiO 2 mix composite microparticles, a ratio of 13.5:1 DCM to PLA+TiO 2 +2MP was used and for all 20% TiO 2 mix composite microparticles, 18:1 DCM to PLA+TiO 2 +2mp was used. Table 2 below summarizes the amount of each component used in the formation of the microparticles.
TABLE 2
Sample ID
PLA
TiO 2
2MP
DCM
10% 10:0
1.0160
0.1110
0.0000
10.2
10% 8:2
1.0070
0.1100
0.2792
12.6
10% 6:4
0.4028
0.0448
0.2984
10.1
20% 10:0
0.4122
0.1031
0.0000
9.3
20% 8:2
0.4101
0.1027
0.1282
11.5
20% 6:4
0.3974
0.0997
0.3314
14.9
A sample procedure for the formation of porous composite Titania/PLA microparticles is as follows: 0.4028 g PLA was dissolved in 9.1 mL DCM (4.24%). 0.0448 g TiO 2 (10% w/w in PLA microspheres) anatase powder was added to the PLA solution. 0.2984 g 2MP (6:4 ratio by weight; PLA+TiO 2 :2MP) was dissolved in 1 mL DCM (2.64 M). 1 mL DCM was used for the 2MP, the volume used to dissolve PLA was enough DCM so that the total ratio of DCM to PLA+TiO 2 +2MP was 13.5:1. The PLA+TiO 2 solution was added to the 2MP solution and vortexed for 1 minute to allow for complete suspension of TiO 2 powder. The solution was immediately drawn into a syringe equipped with a 20 G needle and added dropwise to a PVA solution (300 mL; 1%PVA, 0.2% polysorbate 20, and 0.1% NaN 3 ) that was stirred at 300 rpm. The emulsion was stirred for 3 hrs after complete addition to allow the organic solvents to totally evaporate. The emulsion was then filtered through course filter paper. The microparticles were collected and dried under vacuum at 50° C. for 3 hrs.
Example 4
Model Dye Degradation Procedure: The dye degradation was analyzed by exposing 0.0100 g of the microparticles to a 10 mL of 10 ppm rhodamine 6G for 2 hrs under UV irradiation. After 2 hrs the samples were centrifuged at 10,000 RPM for 30 min. The supernatant liquid was removed and measured by UV-Vis spectroscopy and the amount of rhodamine 6G removal was quantified.
Example 5
Model Dye Sorption Procedure: Since the microparticles absorb the dye as well as degrade, the absorption was studied. To determine the amount of absorption, 10 mL of 0.25 M NaOH in methanol was added to the microparticles after removal of the supernatant. The solution was mixed and filtered. The supernatant liquid was analyzed by UV-Vis spectroscopy and the amount of rhodamine 6G that leached out of the particles was quantified.
Example 6
Microparticle Degradation: The biodegradation of the microparticles was analyzed by exposing 0.0100 g of the microparticles suspended in 10 mL of deionized water to UV irradiation. UV irradiation was provided by two 18 inch long 60 Watt UV fluorescent lamps. The lamps were mounted 20 cm above the surface of the suspensions in a cabinet without any additional illumination. The samples were exposed for a two week period and removed after exactly 14 days. Samples were dried at room temperature under vacuum and the mass was taken. The values reported are the percent of the original mass that was not recovered.
Example 7
Microparticle Digestion: The TiO 2 /PLA microparticles were digested to extract the titania from the polymer matrix for measurements. For this, 0.05 g of microparticles was added to a vial. To the vial, 10 mL of 1.00 M NaOH was added. The solution was stirred under ambient conditions for 72 hrs. The aqueous solution was decanted off and then the remaining solid was rinsed with 10 mL DI water followed be decanting the liquid 3 times. The solid was then allowed to dry in a desiccator overnight.
Example 8
UV-Vis: UV-VIS spectroscopy was performed using a Cary 50 spectrometer. A baseline correction was used before measurements were taken.
Example 9
XPS: A PHI 5000 Versaprobe imaging x-ray photoelectron spectrometer (XPS), operating a monochromatic, focused Al K-α x-ray source (E=1486.6 eV) at 25 W with a 100 μm spot size, was used to determine the chemical bonding of the samples. The samples were grounded and charge neutralization was provided by a cold cathode electron flood source and low-energy Ar-ions. All measurements were taken at room temperature and at a pressure of 2×10 −6 Pa; the system base pressure is 5×10 −8 Pa. The energy scale was calibrated with reference to the Ag 3d peak. Surface contamination is removed with Ar-ion sputter etching for 1 min at 1 kV; this removes 2.6 nm from the surface. Surface cratering, due to sputter etching, is limited by rastering the beam across a 2×2 mm 2 area. Survey scans, with pass energy of 187 eV and 1 eV step size, and high-resolution scans, with pass energy of 23.5 eV and 0.2 eV step size, were taken both before and after surface cleaning by sputter-etching. The chemical compositions and bonding states of the films were determined using Multipak v9.0.
Example 10
Raman: Raman spectroscopy was performed using a dilor XY Laser Modular Spectrometer. An Olympus BH-2 microscope with a modified Newport micrometer stage made from two center drilled 426 series stages was used as the sample area. A liquid nitrogen cooled Spec 10 system CCD was used as a detector. A Dragon Lasers (532GLM300) 532 nm, 300 mW laser was used for excitation and Keiser Optical Systems 1.0 in. Holographic SuperNotch-Plus Notch Filter with a central wavelength of 532.0 nm and a bandwidth of approximately 100 wavenumbers was used to subtract out residual laser light.
Example 11
XRD: X-Ray Diffraction spectra were collected using a Seimens D500 X-Ray Diffractometer equipped with a copper tube and a graphite monochromater. The spectra were measured from 2λ from 20° to 80° with a 0.04° step size and a dwell time of 6 secs at each step.
Example 12
SEM: SEM images were obtained using a JEOL 7000 Field Emission SEM instrument. An Oxford Instrument INCAx-sight EDX spectrometer attached to the SEM was used to obtain EDX spectrograms.
Example 12
TABLE 3
Dye degradation results for all samples. Values are in mg of dye per g of microparticles
Absorption +
Degradation
Absorption
Degradation
Sample
(mg)
(mg)
(mg)
Anatase TiO 2
4.605 ± 0.0613
—
4.605 ± 0.0614
10% Composite, least porous
6.588 ± 1.20
0.9861 ± 0.311
5.602 ± 1.41
10% Composite, porous
6.447 ± 0.545
1.265 ± 0.143
5.182 ± 0.679
20% Composite, least porous
7.262 ± 0.798
0.8882 ± 0.0338
6.373 ± 0.800
20% Composite, porous
6.163 ± 1.60
1.397 ± 0.269
4.766 ± 1.86
20% Composite, most porous
6.766 ± 0.429
1.209 ± 0.0929
5.557 ± 0.339
10% in situ, least porous
3.542 ± 0.0613
1.260 ± 0.0339
2.282 ± 0.0953
10% in situ, porous
3.507 ± 0.106
1.358 ± 0.0897
2.149 ± 0.160
10% in situ, most porous
2.550 ± 0.487
1.906 ± 0.0897
0.6445 ± 0.420
20% in situ, porous
3.400 ± 5.19 × 10
1.456 ± 0.235
1.945 ± 0.235
20% in situ, most porous
1.877 ± 0.342
1.632 ± 0.0587
0.4003 ± 0.0845
10% in situ, most porous, 15 min
3.684 ± 0.0613
1.655 ± 0.207
2.029 ± 0.264
sol-gel
10% in situ, most porous, 30 min
2.550 ± 0.487
0.7512 ± 0.212
1.657 ± 0.552
sol-gel
10% in situ, most porous, 45 min
2.054 ± 0.162
0.7317 ± 0.122
1.323 ± 0.0895
sol-gel
10% in situ, most porous, 60 min
1.594 ± 0.213
0.7121 ± 0.244
0.8819 ± 0.0714
sol-gel
20% in situ, most porous, 15 min
3.507 ± 0.213
1.475 ± 0.0339
2.031 ± 0.215
sol-gel
20% in situ, most porous, 30 min
2.515 ± 0.342
1.465 ± 0.122
1.050 ± 0.401
sol-gel
20% in situ, most porous, 45 min
1.877 ± 0.585
1.456 ± 0.269
0.6368 ± 0.215
sol-gel
20% in situ, most porous, 60 min
1.240 ± 0.221
1.319 ± 0.148
0.2555 ± 0.125
sol-gel | Despite significant progress in the synthesis of nanocomposite materials, integration of several components with various functions remains a big challenge, which significantly limits control over nanocomposite properties. The disclosure provides a multifunctional micro particle based on incorporation of titania nanoparticles combined into a porous polylactic acid (PLA) matrix. PLA is used as a biodegradable and biocompatible polymer and titania nanoparticles represent photocatalytically active nanofillers capable of degradation of organic compounds under solar irradiation. Titania nanoparticles are integrated with PLA by using ‘mixed’ and ‘in situ grown’ approaches. The hybrid systems effectively absorbed and degraded organic impurities from water. The sorption capacity, dye degradability, and PLA disintegration were controlled by varying the concentration of incorporated titania. The hybrid degradable systems can be applied as novel non-toxic photocatalytic materials for such as environmental cleanup of contaminated waters. | 1 |
TECHNICAL FIELD
[0001] This disclosure relates to the field of transmission systems. More particularly, the disclosure pertains to a filter assembly.
BACKGROUND
[0002] Automatic transmission fluid serves many functions in a modern automatic transmission. Pressurized fluid may be used to engage friction clutches in order to establish a power flow path with a desired speed ratio. Fluid lubricates gears and bearings. Excess heat is removed by fluid flowing over various components. When the fluid contain contaminants, it may be less effective in these functions and may cause failures such as stuck valves. Therefore, transmissions often include fluid filters.
[0003] Filters may be placed on either the inlet (low pressure) side of a transmission pump or on the outlet (high pressure) side of a transmission pump. Transmission oil filters typically contain a filtration media. The media may be pleated to increase the surface area in a limited space.
SUMMARY OF THE DISCLOSURE
[0004] A transmission includes a filter element, a filter cover, and a filter base. The filter element has a filtration portion and an extension. The filtration portion has side walls defining a top edge and supporting filtration media. The extension is joined to the filtration portion below the filtration media. The filtration portion and the extension define an element bottom edge. A height of the extension may be less than a distance between the filter element bottom edge and a top of the filtration media. The filter cover is in contact with the top edge. The filter cover defines a filter outlet adjacent to the filtration portion. The filter cover also defines a bottom cover edge. The filter base defines a filter inlet adjacent to the extension. The filter base is sealed against the element bottom edge and the cover bottom edge, for example by a single continuous weld. An interior height of the cover may be equal to a distance between the filter element top edge and the filter element bottom edge such that the filter element bottom edge and the cover bottom edge are coplanar. A valve body may extend over the inlet and extend lower than the top edge or lower that a top of the filtration media. The transmission may be filled with transmission fluid such that, when the transmission is inclined, the inlet is below the fluid surface and the filter base adjacent to the filtration portion is above the fluid surface.
[0005] A transmission filter is assembled by placing a cover over an element and joining a base to bottom edges of the cover and of the element with a continuous sealing joint. The cover is placed over the element such that a surface of the cover defining an outlet contacts a top edge of the element to align the bottom edge of the element with a bottom edge of the cover. The element has filtration media extending a first distance above the element bottom edge. The element has an extension with a height relative to the element bottom edge less than the first distance. The base defines an inlet adjacent to the extension.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a schematic diagram of a vehicle transmission.
[0007] FIG. 2 is a cross section of a first oil filter in a transmission sump.
[0008] FIG. 3 is a cross section of a second oil filter in a transmission sump.
[0009] FIG. 4 is a cut-away pictorial view of the second oil filter.
[0010] FIG. 5 is an exploded view of the second oil filter.
[0011] FIG. 6 is a pictorial view of the second oil filter.
DETAILED DESCRIPTION
[0012] Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations.
[0013] FIG. 1 schematically illustrates a transmission hydraulic system. Dash-dot lines indicate mechanical power flow. Solid lines indicate flow of hydraulic fluid. Dashed lines indicate electrical signals. Transmission input shaft 10 is connected to the vehicle crankshaft. Power from the engine is delivered to torque converter 12 which drives turbine shaft 14 . Clutches within gearbox 16 are engaged to establish a power flow path from turbine shaft 14 to output shaft 18 . Different power flow paths having different speed ratios may be established by engaging different clutches. In a rear wheel drive transmission, output shaft 18 is connected to a driveshaft which transmits the power to a rear differential and then to rear wheels. In a four wheel drive vehicle, a transfer case may be installed between the output shaft and the driveshaft to divert a portion of the power to a front differential and then to front wheels. In a front wheel drive vehicle, the output shaft may transmit power to a front differential via gears or a chain.
[0014] Some engine power is diverted to drive transmission pump 20 . Transmission pump 20 draws fluid from sump 22 , through filter 24 , and delivers the fluid, at increased pressure, to valve body 26 . The pressure at which fluid enters the valve body may be called line pressure. Controller 28 commands a network of control valves within the valve body to deliver fluid to torque converter and gearbox components at desired pressures less than line pressure and at desired flow rates. Fluid drains from the control valves and from the gearbox back into sump 22 .
[0015] FIG. 2 is a partial cross section of filter 24 , valve body 26 and sump 22 . When the vehicle is on level ground and either stationary or traveling at constant speed, the top of the fluid in the sump is represented by dotted line 30 . Pump 20 draws the fluid through filter inlet 32 , through filtration media 34 , and through filter outlet 36 . The filtration media may be pleated to increase the surface area within the constrained axial distance available. When the vehicle decelerates or is on a downhill incline, the fluid may move forward in the sump such that the top of the fluid follows dotted line 30 ′. This circumstance does not pose a problem with respect to filter 24 . However, when the vehicle accelerates or goes up a hill such that the top of the fluid follows dotted line 30 ″, the pump may draw air instead of fluid. If this occurs for a brief interval, the air may cause an unpleasant noise. If the situation persists, the transmission may cease to function or become damaged. Moving the filter farther rearward may not be possible due to the space required for the valve body or other transmission components.
[0016] FIGS. 3 and 4 show a revised filter design 24 ′. Modified filter 24 ′ includes an extension channel 38 . The height h of the extension channel permits packaging the extension underneath the valve body 26 . The height h of the extension channel is less than the distance D between the bottom of the filter and the top of the filtration media. Therefore, the filtration media 34 does not extend into the extension channel 38 . Inlet 32 ′ is in the extension channel 38 as opposed to being under the filtration media 34 . In this location, inlet 32 ′ draws fluid regardless of the vehicle acceleration rate or the road incline.
[0017] FIG. 5 illustrates a method of assembling filter 24 ′. The filter is assembled from three parts: a filter element 40 , a cover 42 , and a base 44 . Each of these parts may be made of plastic (except for the filtration media 34 ). Filter element 40 has side walls 46 that define a top edge 48 and a portion of a bottom edge 50 . Top edge 48 and bottom edge 50 are separated by a vertical distance H. The volume surrounded by the side walls is called the filtration portion. The filtration portion is open on both the top and on the bottom. The filtration media 34 is joined to the inner surface of the side walls between the top edge and the bottom edge. An extension extends from one of the side walls below the filtration media. The extension is open on the bottom but closed on the top. The bottom of the extension defines the remainder of the bottom edge of the filter element. The extension portion has a height h which is less than H.
[0018] In a first assembly step, cover 42 is placed over filter element 40 . Cover 42 has side walls 54 which partially define a bottom edge 56 and an extension 58 which defines the remainder of the bottom edge 56 . The extension 58 is open on the bottom and closed on the top. Outlet channel 36 is formed into the top 60 of the cover. The bottom surface of the top 60 is separated from the bottom edge of the cover 56 by the distance H. Consequently, when the cover is placed over the filter element with the top edge 48 of the filter element in contact with the bottom surface of the top of the cover, the bottom edges 50 and 56 of the filter element and the cover respectively are aligned.
[0019] In a second assembly step, the filter element and the cover are placed on the base 44 . The bottom edges 50 and 56 of the filter element and the cover respectively fit tightly against the flat top surface 62 of the base. In a third assembly step, heat is applied to a bottom surface of the base opposite the bottom edges 50 and 56 of the filter element and the cover. This heat momentarily melts the plastic. When the plastic re-hardens, the bottom edges of the filter element and the cover become welded to the base. The heat is applied around the full perimeter to form a continuous weld 64 (visible in FIG. 3 ). In addition to fastening the components, this weld forms a seal which forces any fluid that enters inlet 32 ′to flow through filter media 34 before exiting outlet 36 . Alternatively, this continuous, sealing joint could be formed by adhesive. The completed filter is shown in FIG. 6 .
[0020] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the invention that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. As such, embodiments described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics are not outside the scope of the disclosure and can be desirable for particular applications. | A transmission oil filter is assembled from a filter element, a base, and a cover. Each of the three pieces extends beyond the filtration media to form an inlet channel. The inlet channel is low enough to fit under a valve body. Placing the inlet in this channel ensures that the inlet draws transmission fluid at road gradients and acceleration rates at which an inlet under the filtration media would draw air. | 5 |
[0001] This invention relates to a method of generating heat for use in a heating system and in particular a domestic heating system.
[0002] It is well known that many chemical reactions are exothermic, i.e. they produce heat, and examples of such reactions include acid-base reactions.
[0003] The present invention makes use of a controlled exothermic reaction to produce heat which is then exchanged in a heat exchanger to provide a usable source of heat for heating a fluid such as the water in a domestic water supply.
[0004] Accordingly, in a first aspect, the invention provides a method for producing a supply of a heated fluid, which method comprises passing the fluid through a heat exchanger unit where it is heated by a heat source; characterised in that the heat source derives heat from the exothermic reaction of two or more chemical reactants.
[0005] The exothermic reaction may take place inside a reactor within the heat exchanger. Alternatively, the reactants may be mixed together in a vessel that is separate from the heat exchanger unit, and a stream of the mixed reactants and/or their reaction products may be passed through the heat exchanger to serve as the heat source.
[0006] In one embodiment, the invention provides a method for producing a supply of a heated fluid, which method comprises passing the fluid through a heat exchanger unit, wherein the heat exchanger unit comprises:
(a) a heat exchanger element through which the fluid may flow; (b) a reaction chamber having at least one inlet through which reactants may be introduced into the reaction chamber, and at least one outlet through which spent reactant may be removed from the reaction chamber; (c) a first dosing unit for introducing a controlled amount of a first reactant through an inlet into the reaction chamber; and (d) a second dosing unit for introducing a controlled amount of a second reactant through an inlet into the reaction chamber;
wherein the first and second reactants react exothermically and the heat thereby produced is exchanged with the fluid passing through the heat exchanger element, the introduction of the first and second reactants into the reaction chamber being controlled to produce a required level of heating.
[0011] The fluid can be a gas or a liquid.
[0012] In one embodiment, the fluid is a gas.
[0013] In another embodiment, the fluid is a liquid, one particular example of which is water.
[0014] The heat exchanger element is in thermal contact with the reaction chamber. In one embodiment, the heat exchanger element passes through the reaction chamber. For example, the heat exchanger element can take the form of a pipe passing through the reaction chamber.
[0015] It will be appreciated that the fluid does not come into contact with the reactants.
[0016] The reaction chamber has at least one inlet and at least one outlet. Each reactant may be provided with its own inlet. Alternatively, a pre-mixing chamber may be provided into which the first and second reactants are introduced prior to introducing them into the reaction chamber. It is preferred, however, that each reactant has its own inlet.
[0017] Dosing units are provided for introducing the first and second reactants into the reaction chamber in a controlled manner so as to produce a required level of heating. Each dosing unit can take the form of a container (e.g. a hopper or a tank) having an aperture that may be opened or closed to permit a reactant to move towards the reaction chamber. The or each reactant can be conveyed to the reaction chamber by means of a gravity feed. Alternatively or additionally, a pump or other conveying device (e.g. an auger or screw) may be used.
[0018] One or more sensors may be provided for measuring the temperature of the fluid when it exits the heat exchanger. The sensors are typically connected to a controller which may in turn be connected to the dosing units and/or a valve at each inlet into the reaction chamber. Sensors may also be provided for monitoring the rate of flow of reactants into the reaction chamber.
[0019] One or more reaction monitoring sensors may also be provided for monitoring the extent of reaction between the reactants. A reaction monitoring sensor (which may be for example a pH sensor) may be disposed in the vicinity of, or at, the or each outlet to determine whether or not the reaction between the reactants has been completed. The reaction monitoring sensor may be linked to the controller and/or directly to a valve or other closure device closing each outlet. The valve or other closure device may be actuated to an open position in response to a signal from the reaction monitoring sensor or the controller to allow spent reactant to exit the reaction chamber.
[0020] In each of the foregoing aspects and embodiments of the invention, the reactants (e.g. the first and second reactants) are preferably an acid and a base respectively.
[0021] The acid and base are preferably selected and/or formulated so as to provide an extended reaction time thereby giving a more prolonged release of heat.
[0022] Particular examples of acids are those having a pKa value of >0, more typically >2 and preferably >3, e.g. a pKa in the range 3 to 7. Where the acid is polybasic (e.g. citric acid), the foregoing limits refer to the first ionisation).
[0023] Particular acids are polybasic acids.
[0024] A preferred acid is citric acid.
[0025] Examples of bases are those having a pKb value of >0, more typically >2 and preferably >3, e.g. a pKb in the range 3 to 7.
[0026] Particular bases are basic amines and in particular mono-, di- and trialkylamines. The bases, particularly the more volatile amines such as ethylamine (boiling point 16.6° C.) may be provided in the form of an aqueous solution or a gel.
[0027] One group of preferred bases consists of mono-, di- and trialkylamines in which each alkyl group contains from 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms and most preferably 1 or 2 carbon atoms. Such bases include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine. Other bases that may be used include alkali metal hydroxides such as sodium hydroxide (caustic soda) and carbonates such as sodium carbonate
[0028] A particularly preferred base is ethylamine, for example in the form of a 50-70% aqueous solution or gel.
[0029] The acid and base and/or their physical form are selected so that when they are mixed (e.g. introduced into the reaction chamber), they provide a sustained release of heat rather than a rapid sudden increase in temperature followed by a similarly rapid fall in temperature. The sustained release of heat may be achieved by using relatively weak acids or bases that react relatively slowly. Alternatively, or additionally, the acid and/or the base may be formulated and/or presented in a physical form whereby reaction between them is slowed down. For example, depending on the natural physical state of the acid and the base, they may be introduced in the form of coated particles (e.g. coated powders or granules) or gels in which the coatings or gel components slow down the reaction between the acid and bases.
[0030] In one embodiment, the base may be in liquid or gel form and the acid may be in solid form. One such combination of acid and base is the combination of citric acid in solid form and aqueous ethylamine.
[0031] In another embodiment, the base is in solid form and the acid is in liquid form.
[0032] The reaction between the acid and the base may be carried out in the absence of water or in the presence of water. In one embodiment, no water is added to the reaction mixture.
[0033] In one preferred mode of operation, where a reaction chamber forms part of the heat exchanger, metered amounts of the first and second reactants are introduced into reaction chamber and the temperature of the fluid (e.g. water) emerging from the heat exchanger is monitored, further metered amounts of the first and/or second reactants being introduced once the temperature of the fluid falls below a predetermined FIGURE.
[0034] In a further aspect, the invention provides a heat exchanger unit for heating a fluid, the heat exchanger unit comprising:
(a) a heat exchanger element through which the fluid may flow; (b) a reaction chamber having at least one inlet through which reactants may be introduced into the reaction chamber, and at least one outlet through which spent reactant may be removed from the reaction chamber; (c) a first dosing unit for introducing a controlled amount of a first reactant through an inlet into the reaction chamber; and (d) a second dosing unit for introducing a controlled amount of a second reactant through an inlet into the reaction chamber; and optionally (e) one or more sensors for (i) monitoring a parameter indicative of the completeness of the reaction between the reactants; and/or (ii) the temperature of the fluid and/or (iii) the rate of flow of reactants into the reaction chamber; and (f) a controller operatively linked to the one or more sensors for controlling flow of reactants into the chamber and flow of spent reactant out of the chamber.
[0041] The invention will now be illustrated in more detail (but not limited) by reference to the specific embodiment shown in the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
[0042] FIG. 1 is a schematic view of an apparatus according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0043] As shown in FIG. 1 , an apparatus for producing heat according to the method of the invention takes the form of a heat exchanger 2 comprising an insulated reaction chamber 4 and a heat exchanger element 6 in the form of a pipe for carrying water through the reaction chamber. The pipe may form part of a domestic water heating system and may be, for example linked to radiators or a hot water tank, or directly to a hot water tap. The pipe may also be insulated.
[0044] The reaction chamber has a pair of inlets 7 and 9 fed by inlet tubes 8 and 10 that are linked to hoppers 12 and 14 . Control valves (not shown) are present in the inlet tubes to control the flow of reactants to the reaction chamber. The first hopper 12 contains a first reactant which may be, for example, powdered citric acid. The second hopper contains a second reactant which may be, for example, aqueous ethylamine or sodium carbonate. The functioning of the apparatus will be described below with reference to citric acid and aqueous ethylamine but it is to be understood that other acids and bases, and indeed other exothermal reaction couples, could be used instead.
[0045] Each of the inlet tubes 8 and 10 has a dosing sensor 13 , 15 , the purpose of which is to monitor the amounts of reactants entering the chamber. At the lower end of the reaction chamber is an outlet 16 which contains a filter to prevent larger particles of spent reactant from passing into the waste pipe. Arranged immediately above the outlet is a sensor 18 for measuring the pH of the reaction mixture. The outlet 16 is connected to a waste pipe 24 that carries spent reactants to a waste storage container (not shown).
[0046] In use, water (e.g. forming part of a domestic water supply) is pumped through the pipe 6 in the direction of the arrows. Citric acid in fluid form is gravity fed from the hopper 12 through the inlet tube 8 and inlet 7 into the reaction chamber 4 . The quantity of citric acid introduced is measured by the dosing sensor 13 and the flow from the hopper is stopped by means of a valve once a predetermined amount of citric acid has passed into the reaction chamber 4 . At the same time (or sequentially before or after the citric acid has been introduced), 50-70% aqueous ethylamine or an ethylamine-containing gel or sodium carbonate is fed from the hopper 14 through inlet tube 10 and inlet 9 into the reaction chamber 4 . It is preferred that an excess of ethylamine is used so that the reaction mixture is in the form of a slurry thereby facilitating flow of the mixture through the reaction chamber towards the outlet. The citric acid reacts exothermically with the ethylamine to form a fluid. The heat given out by the reaction causes the contents of the reaction chamber to increase in temperature and, consequently, water passing through the pipe 6 is heated. Using the combination of citric acid and aqueous ethylamine, it has been found that a combined weight of 300 g of reactants produces an output of 1 kW and was able to heat 15 litres of water by 1° C. over a 5 hour period. Typically the heating effect available from a single charge of citric acid and single charge of ethylamine lasts between 4 hours and 24 hours.
[0047] The reaction chamber can be topped up with further charges of citric acid and aqueous ethylamine as necessary. A temperature gauge may be positioned in the pipe 6 downstream of the heat exchanger to monitor the temperature of the water. The temperature gauge may be linked to the controller 20 . When the temperature falls below a predetermined value, the controller may actuate valves not (shown) to cause further charges of the citric acid and aqueous ethylamine to be introduced into the reaction chamber.
[0048] An advantage of using citric acid and aqueous ethylamine as the reactants is that the citric acid is a naturally occurring substance and hence is available from renewable sources. The ethylamine, whilst not commercially available from natural sources, can be subsequently be regenerated from the citrate salt isolated as the waste product from the reaction.
[0049] The heating method and apparatus of the invention can be used in situations where conventional energy sources for heating water are not available or may be used to supplement conventional energy sources. The only waste product from the method is a water soluble fluid or slurry that can be collected and taken away either for disposal or for recycling.
[0050] The embodiment illustrated in FIG. 1 represents merely one way of putting the invention into effect and it will readily be apparent that numerous modifications and alterations may be made to the specific embodiment shown without departing from the principles underlying the invention. All such modifications and alterations are intended to be embraced by this application. | The invention provides a method for producing a supply of a heated fluid, which method comprises passing the fluid through a heat exchanger unit ( 2 ) where it is heated by a heat source ( 4 ); characterised in that the heat source ( 4 ) derives heat from the exothermic reaction of two or more chemical reactants. The chemical reactants are preferably an acid and a base. | 5 |
This application claims priority from U.S. provisional patent application Ser. No. 60/552,963, filed Mar. 12, 2004, entitled “SEGMENTED SQUEEGEE FOR STENCILING” and, the disclosure of which is incorporated herein, in its entirety, by reference.
FIELD OF THE INVENTION
The present invention generally relates to the use of squeegees in the production of printed wiring boards (“PWBs”), and more particularly to an apparatus and method for utilizing a segmented squeegee on PWBs.
BACKGROUND OF THE RELATED ART
The production of PWBs includes a variety of techniques to deposit solder paste on a substrate. One method of depositing solder paste includes stenciling. This method includes the use of a stencil with cutouts in the stencil corresponding to the desired solder pattern for a PWB. The stencil, typically constructed of metal, is applied to the surface of a PWB and solder paste is applied to the stencil. A straight, rigid edge element, commonly referred to as a squeegee, is pressed down on the stencil and is wiped or moved across the stencil to deposit an even, smooth portion of solder paste into the cutouts of the stencil. Once the squeegee and stencil are removed, a solder pattern is left behind on the PWB.
The print quality of the PWB depends on the consistency of the dimensions and thickness of the solder paste after deposition. The dimensions and the patterns of the stencil in the stenciling process typically control the amount and thickness of the deposited solder paste. However, accurate deposition of the solder paste requires the stencil to be flush or in contact with the surface of the PWB as solder paste is deposited. Typically, the stencil is forced into contact with the PWB by the squeegee during the stenciling process.
Unfortunately, the non-coplanarity of PWBs significantly affects the print quality of the stenciling process because contact between the stencil and the PWB cannot be maintained during the stenciling process. As shown in FIG. 1 , despite downward pressure from the squeegee, the stencil may not remain in contact with the PWB during stenciling if the warpage or non-coplanarity creates valleys or low lying depressions. As a result, printing quality may be insufficient to meet minimum standards, which results in additional production costs, repetition of work, and increased use and wear on production equipment.
The effect on print quality is particularly problematic for large PWBs. As the size of the PWB grows, the warpage or non-coplanarity typically worsens. This makes stenciling on large sized PWBs difficult with conventional equipment. Unfortunately, most large sized boards contain warpage and non-coplanarity characteristics that are incompatible with the use of conventional equipment, even if the boards meet standard specifications (0.75% max warpage per inch), such as IPC-2221 for surface mount technology.
The conventional equipment available for stenciling solder paste or adhesives on large size PWBs, such as boards greater than 18×24 inches, includes a metal stencil and a long, straight, rigid squeegee. The conventional squeegee is typically greater than 18 inches long and constructed from metal, generally stainless steel.
Stenciling large sized PWBs using a conventional long, straight squeegee results in unacceptable print quality because the squeegee is incapable of conforming to the non-coplanarity of the large sized boards. For example, as solder paste is spread over the stencil, a long, straight, rigid squeegee rides on the peaks of a warped large sized board without adequately pressing into the low lying areas of the board. As a result, conventional squeegees inadequately maintain contact between the stencil and the surface of the PWB. Consequently, deposition of solder paste onto low lying areas of a warped large sized board is inconsistent and insufficient to meet minimum print quality.
In previous attempts to overcome non-coplanarity have included increasing the downward pressure from the squeegee, using a flexible squeegee, and even trying to improve the coplanarity requirements on PWBs. Unfortunately, increased pressure from the squeegee results in damage to the stencil and the underlying PWB during the stenciling process. Further, increased pressure and friction between the stencil and squeegee results in significantly increased wear of and increased replacement of stenciling equipment.
Another attempt includes the use of flexible squeegees, which provide some ability to conform to the contours of the PWB. However, flexible squeegees are significantly less durable and more difficult to clean. While rigid squeegees provide a durable and consistent edge, which is necessary for uniform and accurate solder deposition, flexible squeegees have edges that degrade quickly under repeated use and cleaning.
Finally, attempts to require more consistent and coplanar PWBs are not practical for large sized PWBs. The increased cost of producing PWB with greater copalanarity is prohibitive, especially due to the fact that much of the warpage of the PWB is due to local heating and cooling during subsequent processing of the PWB.
Therefore, there exists a need for a squeegee capable of improving PWB print quality and compensating for the non-coplanar characteristics of large sized boards.
SUMMARY OF THE INVENTION
One embodiment of the present invention generally relates to a squeegee assembly for applying a medium to a surface. The squeegee assembly includes a plurality of squeegee segments and a support structure. The plurality of squeegee segments and the support structure are joined by a plurality of independent linkages.
Another embodiment of the present invention relates to a configuration of the squeegee segments. The squeegee segments are positioned in a staggered and overlapped configuration. The squeegee segments allow excess solder paste to be transferred across the stencil in the squeegee direction and in a substantially perpendicular direction to the squeegee direction.
Another embodiment of the present invention relates to a method of stenciling a medium onto a top surface of a substrate. The method steps include positioning a stencil on the substrate, such that the bottom surface of the stencil is in substantial contact with the top surface of the substrate and applying solder paste to the top surface of the stencil. The method also includes squeegeeing the top surface of the stencil with a plurality of independent squeegee segments in a predetermined direction and maintaining substantial contact, beneath each of the plurality of independent squeegee segments, between the bottom surface of the stencil and the top surface of the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming the present invention, it may be believed the same will be better understood from the following description taken in conjunction with the accompanying drawings, which illustrate, in a non-limiting fashion, the best mode presently contemplated for carrying out the present invention, and in which like reference numerals designate like parts throughout the figures, wherein:
FIG. 1 is a front view of a prior art stencil and squeegee assembly;
FIG. 2 is a front view of a segmented squeegee and stencil according to one embodiment of the present invention;
FIG. 3 is a top view of a segmented squeegee and stencil according to one embodiment of the present invention;
FIG. 4 is a detailed front view of a squeegee segment according to one embodiment of the present invention; and
FIG. 5 is a detailed side view of a squeegee segment according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
For simplicity and illustrative purposes, the principles of the present invention are described by referring mainly to exemplary embodiments thereof. However, one of ordinary skill in the art would readily recognize that the same principles are equally applicable to, and can be implemented in, many types of printing or stenciling processes and that any such variations do not depart from the true spirit and scope of the present invention. Moreover, in the following detailed description, references are made to the accompanying figures, which illustrate specific embodiments. Electrical, mechanical, logical and structural changes may be made to the embodiments without departing from the spirit and scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense and the scope of the present invention is defined by the appended claims and their equivalents.
In FIG. 1 , a prior art embodiment of a conventional stenciling assembly is shown. The conventional stenciling assembly includes a straight, long squeegee 10 held by a support structure 15 and a support link 30 . Due to the structural demands and the need to wash and clean the equipment, the support structure 15 , support link 30 , and long squeegee 10 typically are constructed from a strong rigid material such as steel.
The conventional stenciling assembly shown in FIG. 1 illustrates an example of the disadvantages of the long squeegee 10 . As shown, PWBs 50 is warped such that the two sides of the PWB 50 are raised with a low lying valley in the center. Accordingly, a gap 52 between the PWB 50 and the squeegee 10 may be present during deposition of the solder paste 70 . The conventional squeegee 10 is incapable of bending or flexing with the PWB 50 . As a result, the stencil 60 does not remain in contact with the surface of the PWB 50 during deposition of solder paste 70 .
The stencil 60 typically controls the thickness and pattern of solder paste 70 deposited on the PWB 50 . As shown in FIG. 1 , the center of the PWB 50 and the stencil 60 are not in contact due to the warpage and the gap 52 . Accordingly, the amount of solder paste 70 deposited on the center of the PWB 50 may be sporadic or inconsistent with the outer sides of the PWB 50 . The inconsistency may range from only slight deposition of solder paste 70 to complete lack of deposition of solder paste 70 in the low lying sections of a warped PWB 50 .
Due to the concentration of stresses on the high sections of a warped PWB 50 (shown as the outer sides in FIG. 1 ), deposition of solder paste on high sections of the PWB 50 may also be too thin or otherwise inconsistent. Even slight inconsistencies in the application of solder paste 70 on a PWB 50 may be unacceptable in certain applications such as high reliability systems for space applications and/or military applications. As a result, the use of conventional stenciling equipment on large PWBs increases production costs through unnecessary repeated use and wear of equipment and low quality control.
It should be understood that the non-coplanarity of the PWB 50 shown in FIG. 1 is only an example. As would be obvious to one of ordinary skill, large sized PWBs may be warped in many different configurations to which the application of the present invention is intended to apply. For example, the PWB may be warped in the opposite direction of that shown in FIG. 1 with two sides that are lower than a high section in the center. Further, a single PWB may include multiple high sections and/or multiple low lying sections.
Referring now to FIG. 2 , a segmented squeegee stenciling system according to one embodiment of the present invention is shown in a front view. As with the conventional system of FIG. 1 , a support structure 20 provides the structural foundation for the squeegee during the stenciling process. However, instead of having a single long rigid squeegee 10 , the embodiment of the present invention shown in FIG. 2 includes squeegee elements or segments 100 A, 100 B, 100 C, and 100 D.
Each of the squeegee segments 100 A, 100 B, 100 C, and 100 D are connected to the support structure 20 with a mechanical linkage or connection 105 . The linkage 105 includes a lower beam or lower squeegee holder 110 , a hinge or flexible joint 120 , a upper beam or upper squeegee holder 130 , and a biasing member 140 . The segmented squeegee assembly connects via a bracket or connector 80 to a transmission or motor for moving the segmented squeegee assembly during the process of stenciling. It should be noted that the linkages 105 are independent and permit independent movement of each of the squeegee segments 100 A, 100 B, 100 C, and 100 D.
The squeegee segments 100 A, 100 B, 100 C, and 100 D and their independent movement allow for each segment to exert independent forces and individually apply the soldering paste 70 . Because each segment is responsible for a smaller section of the stencil 60 and the PWB 50 , less force may be required to maintain contact between the stencil 60 and the PWB 50 . This may reduce the total amount of force required and reduce the amount of stress applied to the stencil 60 and the PWB 50 during the stenciling process. Further, the reduced total force may decrease the wear on the squeegee and stencil, prolonging the usable life of the components.
The biasing member 140 biases each of the squeegee segments 100 A, 100 B, 100 C, and 100 D such that the squeegee segments 100 A, 100 B, 100 C, and 100 D conform to the surface of the PWB 50 as shown in FIG. 2 . The hinges 120 allow the squeegee segments 100 A, 100 B, 100 C, and 100 D to rotate and align the flat surface of the squeegee segments 100 A, 100 B, 100 C, and 100 D with the localized surface of the PWB 50 under each squeegee segment. The squeegee segments 100 A, 100 B, 100 C, and 100 D, as shown in FIG. 2 , are configured to independently maintain contact between the stencil 60 and the PWB 50 despite the curvature of the PWB 50 .
The individual squeegee segments 100 A, 100 B, 100 C, and 100 D are shorter in length than the conventional squeegee 10 , allowing the smaller squeegee segments to press down, between the high sections of the PWB 50 , into the low-lying areas. By comparison, the long squeegee 10 , as shown in FIG. 1 , rests on the outer sides of the PWB 50 without extending down to the gap 52 .
FIG. 2 also illustrates how the squeegee segments 100 A, 100 B, 100 C, and 100 D impart consistent downward forces on the stencil 60 and the PWB 50 despite whether or not the squeegee segments fall on high sections or low sections of the PWB 50 . Because of the independent action of the squeegee segments of the present invention, the stencil 60 maintains contact with the curvature of the PWB 50 during the process of solder paste deposition without forcing the PWB 50 to flex or change shape during stenciling. The biasing member 140 and the hinge 120 may apply a downward force on each of the squeegee segments 100 A, 100 B, 100 C, and 100 D to locally press the stencil 60 onto the PWB 50 . By maintaining contact between the stencil 60 and any low-lying areas of the PWB 50 , the consistency of the deposition of the solder paste 70 may be improved without additional localized stress on the high sections of the PWB.
The support structure 20 is illustrated as a solid plate approximately the same width as the squeegee segments 100 A, 100 B, 100 C, and 100 D. However, the support structure 20 may include hollow structures, beams, tubes, or other structures known to one skilled in the art so long as the structure is capable of withstanding the forces exerted through connector 80 and supporting the squeegee segments 100 A, 100 B, 100 C, and 100 D. The support structure 20 must also be sufficiently stiff such that the support structure 20 may react against the biasing members 140 during the stenciling process in order to press the stencil 60 into contact with the surface of the PWB 50 and to maintain consistent contact as the support structure 20 moves.
It should be noted that the hinge or joint 120 and the biasing member 140 are configured to provide each of the squeegee segments 100 A, 100 B, 100 C, and 100 D with two degrees of freedom of motion. The first degree of freedom includes vertical movement up and down with the biasing member 140 forcing the squeegee segments in a downward direction. The second degree of freedom includes angular movement about the joint or pivot point 120 .
The two degrees of freedom of motion enables each of the squeegee segments 100 A, 100 B, 100 C, and 100 D to engage to PWB 50 with as little gap between the squeegee segments 100 A, 100 B, 100 C, and 100 D and the PWB 50 as possible. For example, in FIG. 2 , the squeegee segment 100 A engages the PWB 50 at an angle with the right hand side of the squeegee segment 100 A engaging the PWB 50 at a higher point that the left hand. The squeegee segment 100 A rotates about the joint 120 to achieve the orientation shown.
The biasing member 140 provides the ability to for the squeegee segments 100 A, 100 B, 100 C, and 100 D to apply consistent downward forces and to engage the PWB 50 at different elevations as seen in FIG. 2 . For example, the squeegee segments 100 B and 100 C extend further into the low-lying areas in the center of the PWB 50 . The squeegee segments 100 A, 100 B, 100 C, and 100 D may be capable of about 0.010 inches of vertical travel and about 2 degrees of rotation about the flexible joint 120 .
Referring now to FIG. 3 , the configuration of the squeegee segments 100 A, 100 B, 100 C, and 100 D according to an embodiment of the present invention is shown in a top view. The squeegee segments 100 A, 100 B, 100 C, and 100 D may be configured into a staggered and overlapped configuration. The squeegee segments may be moved across the stencil 60 and the PWB 50 in the direction shown as arrow A in FIG. 3 . This staggered and overlapped configuration allows excess solder paste to be transferred across the stencil 60 in the direction of arrow A and in a direction perpendicular to arrow A. The staggered and overlapped configuration also allows the squeegee segments 100 A, 100 B, 100 C, and 100 D to individually interact with the PWB surface without interference with other segments to remove excess solder paste without leaving streaks or solder clumps.
The staggered and overlapped configuration also improves consistency by continuously removing excess solder paste forward and to the side of the PWB 50 during the stenciling process. While the prior art allows solder paste to clump and build up in front of the single squeegee 10 , the staggered and overlapped configuration directs clumps and excess solder paste to the side. This may reduce solder paste clumps and excess accumulation from creating divots or other inconsistencies in the solder paste as the squeegee segments pass over the deposition patterns in the stencil 60 .
The staggered and overlapped configuration of the squeegee segments 100 A, 100 B, 100 C, and 100 D includes each of the squeegee segments 100 A, 100 B, 100 C, and 100 D being angularly disposed from the direction of arrow A. The angle of each squeegee segment 100 A, 100 B, 100 C, and 100 D, as shown in FIG. 3 , directs (as a function of squeegee speed) excess solder paste 70 toward the top of FIG. 3 as the squeegee assembly travels in the direction of arrow A. It should be noted that, although the squeegee segments are allowed to rotate about hinge 120 as shown in FIG. 2 , the angular position of the squeegee segments 100 A, 100 B, 100 C, and 100 D as shown in FIG. 3 may be substantially fixed. These angular positions allow the staggered and overlapped configuration to drive excess solder paste to the side of the PWB 50 without allowing clumps to be left behind by the squeegee or to excessively build up on the squeegee during stenciling.
As solder paste 70 is pushed forward and to the side by the angular position of the squeegee segments 100 A, 100 B, 100 C, and 100 D, some amount of solder paste 70 falls to the side of each squeegee segment and is left behind. To avoid any solder paste 70 being left behind on the stencil 60 , the squeegee segments 100 A, 100 B, 100 C, and 100 D are staggered and overlapped. The squeegee segments 100 A, 100 B, 100 C, and 100 D are staggered in the direction of arrow A with squeegee segment 100 A being position behind squeegee segment 100 B. Likewise, squeegee segment 100 B is behind squeegee segment 100 C, which is behind squeegee segment 100 D. Further, the squeegee segments are overlapped as shown by the overlap 150 between squeegee segments 100 A and 100 B.
The overlap 150 and staggered positioning allows for the staggered and overlapped configuration where each squeegee segment picks up the solder paste 70 left behind by the squeegee segment in front. This staggered and overlapped effect provides a stenciling process that avoids leaving solder paste clumps behind and avoids having excessive build up of solder paste on the squeegee segments 100 A, 100 B, 100 C, and 100 D during stenciling. The squeegee segment 100 A pushes excess solder paste 70 to the side of the stencil 60 and away from the PWB 50 . Then, the excess solder paste 70 may be easily cleaned or removed without affecting the PWB 50 under the stencil 60 .
It should be noted that the squeegee segments 100 A, 100 B, 100 C, and 100 D provide independent action between the segments such that each segment can maintain contact, through the stencil, with the PWB as the squeegee segments are wiped across the stencil in the direction of arrow A. As opposed to the conventional squeegee 10 and the gap 52 , the squeegee segments 100 A, 100 B, 100 C, and 100 D may eliminate a substantial amount of gap 52 , as shown in FIG. 1 , and minimize any gap under the individual segments. By reducing any gaps between the PWB 50 and the stencil 60 , the squeegee segments 100 A, 100 B, 100 C, and 100 D may reduce the uneven or inconsistent deposition of solder paste 70 .
FIG. 3 illustrates one embodiment of the staggered and overlapped configuration according to the present invention. However, the staggered and overlapped configuration of the squeegee segments may be changed or reconfigured without deviating from the true spirit and scope of the present invention. The angular position of the squeegee segments 100 A, 100 B, 100 C, and 100 D may be varied or even reversed such that the squeegee segments 100 A, 100 B, 100 C, and 100 D work in concert to drive the solder paste 70 forward and to either side or even both sides of the PWB 50 .
FIG. 3 also shows the squeegee segment 100 D as the most forward squeegee segment in the configuration. However, squeegee segment 100 A may be positioned to in the most forward position with the squeegee segments 100 B, 100 C, and 100 D staggered in the opposite direction of that shown in FIG. 3 . It is also contemplated that the configuration of the squeegee segments could represent an arrowhead shape where the squeegee segments push solder paste to both sides of the stencil 60 .
It is important to note that the configuration of the squeegee segments 100 A, 100 B, 100 C, and 100 D as shown in FIGS. 2 and 3 is only representative in nature. The number of the squeegee segments may be more or less depending on the individual size of the squeegee segments, the type of staggered and overlapped configuration, and the overall size of the stencil. Although the squeegee segments are shown having identical shape and size, the squeegee segments may be shaped and sized differently, especially to avoid squeegee segment edges from passing over sensitive components of the PWB 50 and/or cutouts in the stencil 60 .
Referring now to FIG. 4 , a detail front view of the mechanical linkage 105 is shown. The link 105 connects the squeegee segments 100 A, 100 B, 100 C, and 100 D with the support structure 20 . The biasing member 140 is fastened to the support structure 20 and to the upper squeegee holder 130 . The biasing member 140 biases the upper squeegee holder 130 in a downward direction such that the squeegee segments 100 A, 100 B, 100 C, and 100 D may be biased against the stencil 60 and the PWB 50 .
FIG. 5 illustrates a cross sectional view of the upper squeegee holder 130 , the hinge 120 , the lower squeegee holder 110 and the squeegee segment 100 A. The pin 122 is shown passing through the upper and lower squeegee holders and creating the hinge 120 .
The lower squeegee holder 110 and the upper squeegee holder 130 are joined by a hinge or joint 120 . As shown in FIG. 4 , the hinge 120 includes an end of the upper squeegee holder 130 and an end of the lower squeegee holder 110 with a hole in each. A pin 122 is placed through the holes in the upper and low squeegee holders 110 and 130 such that the lower squeegee holder 110 and the squeegee segment 100 A can rotate about the pin 122 .
Although, the hinge 120 is shown in FIGS. 4 and 5 as a standard hinge, the hinge 120 may include many different types of rotating members or joints and be constructed from many different methods known to those skilled in the art. It is also contemplated that in other embodiments the connection between the upper and lower squeegee holders may not have any moving parts but may include flexible material that is designed or constructed to flex in the same direction as the hinge shown in FIG. 4 but to be stiff in other directions. The upper and lower squeegee holders may also be a single element with a flexible or weakened section representing the hinge 120 .
In FIGS. 4 and 5 , the hinge 120 is shown positioned equally between the biasing member 140 and the squeegee segment 100 A. However, the hinge 120 may be positioned at different heights. The hinge 120 may also be mounted directly to the biasing member 140 or the squeegee segment 100 A such that one of the upper or lower squeegee holders may no longer be needed.
The biasing member 140 is shown as a common commercially available coil spring and is made up of spring steel. The biasing member 140 accommodates an up-down movement of the holder 130 as the squeegee segments 100 A, 100 B, 100 C, and 100 D follow the height of the PWB surface. This up-down movement is typically less than 0.010 inch. An alignment pin (not shown) may be used to prevent the squeegee segments 100 A, 100 B, 100 C, and 100 D from rotating about the axis of the upper squeegee holder 130 due to the flexibility of the biasing member 140 . As would be obvious to one of ordinary skill, the alignment pin may engage the support structure 20 and the upper squeegee holder 130 as necessary to control any squeegee segment rotation about the axis of the upper squeegee holder 130 and to maintain the squeegee segment orientation as shown in FIG. 3 . Although the biasing member is shown as a common coil spring, the biasing means may also be accomplished using other springs and elements as would be obvious to one of ordinary skill. For example, the biasing member 140 may be commercially available hard (shore D 40 to 80) rubber bumpers, or beryllium-copper springs.
Although the embodiment shown in FIGS. 2-5 is directed toward the deposition of solder paste on a PWB, the segmented squeegee assembly described may be used to deposit controlled amounts of other mediums. For example, the present invention may be used to deposit adhesives dots on PWBs or to deposit controlled amounts of fill material in vias, i.e. holes in PWBs.
While the invention has been described with reference to the exemplary embodiments thereof, those skilled in the art will be able to make various modifications to the described embodiments without departing from the true spirit and scope. The terms and descriptions used herein are set forth by way of illustration only and are not meant as limitations. In particular, although the method has been described by examples, the steps of the method may be performed in a different order than illustrated or simultaneously. Those skilled in the art will recognize that these and other variations are possible within the spirit and scope as defined in the following claims and their equivalents. | The present invention relates to a segmented squeegee for depositing a medium onto a surface, such as depositing solder paste onto a printed wiring board. The segmented squeegee may include a plurality of independent squeegee segments or elements, a support structure and a plurality of independent connections or linkages connecting the squeegee segments to the support structure. The segmented squeegee may be used in connection with a conventional stencil such that the independent linkages and the squeegee segments may be structured and arranged to maintain substantial contact between the stencil and the printed wiring board. | 1 |
BACKGROUND
Procaterol has the chemical name 8-hydroxy-5]1-hydroxy-2-(1-methylethyl)amino]butyl]-2-(1H)-quinolone. It is known as a bronchodilator and has selective beta-adrenergic agonist activity. The compound and its preparation are described in U.S. Pat. No. 4,026,897, which is hereby incorporated by reference.
While the drug is highly efficacious, its use is subject to such problems as dose dumping and high drug usage requirements.
THE INVENTION
It has been discovered that procaterol and pharmaceutically acceptable salts thereof can be administered via the use of a transdermal system.
In a preferred embodiment, procaterol HCl is combined with linoleic acid, propylene glycol, triacetin, Wickenol R535, and Aerosil R200 to produce a gel composition which is used in combination with a barrier membrane as part of a multilaminated product to deliver the drug transmembranally, e.g., transdermally, to a subject.
ADVANTAGES
The delivery system of the invention has several advantages over other procaterol-based formulations. The gastrointestinal problems often associated with some drugs which are administered orally are eliminated.
The gradual release of the drug via membranal tissue, e.g., on the skin or in the nasal passage(s), minimizes the risk of dose dumping and other side effects.
In addition, the use of the instant system would result in a reduction in overall drug loading dose.
Furthermore, a patch or other transdermal device serves as a reminder to the patient to administer the proper dosage.
These and other advantages of the invention will become apparent upon consideration of the following description of the invention.
DESCRIPTION OF THE INVENTION
The invention deals with:
a device used to administer compositions through living cutaneous tissue, e.g., a patch. Such a device is preferably a multilayer laminate comprising
(a) an impermeable backing whose perimeter contains an adhesive;
(b) a composition of a drug component admixed in a gel or saturated sponge layered on the inside of the backing;
(c) a barrier membrane covering the composition, and
(d) a release liner covering the barrier membrane.
The barrier membrane used in such a device is generally a porous plastic material having a thickness of about 0.01 to about 0.08, preferably 0.02 to 0.04 mm.
Suitable plastic materials include those which are chemically inert to the components of the composition.
Thus, polyolefins, e.g., polypropylene, polyethylene, and polyesters, e.g., polyethylene terephthalate, or nylon are operable. Polypropylene is preferred. Blends of plastics are operable.
The impermeable backing to be used to support the composition and porous membrane layers should be about 2 mil to about 5 mil in thickness. It should be a strong, yet flexible material so that a bandage, foil, or other suitable supportive structure could be fashioned using it. Suitable materials include aluminum, metallized polyester, polyurethane, polyethylene, and the like.
The perimeter of the impermeable backing contains a silicone or acrylic medicinal grade adhesive laminate on the backing for sticking to cutaneous tissue.
The release liner which covers and holds in place both the drug gel (drug in the transmembranal composition) and the barrier membrane, is made of polyethylene or silicone coated film. The release liner is removed when placing the device or patch onto cutaneous tissue.
The composition or drug gel suitable for the transmembranal administration of procaterol contains:
(a) about 0.1 to about 5 weight percent procaterol or a pharmaceutically acceptable salt thereof,
(b) about 5 to about 30 weight percent of an essential acid;
(c) about 15 to about 40 weight percent of a solvent for (a), and
(d) about 25 to about 55 weight percent of a cosolvent for (a).
The basic components of the instant compositions are three: (1) a drug component, (2) a permeation enhancement component, and (3) a carrier component.
The phrase "procaterol and pharmaceutically acceptable salts thereof" is intended to include all forms of procaterol and/or its analogs which have medicinal utility. Thus, procaterol, procaterol HCl, procaterol lauryl sulfate, and the like are contemplated. Mixtures may be used.
While the use of a procaterol-based drug is essential to the invention, the use of other beneficial substances is also contemplated. Thus, sedatives, tranquilizers, antihistamines, cardiotonics, cognition activators, and the like may be included in the compositions of the invention.
Generally, the drug component will comprise about 0.1 to about 5.0, preferably 0.5 to about 1.0, and most preferably about 1.0 percent, of the total composition.
All percentages recited herein are weight percentages based on total composition weight unless otherwise indicated.
The permeation enhancement component is a combination of substances which function to assist in the migration of the drug component(s) through the membranes and into the bloodstream. Thus, any agent(s) which function to hasten the transmembranal passage or systemic release of the drug(s) can be used.
It is required that the permeation enhancement system contain at least one essential fatty acid. While linoleic acid is preferred, other essential fatty acids, such as oleic or linoleic, can be used. Mixtures are operable.
It is also required that the permeation enhancement component contain at least one solvent for the drug component. Useful solvents include, but are not limited to propylene glycol, triacetin, triethyl citrate, dimethylisosorbide, propoxylated cetyl alcohol (Wickenol 171), PEG-8, capric/caprylic triglyarides (Softigen 737) and the like. Mixtures of two or more are operable.
When two solvents are employed, it is preferred that both be present in amounts between about 15 and about 55 percent. A mixture of propylene glycol and triacetin as cosolvents is preferred.
In a propylene glycol/triacetin system, propylene glycol shall be present between about 15 to about 40 percent and preferably about 30 percent; while triacetin should be present at about 25 to about 55 percent, preferably about 40 to about 45 percent, most preferably at about 43.5 percent.
The carrier component contains one or more substantially inert ingredients which function to give the composition physical properties such that it can be effectively administered transmembranally. For example, the carrier component may be a sponge such that the composition will be effectively administered transmembranally and retained behind the barrier membrane. Suitable materials for such sponges include polyethylene, EVA, polyurethane, and the like.
Generally, the carrier(s) used will give the compositions either rheological or form properties such that they can be employed in storable multilayered devices.
Other carriers which give useful characteristics to the gel compositions of the invention are thixotropic agents. Colloidal silicas, such as Aerosil R200 (a commercial product of DeGussa) are preferred siliceous thixothropic agents. Other fillers include thixcin, cetyl alcohol, fatty acid triglycerides, and the like. Mixtures are operable.
An alternate and sometimes preferred carrier system may comprise about 0.01 to about one percent, preferably about 0.5 of an antiirritant such as Wickenol R535 and about one to about ten percent, preferably about five percent thixotropic agent. The composition is preferably used in a gel as one layer of a device to be affixed to the skin.
Other conventional adjuncts, e.g., colorants, perfumes, stabilizers, and the like can also be employed in suitable quantities in the compositions of the invention.
The following example illustrates one embodiment of the invention.
EXAMPLE
The gel described below was employed within a system consisting of a multilaminated impermeable backing of polyester heat sealed to the barrier membrane which is porous polypropylene of 0.02 to 0.04 μm thickness.
The drug-containing gel composition contained:
______________________________________Ingredients Percent (%)______________________________________(1) Procaterol HCl 1.00(2) Linoleic acid 20.00(3) Propylene glycol 30.00(4) Triacetin 43.50(5) Wickenol R535 0.50 (wheat germ glycerides)(6) Aerosil R200 5.00 (Colloidal Silicon Dioxide)______________________________________
In vitro permeation experiments carried out utilizing the transdermal gel system have demonstrated superior permeation profiles for procaterol across hairless mouse skin when compared to a PVC/VA matrix system. The permeation profile is set out in FIG. 1.
The other ingredients (layers) used in the patch were polyester backing and acrylic adhesive.
DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a graph which plots the cumulative amount of drug which permeated hairless mouse skin against time. The graph is based on data generated in the example and shows in vitro permeation of procaterol HCl across hairless mouse skin from Hercon patch and 0.2 to 1% gel utilizing the flow thru cells.
FIG. 2 is a cross-sectional and a topview of the multilayer laminate, the patch.
"1" is the impermeable backing;
"2" is the drug gel composition;
"3" is the barrier membrane;
"4" is the release liner, and
"5" is the adhesive on the perimeter of the impermeable backing.
Reasonable variations, such as those which would occur to a skilled artisan, can be made herein without departing from the scope of the invention. | The administration of a bronchodilator to a subject can be carried out using a new transdermal delivery system, a multilayer laminate where the drug is mixed in a gel which must pass through a barrier membrane prior to administration on the skin. | 0 |
BACKGROUND OF THE NEW VARIETY
The present invention relates to a new and distinct variety of apple tree, ‘Malus domestica Mil’, and which is denominated varietally as ‘Moana,’ and more particularly to an apple tree which bears a distinctive and attractively colored round apple having a firm and crisp flesh texture and which further can be stored for commercially acceptable periods of time with little deterioration in the overall quality of the fruit.
ORIGIN AND ASEXUAL REPRODUCTION
It has long been recognized that a very important factor contributing to the success of any variety of apple tree bearing fruit for the fresh market is its ability to produce an attractively colored fruit which has good handling characteristics, and a distinctive flavor. The new variety ‘Moana’ is noteworthy, and distinguishable from the varieties it is most closely similar to, in producing an attractively and distinctly colored fruit having a skin color which is about 95% to 100% solid red flush, and which further has an attractive globose shape. The new variety is harvested during the same season where other known, and closely similar varieties such as the ‘Nagafu-6’ (unpatented) apple tree; ‘Candy’ (U.S. Plant Pat. No. 18,661); ‘CABp’ Fuji (U.S. Plant Pat. No. 17,914); and the apple tree variety ‘DT2,’ often referred to as the ‘Aztec Fuji’™ (unpatented), are harvested, and under the ecological conditions prevailing in Upper Moutere, Nelson, New Zealand.
The new variety of apple tree, ‘Moana’ was discovered as a limb sport mutation of a ‘Nagafu-6’ (unpatented) Fuji apple tree which was then growing in a cultivated orchard controlled by the inventors, and which is located at Upper Moutere, Nelson, New Zealand in May, 1996, during routine orchard operations. The inventors recognized the novel characteristics of the new variety of apple tree and then marked it for subsequent observation. Thereafter, the inventors removed bud wood from the chance sport and grafted it into several test trees growing in the same orchard. This first asexual reproduction of the variety occurred during October, 1998. The new variety ‘Moana’ has been observed since that time, and the first fruit was produced from these asexually reproduced trees and evaluated during April-May, 2001. Following confirmation that the fruit produced by these first asexually reproduced trees were true to the original chance sport, more bud wood was removed from the original sport and grafted over to production trees then growing in the same orchard in October, 2001. Fruit produced by these subsequent asexually reproduced trees have been evaluated and are true to the fruit produced by the original chance sport. All subsequent asexual reproductions have confirmed the unique characteristics of this new apple tree.
The present variety ‘Moana’ is readily distinguishable from the ‘Nagafu-6’ (unpatented) Fuji apple tree from which it was derived as a chance sport by producing a globose shaped fruit having a skin color which is about 95% to 100% solid red flush. In relative comparison, the fruit produced by the ‘Nagafu-6’ (unpatented) Fuji apple tree produces fruit having a skin color which is about 30-40% solid red flush with some weak stripes. Further, the new variety is distinguishable from other closely related varieties such as the ‘Candy’ apple tree (U.S. Plant Pat. No. 18,661) and which produces fruit having a skin color which is about 90-100% solid red flush with prominent stripes; and the fruit of the ‘DT2’ (unpatented) Fuji apple tree which has a skin color which has a solid red flush with weak stripes. Further, ‘CABp’ Fuji apple tree (U.S. Plant Pat. No. 17,914) produces fruit having a skin color which is about 50-66% solid red flush and which has more prominent striping (95%-100%).
SUMMARY OF THE VARIETY
The ‘Moana’ apple tree is characterized principally as to novelty by producing a unique, attractively colored, globose shaped apple which is ripe for harvesting and shipment about April 15 through early May, under the ecological conditions prevailing in Upper Moutere, Nelson, New Zealand.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are color photographs of the present variety. These photographs depict the whole fruit as would be seen on a typical branch of a tree, and the flowering characteristics of the new variety. These colors are as nearly true as reasonably possible with a color reproduction of this type. Due to chemical development, processing and printing, the leaves and fruit depicted in these photographs may or may not be accurate when compared to the actual specimen. For this reason, future color references should be made to the color plates (Royal Horticulture Society Colour Chart), and descriptions provided hereinafter. Occasionally common color names will also be used.
FIG. 1 shows the fruiting habit of the present variety. The apples as seen in this photograph are sufficiently matured for harvesting and shipment.
FIG. 2 depicts the flowering characteristic of the present novel apple tree.
NOT A COMMERCIAL WARRANTY
The following detailed description has been prepared to solely comply with the provisions of 35 USC §112, and does not constitute a commercial warranty (either expressed or implied), that the present variety will, in the future, display the botanical or other varietal characteristics as set forth in this application. Therefore, this disclosure may not be relied upon to support any legal claims, which include, but are not limited to breach of warranty of merchantability, fitness for any particular purpose, or non-infringement which is directed in whole, or in part, to the present variety.
DETAILED DESCRIPTION
Referring more specifically to the pomological details of this new and distinct variety of apple tree, the following has been observed under the ecological conditions prevailing at the orchard of the inventors which is located near Nelson, New Zealand. All major color code designations are by reference to The R.H.S. Colour Chart, 4th Edition provided by The Royal Horticulture Society of Great Britain.
Tree:
Size. —Considered average for the species. Height. —About 4 meters. Crown diameter — about 3.5 meters when measured at a height of about 1 meter above the surface of the earth. These measurements were taken from trees which were about 7 years old. Vigor. —Average for the species. Tree type. —Ramified. Growth habit. —Considered spreading; Tree Bearing: Mixed containing both spurs and long shoots.
Trunk:
Size. —Considered average for the species. Diameter. —About 11 cm. when measured at a distance of about 20 cm. above the graft union. Bark texture. —Considered smooth. Bark color. —Grey-green (RHS 197D). Bark lenticels. —Size — About 9 mm. long, and about 1 mm. wide. Bark lenticel color. —Grey-yellow (RHS 161A). Lenticel density. —About 5 lenticels per square cm.
Branches:
Size. —About 32 mm. in diameter when measured on 4 year old branches which are located about 50 cm. from the main trunk. Crotch angle. —Variable from about 20 degrees below, to about 40 degrees above horizontal. Branch color. —Grey-brown (RHS 199A). Lenticels. —Size — About 4 mm. long, and about 1 mm. wide. Lenticel color. —Grey-yellow (RHS 161A). Lenticel density. —About 9 lenticels per square cm. Hardiness. —Considered hardy under the current ecological conditions as experienced in Nelson, New Zealand. Chilling requirement. —Considered similar to that required for other patented and unpatented varieties of ‘Fuji’ apple trees growing in the same geographical area. One year old growth. —Size — Considered average for the variety. About 40 cm. in length, and about 5 mm. in diameter. One year old growth. —Surface texture — Considered moderately pubescent. One year old growth. —Surface color — Grey-orange (RHS 174A). One year old growth. —Internode length — About 3 to about 3.5 cm. One year old growth. —Pubescence — Present, and considered medium for the variety.
Flowers:
Flower buds. —Numbers — Typically, 1 per spur will be found. Flower buds. —Shape — Considered pointed. Flower buds. —Length — About 8.5 mm. Flower buds. —Diameter — About 4.1 mm. Flower buds. —Color — Grey (RHS 201C). Flower size. —About 38 mm. when fully opened. Flowers per cluster.— 5 or 6 flowers will typically be found. Flower petals. —Generally — 5 flower petals will typically be found in each flower. Flower petal orientation. —The flower petals are touching. Flower petal length. —About 22 mm. Flower petal width. —About 12 mm. Flower petal apex. —Generally speaking, the apex shape is rounded. Flower petal marginal form. —Considered smooth. Flower petals. —Upper Surface Color — Predominately white (RHS 155C). Flower petals. —Lower Surface Color — The lower surface of the flower petal has faint staining of a red-purple color (RHS 73B) when the flower is fully opened. Sepals. —Length — About 5 mm. Sepals. —Width — About 2 mm. Sepal color. —Green (RHS 145A). Pedicel. —Length — About 29 mm. Stamens. —Number — Numerous. The number of stamens is not distinctive of the present variety. Anthers. —Length — About 5 mm. Anthers. —Color — Yellow (RHS 11C). Pistil. —Length — About 8 mm. Only one pistil is found per flower. Pistil. —Color — Green (RHS 145C). Flowering time. —Considered average for the variety. In 2008, full bloom was achieved on 14 October under the ecological conditions prevailing near Nelson, New Zealand. Pollination. —Any diploid cultivar other than a Fuji or Fuji sport which flowers at a similar time can serve as an adequate pollinizer for ‘Moana.’
Leaves:
Leaf orientation relative to the shoot. —Considered upwardly oriented. Leaf length. —On average about 79 mm. when measured on 1 year old shoots. Leaf Stipules — Shape — Lanceolate; Leaf Stipules — Width — about 2.5 mm; Leaf Stipules Length — about 8.3 mm. Leaf width. —About 47 mm., on average. Leaf shape. —Considered ovate. Apex shape. —Acuminate. Base. —Shape — Obtuse. Marginal form. —Considered crenate. Upper leaf color. —Yellow-green (RHS 147A). Lower leaf color. —Green (RHS 138B).
Fruit:
Size at commercial maturity. —Considered large and having a height of about 69 mm. and a diameter of about 80 mm. Fruit weight. —On average at commercial maturity, the respective fruit weighs about 200 grams. This is not distinctive of the present variety because fruit weight can be so easily effected by prevailing cultural practice and ambient environmental conditions. Fruit shape when considered in profile. —Globose. Position of maximum fruit diameter. —Approximately the middle of the fruit. Fruit ribbing. —Not detected. Aperture of eye. —Considered closed. Size of the eye. —Considered small for the species. Locules — Number — 5; Locule Width — about 11.7 mm.; Locule Depth — about 5.2 mm.; Locule Length — about 13.2 mm. Eye basin. —Size — About 10 mm. in depth and about 25 mm. in width. Stalk. —Size — About 2 mm. in diameter, and having a length of about 22 mm. Stalk. —Color — Grey-brown (RHS 199A). Stalk cavity. —Size — About 14 mm. in depth and about 29 mm. wide. Lenticels. —Size — Considered medium to large for the species; Lenticel Density — about 4 per square centimeter. Skin bloom. —Generally — Considered present. Skin greasiness. —Absent. Ground color of the Skin. —Yellow-green (RHS 154C). Skin over color. —Grey-purple (RHS 185A). Over color pattern. —Solid flush. Over color. —Amount — Considered high, about 95% to about 100%. Russet. —Generally — When considered around the eye basin, it is absent or very low. Further, the russet on the cheeks is considered low to moderate for the species. A moderate amount of russet is found in the vicinity of the stalk cavity. Fruit flesh. —Texture — Considered average, firm and crisp and having a fruit pressure at about 6.5 kg. to about 7 kg; Brix — about 13. Flesh color. —White (RHS 155B). Seed numbers.— 9 per fruit will be found; Seed Size—about 9.4 mm. long and about 4.9 mm. wide. Seed color. —Grey-orange (RHS 166A). Maturity for commercial harvesting and shipment. —About April 15-April 30 under the ecological conditions prevailing near Nelson, New Zealand. Fruit use. —A fresh fruit apple for local and long distance markets; Fruit Aroma — Considered sweet. Fruit storage. —Similar to that experienced by the various commercially available ‘Fuji’ cultivars. Resistance to diseases. —No particular susceptibilities were noted.
Although the new variety of apple tree herein denominated as ‘Moana’ possesses the described characteristics when grown under the ecological conditions prevailing near Nelson, New Zealand, it is to be understood that variations of the usual magnitude and characteristics incident to changes in growing conditions, fertilization, pruning and pest control are to be expected. | A new and distinct variety of apple tree ‘Malus domestica Mil’ named ‘Moana’ is described and which is characterized by a date of maturity of April 15th or later under the ecological conditions prevailing near Nelson, New Zealand. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a liquid storing container, a liquid ejection head cartridge (which will sometimes be referred to hereinafter as an ink jet head) equipped with the same container and a liquid ejection head (which will sometimes be referred to hereinafter as an ink jet cartridge), and an liquid ejection recording apparatus (which will sometimes be referred to hereinafter as a liquid jet recording apparatus) in which the same cartridge is mounted for recording, and more particularly to a liquid storing container having an internal structure improved for stabilizing a liquid supply property, a liquid ejection head cartridge carrying the same container and a liquid ejection head, and a liquid ejection recording apparatus incorporating the same cartridge for recording.
2. Description of the Related Art
In general, an ink tank (including a type of being integrated with a recording head and a type in which an ink tank is replaceable separately) serving as a liquid storing container for use in the field of liquid jet recording (which will equally be referred to hereinafter as an ink jet recording) has a construction to adjust the holding capability of an ink stored in the ink tank for achieving excellent ink supply to a recording head which ejects a liquid (a liquid to be used for recording; including a type containing a coloring component(s), and a type not containing a coloring component but which acts on a liquid containing a coloring component for upgrading the recording quality, which hereinafter will be referred to simply as an ink). This holding capability is called negative pressure, because it is for making the pressure in an ink ejecting section of a recording head negative with respect to the atmosphere (a member for production of such a negative pressure will equally be referred to hereinafter as a negative pressure producing member).
As one of the easiest ways of producing such a negative pressure, there has been known a means in which an ink absorber made from a porous material such as a urethane foam is provided in an ink tank to utilize a capillary capability the ink absorber.
In addition, there has been proposed an ink tank (which will be referred to hereinafter as a juxtaposed type ink tank) in which, for the purpose of enhancing the volume efficiency of the ink in the interior of the ink tank, a chamber for accommodating the ink absorber and a chamber for storing the liquid directly are juxtaposed so that they are made to partially communicate with each other.
FIG. 10A is a cross-sectional view schematically showing a construction of an ink tank in which, as mentioned above, a chamber for accommodating the ink absorber and a chamber for storing the liquid directly are juxtaposed so that they are made to partially communicate with each other. The interior of the ink tank 10 is partitioned by a partition wall 38 , having a communicating hole 40 , into two spaces. One space is hermetically sealed except the communicating hole 40 of the partition wall 38 serves a liquid storage chamber 36 for storing an ink directly, while the other acts as a negative pressure producing member storage chamber 34 for accommodating a negative pressure producing member 32 . On a wall surface defining this negative pressure producing member storage chamber 34 , there are formed an atmosphere communication section (atmosphere communicating opening) 12 for introducing the atmosphere into a container resulting from ink consumption, and a supply opening 14 having an ink leading member 39 for leading the ink from the tank to a recording head section (not shown). In FIG. 10A, the area in which the negative pressure producing member holds the ink is indicated by an oblique-line section. Additionally, the ink stored in the space is indicated by a mesh section.
In the foregoing construction, on consumption of the ink in the negative pressure producing member 32 by the recording head, air is introduced through the atmosphere communication opening 12 into the negative pressure producing member storage chamber 34 passing into the liquid storage chamber 36 through the communicating hole 40 of the partition wall 38 . Instead, the ink is put from the liquid storage chamber 36 through the communicating hole 40 of the partition wall 38 into the negative pressure producing member 32 in the negative pressure producing member storage chamber 34 (this operation will be referred to hereinafter as an air-liquid replacement operation). Accordingly, if the recording head consumes the ink, the ink is drawn into the negative producing member 32 according to the consumption thereof so that the negative pressure producing member 32 retains a constant quantity of ink to maintain the negative pressure to the recording head approximately constant, thus stabilizing the ink supply to the recording head.
In addition, in the example shown in FIG. 10A, in the vicinity of the communicating section between the negative producing member storage chamber 34 and the ink storage chamber 36 , an atmosphere introducing groove 51 is provided as a structure to promote the introduction of the atmosphere, while, in the vicinity of the atmosphere communicating section, a space (buffer chamber) 44 , not accommodating a negative pressure producing member, is defined by ribs 42 .
In the conventional art, in many cases, the urethane foam has commonly been employed as the aforesaid negative pressure producing member (which is equally referred to as an ink absorber) as mentioned above. However, the urethane foam requires further improvement in the service efficiency of ink; besides, not always exhibiting a suitable characteristic depending on the ink property.
For this reason, this applicant has proposed the use of a fiber made from an olefin-based resin having a thermal plasticity, which shows, as an ink absorber, a superior ink property throughout a wide range.
Meanwhile, in a juxtaposed type tank shown in FIG. 10A, the important factors in the stable supply of an ink are the structure of a communicating hole constituting a connecting section between a negative pressure producing member storage chamber and a liquid storage chamber and the structure on the periphery thereof.
That is, in the case of the juxtaposed type ink tank, the bottom line is the stable introduction of air from the atmosphere communicating section (atmosphere communicating opening) 12 through the atmosphere introducing groove 51 of the partition wall 38 into the liquid storage chamber in connection with the ink consumption. If air is introduced through places other than this air introduction route, an unnecessary air-liquid replacement, not related to the ink consumption, takes place, which can cause an excessive supply of to leak toward the exterior of the tank.
In the case of the use of the urethane foam as the negative pressure producing member, since the urethane foam per se has a structure showing a high elasticity, it comes satisfactorily into contact with the communicating hole and an inner wall surface constituting the periphery thereof in a state accommodated in the negative pressure producing member storage chamber, which hardly causes the aforesaid unexpected air-liquid replacement, thus not creating problems on the practical use.
However, a fiber member involving fibers and displaying more preferable characteristics relating to a characteristic to the ink and a service efficiency as compared with the urethane foam does not exhibit a high elasticity because of its property on the material unlike the urethane foam (particularly, although a fiber member whose felt-like fibers do not run remarkably to one direction shows a relatively high elasticity, a fiber member made to have directionality can depend upon the direction the fibers extend in). Accordingly, sometimes, it does not reach an excellent contacting condition with an inner wall surface of an tank in a state accommodated in the negative pressure producing member storage chamber. Although the prevention from such an event relies upon high-accuracy cutoff, difficulty can be encountered in achieving a desirable cutoff accuracy.
Especially, in the case of the juxtaposed type ink tank in which, as shown in FIG. 10A, the ink supply is made from a lower section of the ink tank and the ink tank and the head are placed in a separated condition, in order to secure the close contact of the ink leading member 39 located in the ink supplying section with a filter placed at the tip portion of a supply pipe set in the head, there is a need to push up the aforesaid ink leading member 39 by the supply pipe when the ink tank is set on a mounting holder attached onto the head. At this time, the bottom surface of the absorber is simultaneously lifted by the influence of the pushed up ink leading member 39 .
In the case of the urethane foam, the material itself has a high elasticity so that its local deformation absorbs the pushed-up ink leading member 39 ; accordingly, variation does not occur in the locating construction of the urethane foam near the communicating hole.
However, the fiber absorber occasionally displays poor elasticity due to the fiber directionality constituting the characteristic of the material; whereupon, the fiber absorber is also pushed up by the pushed-up ink leading member 39 so that variation occurs in the locating construction of the fiber absorber between the ink supplying section and the vicinity of the communicating hole, which tends to establish a passage between the bottom surface of the fiber absorber storage chamber and the bottom surface of the fiber absorber.
In such a juxtaposed type ink tank, the liquid storage chamber except the communicating hole must be sealed hermetically. In addition, for accomplishing stable air-liquid replacement, it is preferable that the communicating hole is covered with the negative pressure producing member.
Nevertheless, in the case of a conventional ink tank of a juxtaposed type juxtaposing a negative pressure producing member storage chamber and a liquid storage chamber as shown in FIG. 10B or 10 C, since the communicating hole for making a connection between the negative pressure producing member storage chamber and the liquid storage chamber is defined by an inner wall organizing the tank bottom surface or the tank side surface, in the case in which the negative pressure such as the aforesaid fiber absorber is accommodated therein, the close adhesion between the fiber absorber and the ink tank case inner wall becomes insufficient due to the aforesaid cause such as the tank connection so that a gap (which will equally be referred to hereinafter as a path, an air path or a ridge line path) develops between the fiber absorber and the ink tank case inner wall; hence, this gap communicates with the communicating hole and further communicates with the external atmosphere, which can incur an unnecessary and expected air-liquid replacement to give rise to an external leak of ink.
FIG. 10D shows one example of an ink tank in which the unnecessary air-liquid replacement has occurred. An air path 60 defines an ink path when once communicating with the liquid storage chamber, thus producing the ink passage toward the supplying section.
FIG. 10E illustrates a section of the ink tank, indicated by oblique lines, where the air path 60 tending to produce the unnecessary air-liquid replacement develops easily. As illustrated, a gap (ridge line path) tends to develop in a ridge line of a joint between the wall surfaces.
As described above, if a fiber absorber having a directionality is employed as the negative pressure producing member, the failure of the close adhesion to the tank inner wall surface or the ridge line tends to occur, and if forcible insertion takes place, buckling will occur in the fiber absorber to incur unexpected ink surplus or to provide, for example, unsatisfactory ink supply ability or insufficient negative pressure.
As described above, if an air path develops to cause ink leakage from an ink supply opening, desirable printing becomes difficult, the ink drops onto a print medium or the printer body is contaminated with the ink, and even there is a possibility of, for example, soiling hands or clothes of the user at the ink tank replacement.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a liquid storing container which is of a juxtaposed type capable of, even if a fiber member having directionality and used as an absorber moves in the interior of a tank at the mounting of the tank, preventing the communication of an air path with an ink chamber so as not to create the aforesaid problems of ink leakage, deterioration of the print quality and others, and further to provide a liquid ejection head cartridge in which the same container and a liquid ejection head are integrated with each other and a liquid ejection recording apparatus in which the same cartridge is mounted for recording.
For achieving this object, in accordance with this invention, there is provided a liquid storing container attachable and detachable to and from recording means, comprising a negative pressure producing member storage chamber made to accommodate a negative pressure producing member and equipped with a liquid supplying section and an atmosphere communicating section, a liquid storage chamber having a communicating hole for establishing a communication with the negative pressure producing member storage chamber and made to define a substantially hermetically sealed space for storing a liquid to be supplied to the negative pressure producing member, a partition wall for establishing a partition between the negative pressure producing member storage chamber and the liquid storage chamber and for defining the communicating hole, and a path made in the vicinity of the communicating hole on the negative pressure producing member storage chamber side for introducing the atmosphere from the negative pressure producing member storage chamber into the liquid storage chamber, wherein the negative pressure producing member is made with a fiber material having directionality and the communicating hole is in a non-contacting condition with a ridge line defined by crossing of the partition wall and an inner wall constituting the negative pressure producing member storage chamber.
With this construction, even if an air path develops between the negative pressure producing member and an inner wall constituting the negative pressure producing member storage chamber or a ridge line portion, it is possible to prevent the air path from communicating through the communicating hole with the liquid storage chamber.
Accordingly, it is possible to prevent unnecessary air-liquid replacement for preventing unnecessary ink leakage from the liquid storing container, and to reduce the necessity to improve the accuracy for avoiding the occurrence of an air path, that is, to improve the margin for facilitating the manufacturing of the liquid storing container. In addition, even if a situation such as drop of the liquid storing container arises, since the possibility of the communication of the air path with the communicating hole is reducible, thus providing a liquid storing container, a liquid ejection head cartridge and a liquid ejection recording apparatus which are capable of improving their reliability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1 C are schematic illustrations useful for describing a first embodiment of the present invention; of these illustrations, FIG. 1A is a perspective view of the first embodiment and FIGS. 1B and 1C are cross-sectional views thereof;
FIGS. 2A and 2B are schematic illustrations useful for describing a second embodiment of this invention; of these illustrations, FIG. 2A is a perspective view of the second embodiment and FIG. 2B is a cross-sectional view thereof;
FIGS. 3A and 3B are schematic illustrations useful for describing a modification of the second embodiment of this invention; of these illustrations, FIG. 3A is a perspective view of the modification and FIG. 3B is a cross-sectional view thereof;
FIGS. 4A and 4B are schematic illustrations useful for describing a third embodiment of this invention; of these illustrations, FIG. 4A is a perspective view of the third embodiment and FIG. 4B is a cross-sectional view thereof;
FIGS. 5A and 5B are schematic illustrations useful for describing a fourth embodiment of this invention; of these illustrations, FIG. 5A is a perspective view of the fourth embodiment and FIG. 5B is a cross-sectional view thereof;
FIGS. 6A and 6B are schematic illustrations useful for describing a fifth embodiment of this invention; of these illustrations, FIG. 6A is a perspective view of the second embodiment and FIG. 6B is a cross-sectional view thereof;
FIGS. 7A and 7B are schematic illustrations useful for describing a sixth embodiment of this invention; of these illustrations, FIG. 7A is a perspective view of the sixth embodiment and FIG. 2B is a cross-sectional view thereof;
FIGS. 8A and 8B are schematic illustrations useful for describing a seventh embodiment of this invention; of these illustrations, FIG. 8A is a perspective view of the seventh embodiment and FIG. 8B is a cross-sectional view thereof;
FIGS. 9A and 9B are schematic illustrations useful for describing an eighth embodiment of this invention; of these illustrations, FIG. 9A is a perspective view of the eighth embodiment and FIG. 9B is a cross-sectional view thereof;
FIGS. 10A to 10 E are schematic illustrations for explaining an object of this invention; and
FIG. 11 is a schematic illustration of a liquid jet recording apparatus to which this invention is applicable.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A detailed description will be given hereinbelow of embodiments of the present invention with reference to the drawings.
Although in the following description of the embodiments an ink is taken as a liquid to be used in a liquid supplying method and a liquid supplying system according to this invention, the liquid which can be put to use is not limited to the ink but also including, for example, a treating liquid for a recording medium in the ink jet recording field.
In addition, in the cross-sectional views, the area in which a negative pressure producing member holds an ink is indicated by an oblique-like section while an ink accommodated in a space is indicated by a mesh section. However, for the purpose of making clear the configurations on the periphery of a communication hole and a cross-sectional configuration thereof, the negative pressure producing member or the ink will sometimes be omitted depending on the illustrations.
Concrete means for achieving the foregoing object will become apparent from the following construction.
(First Embodiment)
FIGS. 1A to 1 C are partially enlarged illustrations of a section of a liquid storing container according to a first embodiment of this invention, lying in the vicinity of its communicating hole. FIG. 1A is a perspective view schematically showing the liquid storing container section, viewed from a negative pressure producing member storage chamber side, and FIGS. 1B and 1C are side cross-sectional views schematically showing the liquid storing container section.
In FIG. 1A, under a partition wall 38 on a negative pressure producing member storage chamber side, a fiber absorber is accommodated, while an atmosphere introducing path 51 is formed to come into contact with the fiber absorber, and a communicating hole 40 is made to communicate with the atmosphere introducing path 51 . As FIG. 1B shows, the communicating hole 40 establishes a communication between a negative pressure producing member storage chamber accommodating a fiber absorber 32 and a liquid storage chamber 36 . In this embodiment, in the interior of the negative pressure producing member storage chamber, a fiber absorber is accommodated which is made with two kinds of fiber materials to have a coaxial configuration in its cross section. The material of the central section of the fiber absorber is made of polypropylene while the material of the circumferential section thereof is made of polyethylene. This invention is not limited to this, but it is also appropriate to use a fiber absorber made from an olefin-based fiber. In this embodiment, the fiber of the fiber absorber is directionally parallel with the bottom surface of the ink tank.
Although the communicating hole 40 is situated in the vicinity of a lower end portion of the partition wall 38 , as illustrated, the outer circumferential section of the communicating hole 40 is not brought into contact with any of the tank case inner walls intersecting the partition wall 38 in the interior of the negative pressure producing member storage chamber.
A state of the aforesaid liquid storing container will be described hereinbelow with reference to FIG. 1 C. Even if the adhesion between the fiber absorber and the tank inner wall is poor or the adhesion between the fiber absorber and the tank inner wall is broken by the push-up of a ink leading member 39 to produce a partial air path 60 , the air path 60 is blocked by the partition wall 38 standing on a lower end side of a partitioning wall so that it does not communicate with the liquid storage chamber 36 to maintain the substantially hermetically sealed condition of the liquid storage chamber; therefore, the unnecessary and unexpected air-liquid replacement does not occur. Whereupon, the air-liquid replacement takes place stably through the atmosphere introducing path, thereby preventing unexpected ink leakage from the ink tank.
In this embodiment, the distance h between the communicating hole 40 and the a lower end surface (bottom surface) of an inner wall of the negative pressure producing member storage chamber is set at approximately 1 mm in consideration of the ink remainder in the liquid storage chamber 36 , the stability of the air-liquid replacement operation and others. This distance h is required to be determined properly on the basis of the kind of the negative pressure producing member, the degree of the push-up of an ink leading member, the tank case dimension and others, and is selectable properly in a range of approximately 0.2 mm to 1.0 mm. Incidentally, even if the distance h is approximately 1 mm, because of sometimes moving to the negative pressure producing member storage chamber side due to the vibrations of the ink generated by the scanning of the ink tank, the ink consumption efficiency does not drop extremely.
(Second Embodiment)
FIGS. 2A and 2B are explanatory illustrations schematically showing a liquid storing container according to a second embodiment of this invention. FIG. 2A is a perspective view of the liquid storing container and FIG. 2B is a cross-sectional view thereof.
The construction of this embodiment is the same as that of the first embodiment except that a lower end side of an outer circumferential section of a communicating hole is formed into a tapered configuration 40 a . In addition to sufficiently exhibiting the above-mentioned effects, this can restrain a corner portion of a fiber absorber on the bottom surface side from being hooked by a lower end portion of the communicating hole to be torn up even when the fiber absorber is inserted into a negative pressure producing member storage chamber from above a tank container for the construction of a tank. Accordingly, it is possible to prevent unstable ink supplying operation stemming from the tearing-up.
Incidentally, as shown in the perspective of FIG. 3 A and in the cross-sectional view of FIG. 3B, it is preferable that the entire surface of the outer circumferential section of a communicating hole is formed to have a tapered configuration 40 b . This can prevent the tearing-up of the absorber at the insertion irrespective of the direction of insertion of the absorber.
(Third Embodiment)
FIGS. 4A and 4B are schematic explanatory illustrations of a portion of a liquid storing container according to a third embodiment of this invention. FIGS. 4A is a perspective view schematically showing the liquid storing container, and FIG. 4B is a cross-sectional view schematically showing thereof.
In comparison with the construction shown in FIGS. 1A to 1 C, in this embodiment, a slight step 61 is formed in the vicinity of a partition wall 38 lying at a bottom section of a negative pressure producing member storage chamber.
This step 61 prevent air path which tends to occur at a ridge line portion defined by a bottom surface and side surface of the negative pressure producing member storage chamber.
(Fourth Embodiment)
FIGS. 5A and 5B are schematic explanatory illustrations of a portion of a liquid storing container according to a fourth embodiment of this invention. FIG. 5A is a perspective view schematically showing the liquid storing container while FIG. 5B is a cross-sectional view thereof.
In this embodiment, a lower end of a communicating hole 40 and a bottom surface portion of a liquid storage chamber 36 are made to be equal in height to each other. With this construction, ink remaining in the liquid storage chamber 36 is avoidable. In addition, there is no need to lower the step h with respect to a negative pressure producing member storage chamber which is made in consideration of the ink consumption as shown in FIGS. 1A to 1 C, and it is possible to freely determine the step in the range of solving the air path problem. Incidentally, if the step is too high, the quantity of ink accommodated by the liquid storage chamber 36 lessens. Accordingly, the step may be determined in consideration of the ink storage quantity.
(Fifth Embodiment)
FIGS. 6A and 6B are schematic explanatory illustrations of a portion of a liquid storing container according to a fifth embodiment of this invention. FIG. 6A is a schematic perspective view and FIG. 6B is a schematic cross-sectional view.
In this embodiment, in addition to the construction of the liquid storing container according to the first embodiment, a groove 62 generating capillary action is made in a lower end portion of a communicating hole 40 . The capillary action produced by this groove 62 can lead an ink in a liquid storage chamber 36 into a negative pressure producing member storage chamber, thus reducing the ink remaining in the liquid storage chamber 36 .
(Sixth Embodiment)
FIGS. 7A and 7B are schematic explanatory illustrations of a portion of a liquid storing container according to a sixth embodiment of this invention. FIG. 7A is a schematic perspective view and FIG. 7B is a schematic cross-sectional view.
In this embodiment, a slope 63 is formed at a step portion on the liquid storage chamber side. The formation of the slope 63 increases the ink storage quantity as compared with the above-described fourth embodiment, and allows the ink to more easily move into a negative pressure producing member storage chamber as compared with the above-described first embodiment, thus reducing the ink which remains in the liquid storage chamber.
(Seventh Embodiment)
FIGS. 8A and 8B are schematic illustrations of a portion of a liquid storing container according to a seventh embodiment of this invention. FIG. 8A is a schematic perspective view while FIG. 8B is a schematic cross-sectional view.
In this embodiment, a rib 64 is formed in the vicinity of a lower end portion and side edge portions of a communication hole 40 of a liquid storing container corresponding to that according to the first embodiment. The formation of the rib 64 can block an air path created toward the communication hole 40 in directions along these portions, thus further improving the reliability of the ink supply.
(Eighth Embodiment)
FIGS. 9A and 9B are schematic illustrations of a portion of a liquid storing container according to an eighth embodiment of this invention. FIG. 9A is a schematic perspective view while FIG. 9B is a schematic cross-sectional view.
This embodiment is similar to the above-described first embodiment except that a partition wall 38 has a tapered section 65 so that the thickness thereof increases toward the bottom of the tank. This construction can improve the close adhesion between an absorber and a tank inner wall at a lower section of the tank, particularly between the partition wall 38 and the absorber to restrain the occurrence of an air path. The other construction is similar to that of the first embodiment.
The constructions described above can be employed individually, or a combination of some of the constructions can exhibit composite effect, thus offering an ink tank with a superior construction which can cut the communication of an air path, if any, with the communicating hole without impairing the ink service efficiency.
It should be understood that the present invention is not limited to the constructions concretely described above, and that it is intended to cover all changes and modifications of the embodiments of the invention herein used for the purpose of the disclosure, which do not constitute departures from the spirit and scope of the invention.
Although the above description relates to the employment of a fiber absorber, the construction according to this invention is also applicable to the use of an urethane foam. If this invention is applied, then the reliability of a tank constructed using a urethane foam becomes higher, and easier manufacturing becomes possible.
FIG. 11 is a perspective view schematically showing an ink jet printing apparatus using the above-described head cartridge. This apparatus is a printer of a full-color serial type having an ink tank integrated head cartridge, attachable/detachable to/from the carriage, for handling four color inks of black (Bk), cyan (C), Magenta (M) and yellow (Y). A head section of a head cartridge to be used in this printer has 128 ejection openings and provides a definition of 400 dpi at a drive frequency of 4 KHz.
In FIG. 11, IJC represent four head cartridges for the inks Y, M, C and Bk, with the recording heads being integrated structurally with ink tanks storing inks to be supplied thereto. Each of the head cartridges IJC is mounted detachably in the carriage by a means not shown. The carriage 82 is engaged with a guide shaft 811 to be slidable therealong, and is connected to a portion of a drive belt 852 driven by a non-shown main-scanning motor. Accordingly, the head cartridge IJC becomes movable along the guide shaft 811 for the main scanning operation. Reference numerals 815 , 816 , 817 and 818 denote conveying rollers extending in substantial parallel with the guide shaft 811 on the rear and front sides of the illustration in the printing area depending on the scanning by the head cartridges IJC. The conveying rollers 815 to 818 are driven by a non-shown feeding motor (not shown) to convey a print medium P. A print surface of this print medium P conveyed is placed in an opposed relation to a plane including the ejection openings of the head cartridges IJC.
A recovery system unit is provided to face a movable area of the cartridge IJC adjacent to a print area of the head cartridge IJC. In the recovery system unit, numeral 8300 designates a cap unit located for the corresponding one of the plurality of cartridges IJC each having a head section. The cap unit is slidable in accordance with the movement of the carriage 82 in the right- and left-hand directions in the illustration, and further movable up and down. When the carriage 82 is at its home position, it is joined to the head section to cap the head section. Additionally, in the recovery system unit, numeral 8401 denotes a blade acting as a wiping member.
Moreover, numeral 850 depicts a pump unit for absorbing ink or the like from the ejection openings of the head sections and the vicinity thereof through the cap units 8300 .
As obvious from the above description, according to this invention, it is possible to prevent an air path occurring the difference in dimension among absorbers or the pushing-up of the absorber at mounting from communicating with the liquid storage chamber, thus providing a liquid storing container which does not cause ink leakage from the ink supply openings.
In addition, it is possible to provide an ink jet head cartridge capable of achieving stable ink ejection.
Still additionally, it is possible to offer a liquid jet recording apparatus capable of accomplishing stable recording. | A liquid storing container attachable and detachable to and from a recording device includes a negative pressure producing member storage chamber which has a bottom wall and opposed side walls and which accommodates a negative pressure producing member and is equipped with a liquid supplying section in the bottom wall and an atmosphere communication section. A partition wall separates the negative pressure producing member storage chamber from a liquid storage chamber and defines a communicating hole for establishing communication therebetween. A path in the vicinity of the communicating hole on the negative pressure producing member storage chamber side introduces the atmosphere from the negative pressure producing member storage chamber into the liquid storage chamber. The negative pressure producing member is made with a fiber material having directionality and the communication hole is offset from the bottom wall. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to an inductive type magnetic thruster, and more specifically, to a pulsed inductive type magnetic thruster incorporating a plurality of parallel-connected one-turn coils for use as an engine in a space vehicle.
2. Discussion
Rocket engines for long term space exploration must meet demanding requirements that may not be as crucial in their present short term counterparts. Currently, experimentation is being conducted into developing engines that will meet the necessary requirements for long duration missions. Considerations include that the components of the engine be extremely durable and reliable. Also, high rocket exhaust velocity is necessary to reduce fuel requirement in order to achieve high useful payloads. These requirements provide a challenging avenue for engineers developing such engines.
Different types of designs have been experimented with over the course of the development of this technology. Generally, chemical propulsion engines are required to provide the initial launch function of a rocket because of their high thrust-to-mass ratios. However, chemical rockets typically exhibit a low propellant exhaust velocity, usually referred to as specific impulse (I sp ) Therefore, other types of engines that do not require the generation of heat for propellant acceleration have been experimented with to provide the high I sp necessary for sustained long term space travel. Specifically, certain electric type engines are known which use either electric fields (Ion Engine) or magnetic fields (direct-current, electrode type engines) for propulsion. However, these types of engines have typically met with various drawbacks limiting their success.
One specific problem has been electrode erosion that becomes an important factor when extended use is required. The need for electrodes can be avoided by the use of inductive type magnetic thrusters which are known to the electric propulsion art. One particular design incorporates a single-turn, flat, spiral induction coil. In that design, multiple parallel connected, single-turn coil sections, that spiral inward from the outside diameter of the annular coil to the inner diameter, are placed on one side of the inductor, with radial current return sections located on the other side of the inductor to form a complete coil. A large number of coils are connected in parallel for low coil parasitic inductance. Capacitors, with spark-gap switches, are inserted at some point in the loop to drive short pulses of electric current, using techniques known to those skilled in the art. A master trigger generator is used to synchronize firing of all of the capacitors. A desirable propellant gas is injected against the coil, which when energized by the capacitor discharge becomes electrically conducting. The magnetic force acting on the electrically conducting propellant generates the rocket engine thrust.
This prior art inductive design still suffers from a number of drawbacks preventing it from being an effective means for long term space travel. What is lacking in this design, and thus is needed, is an inductive type magnetic thruster which utilizes a long life propellant injection valve having better propellant placement for closer inductive coil coupling with the plasma propellant; an electric thruster circuit capable of producing a large initial electric field for efficient ionization; a low parasitic inductance; and the use of solid state switches for improved thruster efficiency and long life mission capability. Of particular importance for the practical implementation of such an improved thruster in a spacecraft electric propulsion system is a coil concept that permits the voltage requirements of the thruster to be met with existing generator technology without requiring the additional mass inherent in the thruster power conditioner. It is an object of this invention to provide for a pulsed inductive thruster which meets the thruster's requirements for effective ionization and efficient thrust generation without requiring special power conditioning for voltage transformation, voltage regulation or filtering.
SUMMARY OF THE INVENTION
Disclosed is a multi-megawatt pulsed inductive thruster (PIT) which comprises a flat spiral coil inductor consisting of a plurality of parallel-connected coils. Current from an array of energy discharge capacitors is introduced into each coil to generate a rapidly increasing magnetic field that will ionize a propellant gas placed in close proximity to the inductor. A fractional turn coil design is used for the inductor in which the coil sections extend from outer to inner radii of the annular spiral in less than one turn. Capacitors discharging into the fractional turn sections act as an inductive Marx Bank producing a one-turn coil EMF equal to the capacitor voltage multiplied by the number of capacitors connected to the coil sections in the loop.
In one embodiment, each parallel coil of the inductor includes four separate coil sections, with two capacitors. A first coil section is connected to a first connecting point on an outer radius of the inductor and travels one-quarter of the way around the inductor to be connected at a first connecting point on an inner radius of the inductor. A second coil section (on the opposite side of the inductor from the first coil section) is connected to the first inner radius connecting point, returns to the outer radius after another one-quarter turn and connects to a second outer radius connecting point. A third coil section is attached to the second outer connecting point, on the same inductor face as the first coil section, and is taken through another one-quarter turn to a second inner radius connecting point where it is attached. A fourth coil section (on the same side of the inductor as the second coil section) completes the last quarter turn of the one-turn loop of the inductor by attaching at the second inner and first outer connecting points. Capacitor/switch combinations are connected at each of the two outer radius connecting point, with the low voltage side of each capacitor connected to the coil section coming from the inside radius and the high voltage side connected to the section that goes to the next inside radius. Upon discharge, the voltage of each capacitor is applied across two coil sections producing an EMF equal to the capacitor voltage. Because two capacitors are used for the one-turn coil, the total EMF for the inductor is twice as great as the capacitor voltage. Thus, a factor of two gain in coil EMF over the power source voltage has been achieved without use of a transformer. In an alternate embodiment, capacitor switch combinations are connected at the inner radius connecting points in addition to those at the two outer connecting points, thereby producing a coil EMF four times as great as the capacitor voltage, again without use of a transformer.
In operation of the PIT, a pulse of gas is injected towards one face of the inductor after the capacitors have become fully charged. When the gas pulse has reached its closest position to the inductor face, the capacitors are simultaneously discharged. The large EMF of the Marx Bank enables a fast rising magnetic field that induces an azimuthal electric field in the propellant gas that is large enough to completely ionize the gas very early in the discharge. The magnetic field produced in the ionized gas (plasma) by the electric currents in the inductor and in the plasma generates a local thrust force density at any point that is equal to the product of the local plasma current with the local magnetic field at that point. The thrust force is the integrated total of all the local force densities over the entire plasma volume. The capacitors are recharged after each discharge and fired again at a steady pulse rate that produces the required continuous average thrust force.
Additional objects, advantages, and features of the present invention will become apparent from the following description and appended claims, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a pulsed inductive thruster (PIT) according to one embodiment of the present invention;
FIG. 2 is a side view of the PIT of FIG. 1;
FIG. 3 is a front view of the parallel connected coil sections of the PIT of FIG. 1;
FIG. 4 is a view of the parallel connected coil sections of the PIT of FIG. 1 (front and rear views are identical);
FIG. 5 is a series of parallel connected capacitors for energizing the inductor of the PIT of FIG. 1; and
FIG. 6 is a single coil and capacitor configuration schematic according to one embodiment of the present invention. The actual inductor has several coil sections parallel-connected in the two-capacitor loop.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description of the preferred embodiments is merely exemplary in nature and is in no way intended to limit the invention or its application or uses.
First turning to FIGS. 1 and 2, a basic understanding of the configuration of a PIT 10, according to one embodiment of the present invention, can be ascertained. FIG. 1 is a perspective view of PIT 10 and FIG. 2 is a side view of PIT 10. PIT 10 includes a flat, annular inductor 12. Inductor 12 comprises a series of parallel individual coils 46 appropriately configured, as will be described hereunder, on a circular substrate 38. Positioned adjacent an outside face of inductor 12 is a gas discharge valve 14. Gas discharge valve 14 is connected to substrate 38 by a conical support 18 proximate the center of substrate 38, as shown. Further, gas discharge valve 14 includes a conical hood 16 for dispersing the gas. As will be described hereunder, a gas, such as argon, is introduced in pulses from a tank (not shown) through valve 14 such that conical hood 16 disperses the gas around the outside of conical support 18 and against the outside face of inductor 12. A cuff 47 prevents loss of gas over the outside rim of inductor 12. FIG. 1 indicates the remaining components of PIT 10 schematically by housing 19 at the back side of inductor 12. As seen in FIG. 2, however, PIT 10 does not incorporate an enclosure such as housing 19. Opposite gas discharge valve 14 and proximate an inside face of inductor 12 is a support plate 26. Support plate 26 is displaced from inductor 12 to prevent magnetic interference with inductor 12. Support plate 26 is connected to substrate 38 by means of support members 22 and 24, also proximate the center of substrate 38 as shown. Support plate 26 is incorporated to support and position a plurality of capacitors. In FIG. 2, only capacitors 28 and 30 are shown, but in practice many more will be included as will be described below. Each of capacitors 28 and 30 is electrically connected to a capacitor charger power source (not shown), a trigger generator 36 and a number of specific coils 46 of inductor 12. In FIG. 2, capacitors 28 and 30 are connected to coils 46 by mean of wires 32 and 34 and to trigger generator 36 by coaxial wires 42 and 44, respectively. Trigger generator 36 is also supported by support plate 26 as shown. Typically, the electrical power required to charge capacitors 28 and 30 is generated by a nuclear-electric power source.
FIG. 3 shows the front (or back) side of inductor 12 incorporating 72 coil sections 20 on each side. Specifically, inductor 12 is configured such that each separate coil section 20 is electrically connected to a connector point 52 at an outer perimeter of annular inductor 12 and electrically connected to a connector point 54 along an inner perimeter of annular inductor 12, as shown. By tracing out a starting point from an outer connector point 52 to an inner connector point 54 along any separate coil section 20, it is apparent that each coil section 20 traverses one-quarter of the total distance around the entire annular inductor 12. Coil sections 20 are arranged on both faces of substrate 38 in this manner. Therefore, the configuration of FIG. 3 could be either face of substrate 38.
Now turning to FIG. 4, the configuration of every coil section 20 of inductor 12 is shown as if substrate 38 were transparent. In other words, there are twice as many coil sections 20 as are shown in FIG. 3, one-half being on one face of substrate 38 and the other half being on the opposite face of substrate 38. By studying FIGS. 3 and 4, and following the description as given above, it will become apparent that four coil sections 20 will make up a complete revolution of each coil 46 around inductor 12. Beginning at any outer connector point 52 a first coil section 20 will travel along one face of substrate 38 and be electrically connected to a first inner connector point 54 completing one-quarter of the revolution around inductor 12. From the first inner connector point 54 a second coil section 20 will travel another one-quarter distance around inductor 12 on the opposite face of substrate 38 and be electrically connected to a second outer connector point 52. Two interconnected coil sections 20 will then have traveled half the distance around inductor 12 in a W-shape. A third coil section 20 will be electrically connected to the second outer connector point 52 and travel another one-quarter of the distance around inductor 12 on the same side of substrate 38 as the first coil section 20 and be electrically connected to a second inner connector point 54. A fourth coil section 20 will be electrically connected to the second inner connector point 54 and travel the remaining distance around inductor 12 on the same side of substrate 30 as the second coil section 20 and be electrically connected to the first outer connector point 52 to form a complete loop of coil 46. A single loop in this arrangement is shown in FIG. 6. In the one embodiment disclosed, there are 36 such coil loops, or 144 coil sections 20 as shown in FIG. 4. Of course, other arrangements of coils, including more or less coil sections or loops, can be used without departing from the scope of the present invention.
Now turning to FIG. 5, support plate 26 supporting the capacitors is shown. As discussed above for FIG. 2, only capacitors 28 and 30 were shown. In practice, however, several more of these capacitors will be incorporated. In one embodiment of the present invention, every four consecutive outer connector points 52 are electrically connected in parallel to a single capacitor. Therefore, for capacitor 28, electrical line 32 will connect to a set of four consecutive outer connector points 52 as will capacitor 30. Consequently, support plate 26 supports 18 capacitors in the embodiment shown in FIG. 5. As is apparent from this description, each separate coil 46, as shown in FIG. 6, includes two capacitors connected to it. A single inductive loop which is electrically connected to more than one capacitor is commonly referred to as an inductive Marx Bank. As will be understood, other arrangements of the capacitors can be incorporated without departing from the scope of the present invention.
Now turning to FIG. 6, a single coil 46 of inductor 12 comprising four separate coil sections 20 as discussed above is shown. At each of the outer connector points 52, the coil sections 20 are connected to capacitors 28 and 30, as shown. It is noted that three other consecutive connector points 52 are electrically connected in parallel to capacitor 28 in substantially the same configuration as shown, as well as for capacitor 30. A switch 60 enables capacitor 28 to be discharged into coil 20 through a connector point 52. Likewise, a switch 62 enables capacitor 30 to be discharged simultaneously into coils 20 through a connector 52. Trigger generator 36 would close switches 60 and 62, as well as all of the other switches associated with the other capacitors, at the same time. The desirability of this Marx Bank configuration in accordance with at least one point of novelty of the present invention will be understood from the description of the operation given below.
By including a series of four coil sections in one loop, with two capacitors in the loop, the voltage of the coil/switch assembly is reduced by a factor of two while still maintaining the high induced EMF of the coil loop that is required for high ionization effectiveness and high thruster efficiency. This voltage reduction capability of the Marx Bank configuration of the PIT makes it possible to match the high EMF thruster to state of the art alternators without requiring a voltage transformer. The consequent mass saving is particularly important for high power spacecraft applications. The transformer mass eliminated by this invention is directly reflected in increased payload capability. An associated advantage of both the large number of parallel coils and the several capacitors used in each coil is the ease with which solid state switches can be incorporated in the low parasitic inductance thruster design. A state of the art feature of the coil geometry, seen in FIGS. 3 and 4, is the decreased coil section spacing toward the outer radius. This is done to compensate for loss of magnetic field due to the fringing effect of the annular inductor.
In operation of PIT 10, each capacitor is simultaneously charged by a voltage source to its charging level. After the capacitors are charged, a pulse of gas is injected by discharge valve 14. The gas is discharged out of conical hood 16 towards inductor 12. When the cloud of gas from conical hood 16 impacts inductor 12 it spreads out across the entire face of inductor 12 forming a sheet of gas. Once the gas hits inductor 12, it also begins to propagate backwards away for inductor 12. After the cloud of gas reaches inductor 12, but before it has a chance to be substantially reflected back, trigger generator 36 discharges all of the capacitors simultaneously. As discussed above, four coil sections 20 combine to form a single loop coil 46. At the outer connector points of each coil 46, a capacitor is connected to the coil 46. Therefore, each coil 46 has two capacitors connected to it. Since each capacitor is discharged at the same time, the EMF induced by the single coil 46 is double the voltage of each capacitor separately.
Upon switch closure of trigger generator 36, the total voltage from capacitors 28 and 30 is applied to each coil 46 causing the current to rise in the coil at a rate di/dt (where di is the change in coil current and dt is the change in time) which is equal to V/L, where V is the sum of the capacitor voltages and L is the thruster circuit inductance. At the instant of switch closure the voltage is large, but so also is the initial inductance of the coil whose magnetic field expands radially and axially away from the coil in the toroidal configuration typical of such a coil when no other current is present. The consequent limiting effect of this large initial inductance on di/dt is serious for the PIT. For it is the azimuthal electric field induced in the gas in front of the inductor by the rapidly varying magnetic field, dB/dt (where dB is the change in magnetic field), due to the coil di/dt that must ionize the gas, and this must happen very early in the capacitor discharge period to achieve high thruster efficiency. The EMF multiplication of the inductive Marx Bank makes it possible to achieve the necessarily large initial di/dt without seriously affecting the voltage requirement of the alternator which powers the thruster. As soon as the gas has become ionized and electrically conductive (a plasma), an intense current sheet forms that confines the magnetic field due to both the coil current and the plasma current to the space between these two current sheets. At this time, when the plasma current sheet is closest to the inductor face, the L which determines di/dt is the parasitic circuit inductance, which is carefully designed to be as small as possible in the present invention so as to maximize dB/dt. The plasma current multiplied by its local magnetic field is the well known force equal to the product of current and magnetic field. This force can also be represented as proportional to the square of the local magnetic field, B 2 . Consequently, it is proportional to the inverse of the square of the parasitic inductance. Also, it is a well known theorem of the PIT that thruster efficiency for fully ionized propellant is directly related to the ratio of maximum thruster inductance (as plasma leaves the thruster) to the initial inductance (parasitic) when the plasma is closest to the inductor. Thus, it is clearly seen that use of the inductive Marx Bank for early ionization, the design for minimum parasitic inductance for high thruster efficiency, and the reduction of the voltage requirement on the alternator are important features of the invention. The associated ease of solid state switching is also an attractive advantage.
The foregoing discussion discloses and describes merely exemplary embodiments of the present invention. One skilled in the art will readily recognize from such discussion and from the accompanying drawings and claims, that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims. | This invention discloses an engine for use in sustained space travel. The engine is of an electric type powered by a nuclear reactor. The electric engine includes a pulsed inductive magnetic thruster. A gas is discharged against an inductor comprising a series of parallel coils arranged in a spiral fashion. Each coil consists of four separate electrically connected coil sections. Each coil section traverses one-quarter of the distance around the inductor from an outer perimeter to an inner perimeter to form a single closed loop. A capacitor is electrically connected to two outer perimeter connector points for each coil forming a Marx Bank arrangement. All capacitors are charged to full charge and discharged simultaneously by a trigger generator immediately after a puff of propellant gas reaches the inductor. The high induced EMF in the inductor caused by the multiple capacitors in series in a single loop creates a rapidly rising magnetic field which ionizes the propellant gas. The current and magnetic field in the ionized gas drives the gas away from the coil creating the thrust which drives the spaceship. | 7 |
FIELD OF THE INVENTION
This invention relates to psyllium-enriched dough products. The dough products may be administered to humans and animals susceptible to or afflicted with hypercholesterolemia to lower serum cholesterol or to individuals in need of dietary regulation. The invention also relates to a method for producing the dough products, in which psyllium is subjected to pretreatment, i.e., pre-wetting.
BACKGROUND OF THE INVENTION
Psyllium is a known mucilaginous material which has found extensive use in bulk laxatives. The source of psyllium is the seeds of plants of the Plantago genus, which grow in certain sub-tropical regions. Since it is believed by those skilled in the art that the active ingredient of psyllium is the psyllium seed gum, which is located primarily in the seed husk, present technology uses the ground seed husk as the source of psyllium. However the whole seed is also known as a psyllium source, as well as the dehusked psyllium seed.
It is well known that psyllium decreases plasma triglycerides and LDL cholesterol, particularly in humans. The specific use of a psyllium hydrophilic mucilloid to lower cholesterol in serum was documented by Anderson et al., Arch. Intern. Med. Vol. 148, February 1988, 292-296 (1988), Anderson et al., Am J. Clin Nutr. Vol.56, p. 93-98, (July 1992). It has been theorized that psyllium, which belongs to a class of gel forming soluble fibers, disrupts the absorption or metabolism of cholesterol by binding, entrapping, absorbing, or otherwise interfering with the reabsorption of bile acids across the intestinal lumen. It is also theorized that the soluble fiber interferes with the intraluminal formation of micelies, resulting in decreased cholesterol and bile acid reabsorption. The end result is that more bile acids and dietary cholesterol are ultimately excreted in the feces, resulting in a decreased level of serum cholesterol.
However, due to its mucilaginous nature, psyllium acquires a slimy or adhesive texture and mouthfeel upon hydration. Psyllium normally forms a gelatinous mass when contacted with water and exhibits poor dispersibility and mixability in water. Psyllium also develops a distinctive, undesirable flavor in the presence of heat and moisture which further limits its use in food products. This slimy mouthfeel is unpalatable and, accordingly, various additives have been incorporated in psyllium-containing ingestible compositions in order to mask the undesirable texture and mouthfeel of the psyllium.
Notwithstanding the undesirable flavor and texture imparted to an ingestible composition by psyllium or psyllium husks, various psyllium-containing foodstuffs have been proposed which purport to take advantage of the natural digestion regulation properties of psyllium, or the satiating or "fullness-feeling" effect of psyllium. See, for example, U.S. Pat. Nos. 3,574,634 and 4,348,379.
In addition, it has been suggested, for example, in U.S. Pat. No. 3,148,114, the whole psyllium husks, such as the ground husks of the seed of Plantago psyllium, lower blood cholesterol upon oral administration thereof. Further, it has also long been known to use small quantities of psyllium, such as less than 1%, as a thickener in foodstuffs, such as in ice cream, puddings and the like.
Finally, U.S. Pat. No. 4,849,222 discloses a medicament composition for reducing blood cholesterol levels in humans and lower animals which comprises a mixture of psyllium seed gum, or source of psyllium seed gum, and a nonabsorbable, nondigestible polyol polyester.
However, as set forth above, the mucilaginous nature of psyllium husks presents grave processing difficulties, and prior attempts to produce a palatable, ready-to-eat food product containing psyllium have not resulted in a satisfactory product to date, particularly, with respect to flavor and texture or mouthfeel.
Attempts have been made to incorporate psyllium into foodstuffs, so that the fiber can be consumed as part of a regular meal or other aspect of a normal diet, without any connotation or association with medicines, as well as with acceptable organoleptic properties. Examples of the patent literature involving psyllium incorporated into foodstuffs are U.S. Ser. Nos. 817,244 and 819,569 both filed Jan. 6, 1992, now U.S Pat. Nos. 5,223,298 and 5,227,248, both of which are incorporated by reference. These patents teach psyllium containing ready to eat cereals. Additional examples of cereals containing psyllium are set forth by Moskowitz, U.S. Pat. No. 4,766,004; Ringe U.S. Pat. No. 5,024,996; and Ringe et al., U.S. Pat. No. 5,026,689. Other foodstuffs which include psyllium are taught in U.S. Pat. Nos. 5,095,008 and 5,950,140 both of which teach cookies with incorporated psyllium, U.S. Pat. No. 5,015,486, which teaches microwaveable muffins, and U.S. Pat. No. 5,024,996 in which teaches almond paste containing compositions, such as marzipan. U.S. Pat. No. 5,164,216 describes bread suitable for microwaving which contain required levels of shortening and fiber. Psyllium mucilloid is mentioned as a potentially useful fiber source; however, no examples of its use are given, nor is there any discussion of problems associated therewith.
In fact, psyllium cannot be routinely incorporated into dough products such as bread. It has been found that "neat" psyllium, when combined with other ingredients, leads to an unpalatable product. The invention described herein, however, teaches a product which overcomes the problems experienced when psyllium is directly incorporated into dough products. It has been found, surprisingly, that the simple step of prewetting psyllium prior to incorporating it into a bread product eliminates the organoleptic objections encountered with non-prewetted psyllium.
It is therefore a principal object of this invention to provide for an effective and economically produced food composition comprising psyllium in a dough product for use in bread or bakery products. A method for the production of the psyllium dough product is also provided herein.
It is a further object of this invention to provide for a bread or bakery composition containing psyllium which is palatable and suitable for human consumption in a food product while providing the benefits of lowered serum cholesterol levels.
SUMMARY OF THE INVENTION
This invention provides for a dough product, i.e., bread or baked food product, enriched with pretreated psyllium, in such a way so as to render the psyllium soluble and palatable in the food product. The pretreatment of psyllium prior to mixing the other bread ingredients provides for a palatable psyllium enriched dough for the manufacture of bread and other baked goods. The invention also provides for a psyllium enriched dough product which also contains an amount of gluten, e.g. vital wheat gluten, which is added during the processing of the psyllium-enriched dough product of this invention and which is responsible for the increase in volume in the final product.
DETAILED DESCRIPTION OF THE INVENTION
It is has been found that pretreating psyllium with water prior to incorporation of other ingredients results in a dough product with satisfactory mouthfeel, texture, and taste. When the psyllium is added directly with other ingredients, the psyllium absorbs the water instantly and prevents gluten development. When the grain, e.g. wheat, is ground and mixed with water, the grain protein forms a complex, semisolid structure called gluten which is both plastic and elastic. Gluten formation and development is important during the baking processes because the gluten expands to accommodate the gases produced by the yeast.
Therefore, before the incorporation of psyllium to the main bread ingredient, e.g., wheat, rye, flour, the psyllium must be pretreated in order to ensure adequate absorption and successful incorporation into the dough product.
The psyllium product may be incorporated in the form of 98% purity extruded psyllium or in the form of cold extruded psyllium containing pellets. According to the cold extrusion process, the psyllium is mixed with flour, sugar and Myvaplex and extruded to form a "cold form" pellet by the cold extrusion process. The pellets are dried and ground for use as psyllium raw material. The ground psyllium manufactured from the cold formed pellets is subjected to a pretreatment process which involves prewetting psyllium with water. By this cold extrusion step, the hydration rate of the psyllium is retarded and allows for the smooth incorporation into the dough product.
This invention will be better understood by reference to the following controls and examples, which are included here for purposes of exemplification and are not to be construed as limitations.
CONTROL 1
This control experiment demonstrates that without a pretreatment step, psyllium cannot be successfully incorporated into a dough product. A sample of 98% purity extruded psyllium, as described below, was used in a bread recipe, as indicated:
______________________________________ Amount % (Dry Basis)______________________________________Bread Flour 350.00 g 68.36Sugar 25.00 g 5.48Dry Milk 9.00 g 1.83Shortening 21.00 g 4.60Water 295.00 g 0.00Psyllium (extruded 98% purity) 82.00 g 16.51Yeast 6.70 g 1.47______________________________________
A 98% purity extruded psyllium product can be used as the starting material. The 98% purity extruded psyllium can be prepared utilizing the following parameters. The psyllium is extruded through a WP/twin screw extruder at a minimum temperature of 240° F. The moisture of the material in the extruder is maintained at approximately 15.5% to about 17.5% water during the extrusion process. The approximate feed rate for the psyllium product is about 15 to 17 kg per minute, preferably at about 16 kg per minute. The finished 98% purity extruded psyllium product has a moisture content of about 6-10%.
The ingredients were combined in an automatic bread baking machine, and manufacturer's instructions were used. The bread product contained approximately 3.4 gms of psyllium per one ounce serving.
The psyllium used in this example was not subjected to cold extrusion or to the prehydration, e.g., prewetting step.
The resulting dough had a very strong psyllium odor during baking. The mixed dough was also very dry and did not remain intact. There was additionally no increase in volume during the rising step. The crumbs were very dense and the crust was very dark, e.g., a brown to black color. The failures in the product were such that it was not subjected to taste testing.
CONTROL 2
Following control 1, another attempt was made to make a psyllium enriched bread with a smaller amount of psyllium, e.g., 3.4 gms of psyllium per two ounce serving (i.e., 1.7 g per slice). Cold extruded psyllium pellets (50%) as described below and in U.S. Ser. Nos. 08/123,342, 08/123,352, filed Sep. 17, 1993, were ground to pass a 1.0 mm screen.
The following ingredients were combined to form 50% cold extrusion pellets:
______________________________________ 55.6 lbs rice flour 48.0 lbs sucrose109.9 lbs psyllium 98% purity 2.0 lbs Myvaplex______________________________________
The cold extrusion process takes place by extruding the above ingredients through a WP twin screw extruder to form the pellets. A cool water bath is applied to the extruder so as to maintain the temperature during the extrusion process. The extruder preferably contains a means to measure the temperature during the extrusion at two zones. Zone 1 is the point at which the mixture is fed through the extruder. Zone 2 is where the mixture is substantially mixed and extruded. During cold extrusion, the temperatures maintained in zone 1 is approximately 60° to 80° F., preferably the temperature is about 73° F. The temperatures in zone 2 is kept at approximately 160° to 180° F., preferably the temperature in zone 2 is about 169° F. The pellets are then extruded through a die and dried for about 50 to 90 minutes, preferably 70 minutes, at about 150° F. to a maximum of 200° F., to a moisture content of approximately 6-10%, preferably about 8%.
After the pellets were formed, they were ground to prepare the psyllium flour. The psyllium of this example, was not subjected to prewetting. The psyllium was used in its dry, ground form. The recipe for this bread is as follows:
______________________________________ Weight (g) Dry Basis %______________________________________Bread flour 290.80 56.58Sugar 30.28 6.61Dry Milk 10.94 2.21Salt 6.03 1.32Shortening 21.94 4.79Water 334.16 0.00Vital gluten flour 48.21 6.79Yeast 6.80 4.19Psyllium (as above) 90.02 12.22______________________________________
Analysis of the product showed that the 50% cold extruded psyllium did not swell as much as the 98% purity extruded psyllium, i.e., the swell volume for the cold extruded psyllium was approximately one half the swell volume for the extruded psyllium. The resulting dough was very dry. In fact, the original recipe called for 309 g of water, but 25g additional water was necessary in order to produce a reasonable dough. The finished loaf had very dense crumbs, with a dark colored crust. The loaf volume was also very small, and similar to that produced in the first control. This bread sample was not palatable to the taste testing team.
EXAMPLE 1
The following example illustrates the efficacy of pretreating the psyllium with water prior to adding the psyllium to the other ingredients of the dough composition. This psyllium dough product contained the following ingredients:
______________________________________Ingredient Amount (g) % Dry Basis______________________________________Bread flour 350.0 67.98Sugar 30.0 6.54Dry Milk 12.0 2.42Salt 3.0 0.65Shortening 21.0 4.58Water 237.0 0.00Yeast 6.7 1.40Psyllium (extruded 98% purity) 82.0 16.42Water 60.0 0.00______________________________________
The amount of psyllium added was such that a one ounce portion of the resulting bread would contain 3.4 g of psyllium.
The psyllium was first prewet with 60 g of water. The other ingredients were mixed before adding the prewetted psyllium to the dough. The first dough consisted of the dough ingredients with the exception of the prewetted psyllium and the yeast. After the dough was kneaded for twenty minutes, the prewetted psyllium and the yeast were added to the dough and further kneaded.
Water was sprayed into the psyllium gradually while the psyllium was mixed, in order to prevent any lumping from occurring. The psyllium particles were kept small in order to maximize incorporation in the dough.
The amount of sugar was increased in this example as compared to Controls 1 and 2 to provide more material for the yeast to act upon. The amount of salt was decreased in this example, to produce a low salt bread product. The same baking protocol as was used in Controls 1 and 2 was followed.
The resulting loaf was small, e.g., approximately one half the size of the standard loaf. The crumb was very dense with very small air cells. However, there is no detectable psyllium odor while the bread is baked and during consumption.
EXAMPLE 2
The following example further illustrates that the psyllium had to be prewetted before addition to the dough in order to achieve acceptable incorporation. The following ingredients were incorporated into a dough composition:
______________________________________Ingredient Amount (g) % Dry Basis______________________________________Bread flour 380.0 75.27Sugar 30.0 6.67Dry Milk 11.0 2.27Salt 6.0 1.33Butter (Margarine) 21.0 4.67Water 249.0 0.00Yeast 6.7 1.43Psyllium (extruded 98%) 41.0 8.37Water 30.0 0.00______________________________________
This dough was prepared in a manner similar to example 3. However, the psyllium percentage, by dry weight, was decreased by 50% so as to yield a product containing 1.7 of psyllium per ounce. The prewetted psyllium was added to the dough with the yeast after the first twenty minutes of kneading.
The finished dough product did not rise as much as the standard loaf, although this loaf had a larger volume than that produced in example 1. The crumb was dense but there was no detectable psyllium odor. The bread was aromatic during the baking process. The bread also had good sensory evaluation and was considered palatable by a tasting team.
EXAMPLE 3
The following examples illustrate a further embodiment according to this invention. The foregoing examples provide for a psyllium dough product which when baked does not rise to the volume of a standard size loaf. The following ingredients were combined according to the process detailed below to prepare a bread product which rises to a standard size loaf.
______________________________________Ingredient Amount (g) % Dry Basis______________________________________Bread flour 292.68 57.23Whole wheat flour 50.53 44.63Sugar 30.19 6.63Dry Milk 11.16 2.27Salt 5.94 1.30Shortening 20.42 4.48Water 249.0 0.00Vital gluten flour 38.80 7.94Yeast 6.71 1.41Psyllium (extruded 98%) 44.41 8.95Water 50.98 0.00______________________________________
As with example 2, the bread product contained 1.7 g of psyllium per ounce.
In order to prepare a dough product which rises to the standard size loaf, a smaller amount of bread flour was used and was replaced with whole wheat flour (graham flour), and vital gluten. The dry ingredients listed above were mixed in a pan and water was added to knead the dough. The prewetted psyllium was processed, as in example 1. Baking was carried out as on the prior examples.
The height of the finished loaf was 4.5 inches in the center and 3.5 inches at the edge. There was a nice crumb texture and cell structure. The loaf had dense crumb structure. The finished product was slightly wet; however, the aroma and texture were deemed acceptable by a tasting team, especially after toasting. No objectionable psyllium taste was detected.
EXAMPLE 4
The following further illustrates the necessity of pretreating the psyllium. The psyllium used in this example is the cold extruded psyllium pellets, ground to prepare the raw material. The following ingredients were combined to prepare the dough product:
______________________________________Ingredient Amount (g) % Dry Basis______________________________________Bread flour 289.28 56.77Sugar 30.23 6.66Dry Milk 11.53 2.35Salt 6.19 1.36Shortening 20.97 4.62Water 259.49 0.00Vital gluten flour 44.86 9.21Yeast 6.80 1.43Psyllium (cold extruded 50%) 90.99 17.59Water 48.21 0.00______________________________________
The example used a cold extruded psyllium (50%) pellet product for the dough composition. The cold extruded psyllium product was prepared according to Control 2 as set forth above and also described in Ser. Nos. 08/123,342, 08/123,352, filed Sep. 17, 1993. The psyllium pellets were ground into a powder. The psyllium powder was then prewetted before adding to the remaining ingredients.
This dough product was baked in the automatic bread baker of example 1, as described supra, but rapid bake mode was used, which is approximately one hour and thirty minutes faster than the earlier bake trials. The resting time between the first and second steps was reduced to only 5 minutes rather then the usual thirty minutes. The yeast was mixed with other dry ingredients rather than introducing it during the resting time. Psyllium (prewet) was added during the rest phase.
The finished dough product had a golden crust. The loaf had very good cell structure and good aroma. The loaf height at the center was five inches and 4.5 inches at the edge. The crumb was damp, probably due to excess water retention by psyllium. It was found that the addition of yeast earlier in the dough processing improves the loaf volume. The bread was deemed the best of all loaves tested.
EXAMPLE 5
The cholesterol lowering effect of the psyllium enriched dough of this invention on certain individuals is confirmed by the following study.
Over the course of six months, a long term intervention study is conducted to test the effect of the psyllium enriched product on the level of serum cholesterol on sample size of 250 hypercholesterolemic individuals. Individuals chosen for this study are at risk for mild abnormalities in their cholesterol levels. Generally, the study targets individuals with plasma LDL-cholesterol levels at 130 to 220 mg/dl, with the proviso that their triglycerides levels are less than 300 mg/dl. There is an initial eight week dietary instruction and stabilization period where lipid criteria are ascertained.
According to the protocol of the intervention study, the individuals participating in the study are divided into four groups. The groups are administered varying number of servings of a psyllium enriched food product to determine whether there is a dose dependent hypocholesterolemic effect. The participants are given a choice of psyllium enriched food products: R-T-E- cereal, bread, snack bars, and pasta, which are packaged in zero and 3 mg psyllium servings.
Group A is given three servings of the placebo product per day and is not administered a psyllium food product at all.
Group B is given two servings of the test product and one serving of the placebo product per day.
Group C is given one serving of the test product and two servings of the placebo product per day.
Group D is given three servings of the test product per dayu.
The serum cholesterol levels are tested periodically during the study by taking blood samples and determining cholesterol level in the serum.
The cholesterol levels decrease from baseline over the course of the study indicating the hypocholesterolemic effect of psyllium enriched products. The study further shows that the decrease in serum cholesterol is in proportion to the dosage units of psyllium product ingested.
EXAMPLE 6
A study was also conducted to test the efficacy of psyllium enriched products in reversing the rise in plasma total cholesterol in hamsters fed a diet with added cholesterol.
The hamsters were administered a diet consisting of 20% protein, 14% fat, 15% sugar, 1% NaCl. The amount of total dietary fiber was targeted at 10%, which includes non-soluble and soluble fiber.
The control group was given a food product without (Product A) and with added cholesterol (Product B). The control product with added cholesterol (Product B) and the psyllium bread test product (Product C) contained about 0.125% cholesterol.
The control products without and with cholesterol (Products A and B) and the psyllium enriched bread product (Product C) contained the following ingredients as a percentage of the entire composition:
______________________________________ A B C______________________________________1. vitamin/mineral 7.95% 7.95% 7.95% amino acid mixture2. Test Material -- -- 39.13. wheat bran 24.0 24.0 10.44. Casein 18.0 18.0 12.05. Safflower Oil 4.0 4.0 3.06. Sucrose 14.3 14.3 9.77. NaCl 0.99 0.99 0.378. Starch 23.8 23.6 10.49. Cholesterol -- 0.125 0.12510. Beef Tallow 7.0 7.0 7.0______________________________________
It was found that the total cholesterol level for hamsters fed with Product A containing no added cholesterol, measured in mg/dl, was 157.0±31.0. It was also found that the total serum cholesterol levels of hamsters fed Product B with added cholesterol, and of hamsters fed on hamsters fed psyllium enriched bread Product C, decreased from 221.7±27.7 to 149.1±21.5. This study establishes that a psyllium enriched bread product fed to hamsters on an elevated cholesterol diet reduces the level of total cholesterol.
The psyllium bread product now having an established hypocholesterolemic effect on an elevated cholesterol diet was then administered to individuals for a taste preference test comparing conventional and psyllium enriched bread.
EXAMPLE 7
The following test was carried out to determine the overall preference for standard white bread and bread with psyllium.
The control white, low fiber bread and psyllium enriched bread was produced according to Applicants' specifications.
Sixty-two panelists were given half a slice of each of the control bread and the test bread both toasted and spread with strawberry jam. The serving size was half a slice of bread. The bread was toasted and spread with one teaspoon of strawberry jam prior to slicing. The illumination was white.
The panelists were asked to determine which bread they preferred. Thirty-one of the sixty-two panelists preferred the test bread with psyllium, p-value=0.500. A significance criteria of p=0.05 was set prior to this test. Based on this test, no preference was found between the standard white low fiber bread and the test bread made with psyllium when served with strawberry jam.
These foregoing examples show that the dough products may be made with prewetted, extruded psyllium. Where the psyllium is subjected to pretreatment with water, the dough is easily handled and the finished product has good aroma and taste. There is little detectable psyllium odor. The examples also show that where psyllium is pretreated according to the processes delineated, the mucilaginous fiber is rendered soluble and dispersable in water.
The examples demonstrate that prewetted psyllium is required to produce an acceptable bread or bakery product. It is especially preferred that the prewetted psyllium be cold extruded psyllium.
The examples all use various ingredients besides yeast, flour and water, which are the minimum ingredients required to make a yeast leavened bread product. It will be understood, e.g., that ingredients such as salt, dry milk powder, sweeteners, shortening, etcetera, are options which, while they may lead to a better product, are not required. In the case of shortening, for example, cholesterol free options, such as margarine or vegetable oil may be used, as can butter. Sugar, honey, molasses, corn syrup etcetera, are examples of sweeteners which may be used. Even in the case of leavening agents, while yeast is by far the most common and preferred leaven, the art is familiar with, e.g., "sourdough" leavens (Lactobacillus), and other leavening agents. More than one leaven may be added as well, such as bicarbonates.
The key ingredient of this invention is the prewetted psyllium. Prewetted psyllium, as will be seen, requires a pretreatment step, i.e., mixing with water. The psyllium so treated may be any form thereof, such as cold, extruded psyllium which has been ground to a powder, extruded psyllium, and so forth. Prewetted psyllium is generally prepared by adding water to the psyllium and allowing the mixture to temper before combining with other ingredients. It is preferred to combine the water and psyllium in a range of from about 0.75:1 to 1.25:1 (by weight). A ratio of 1:1 is particularly preferred.
The tempering period for the prewetted psyllium may vary. The key aspect is that the prewetted psyllium possesses a free flowing nature as compared to the non-prewetted material. The prewetting step must be performed shortly before use because the high water level affects its stability. If the prewetted material is allowed to temper for more than about 24-48 hours, this property is lost. Moreover, an extensive time period may encourage the growth of microorganisms. Therefore, the prewetted psyllium should not be permitted to temper for more than about 24-48 hours. It is especially preferred to allow it to temper overnight (10-12 hours) or even less. It is especially preferred to use the psyllium at no more than about 30 minutes after prewetting treatment.
In some of the examples, vital gluten was added to improve load size of the resulting product. This is a standard additive in commercial leavened bread products, but should not be seen as a requirement of the final product.
A flour component is required in the bread product. Most usually, this will be a wheat flour, such as "bread flour", or white flour. So-called "graham" or whole-wheat flour may be used as well. All mills of these flours are possible in the invention, as are non-wheat flours, such as rye, corn, oat, hybrids such as triticale, and so forth. These flours may be used alone or in combination. When no wheat based flour is used, it may be desirable to incorporate vital gluten or gluten in some form so as to give the baked product strength, stability, and height.
Additional ingredients may be added to the bread products of the invention. Some of these are set forth supra. Others include eggs or egg components, whole milk or fractions of milk, vegetable or fruit ingredients (e.g., carrot, pumpkin, banana, zucchini), whole grains, seeds, flavor extracts, preservatives, and so forth.
The terms "dough product" and "baked product" as used herein are intended to cover any leavened flour containing product. In addition to bread, the terms include breakfast breads, such as croissants, bagels, "English Muffins" and the like; muffins, pizza crusts, leavened pretzels, leavened cakes, sweet rolls, and so forth. The prewetted psyllium is incorporated into the dough so as to yield a product containing anywhere from about 1.0 to about 5.0 grams of psyllium per ounce of product. Generally, it is preferred that the product contain from about 1.5 to about 3.75 grams of psyllium per ounce of product.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, it being recognized that various modifications are possible within the scope of the invention. | The invention provides for a dough product, that is enriched with a psyllium composition. The psyllium may range from about 1.0 to about 5.0 grams per one ounce. The dough product can include an amount of gluten to increase its volume. Also provided is a method for making the dough products. These dough products are useful in lowering serum cholesterol levels as well as for increasing dietary fiber in the diet of the individual consuming them. | 0 |
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a drill bit for drilling bore holes in earthen formations. More particularly, the present invention relates to a drill bit having a plurality of cutters that includes multiple cutting areas.
BACKGROUND OF THE INVENTION
In the exploration of oil, gas, and geothermal energy, drilling operations are used to create boreholes, or wells, in the earth. Drill bits are in the center of such operations, disintegrating earthen formation. A drill bit substantially has a bit body connected by a drill string in one end and a plurality of cutters/cutting elements on the other end of the bit body. Conventionally, these cutters have one cutting area that is made of superhard material, such as polycrystalline diamond. While these cutters have been effective in disintegrating earthen formation, there always has been a need for more effective cutters that can expedite the drilling operations.
SUMMARY OF THE INVENTION
It is a general object of the present invention to provide improved earth boring cutters or cutting elements for a drill bit and improved drill bits.
An earth-boring bit is disclosed. The drill bit has a bit body configured for connection to a drill string. A plurality of cutters is secured to the bit body. The cutters are configured to disintegrate earthen formation as the bit body is rotated by the drill string.
At least one of the cutters comprises a substantially cylindrical first body made of hard metal. A substantially cylindrical first cutting element is attached to an end of the first body. The cutting element is made of a superhard material. A trailing end defines the opposite end of the first body. A first cutting face is located on the first cutting element. A first cutting edge defines a beveled perimeter of the first cutting face. A cylindrical slot is formed in the first body. A substantially cylindrical second body made of hard metal is located in the slot. A substantially cylindrical second cutting element is attached to an end of the second body. The second cutting element is made of a superhard material. A second cutting face is located on the second cutting element. A second cutting edge defines a beveled perimeter of the second cutting face.
In accordance with another exemplary embodiment, the hard metal comprises tungsten carbide. In accordance with another exemplary embodiment, the superhard material comprises polycrystalline diamond. In accordance with another exemplary embodiment, the cutting faces are flat.
One of the principal advantages of the exemplary embodiments is that it provides an additional cutting edge and face to a conventional cutter, which only has one cutting edge and face. Another advantage of the exemplary embodiments is that its additional cutting edge and face can have different orientation from the first cutting edge and face, allowing the bit to disintegrate an area of earthen formation where the first cutting edge and face cannot reach. Naturally, it will improve the effectiveness of a drilling operation, saving significant amounts of time and cost for the operation.
As referred to hereinabove and throughout, the “present invention” refers to one or more exemplary embodiments of the present invention, which may or may not be claimed, and such references are not intended to limit the language of the claims, or to be used to construe the claims in a limiting manner.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects and features of the invention will become more readily understood from the following detailed description and appended claims when read in conjunction with the accompanying drawings in which like numerals represent like elements.
The drawings constitute a part of this specification and include exemplary embodiments to the invention, which may be embodied in various forms. It is to be understood that in some instances various aspects of the invention may be shown exaggerated or enlarged to facilitate an understanding of the invention.
FIG. 1 is a side view of prior art, a drill bit comprising a plurality of single tiered cutters.
FIG. 2 is a side view of a drill bit in accordance with one of the exemplary embodiments.
FIG. 3 is an isometric view of a cutter in accordance with one of the exemplary embodiments and shown in FIG. 2 .
FIG. 4 is an isometric view of a cutter in accordance with another exemplary embodiment.
FIG. 5 is an exploded view of the cutter shown in FIG. 4 .
FIG. 6 is an isometric view of a cutter in accordance with another exemplary embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description is presented to enable any person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. As used herein, “substantially” is to be construed as a term of approximation.
As referenced herein throughout, the term “hard metal” refers to metal that is hard enough to withstand pressures and force necessitated in disintegrating earthen formation during drilling operation. Examples of such hard metal include cemented tungsten carbide and the like. The term “superhard material” refers to material that possesses hardness similar to diamonds and greater than that of hard metal. Examples of such superhard material include polycrystalline diamond, cubic boron nitride, thin-film diamond, and the like.
Referring to FIG. 1 , a side view of a conventional earth-boring drill bit 1 is shown. Conventional earth-boring drill bit 1 comprises a bit body 10 connected to a drill string 30 on one end and a plurality of cutters 20 secured on the other end. As shown, each of the cutters 20 in the conventional earth-boring drill bit 1 has one cutting edge and face.
Referring to FIG. 2 , a side view of an exemplary embodiment of an earth-boring drill bit 1 ′ is shown. Drill bit 1 ′ comprises a bit body 10 ′ connected to a drill string 30 ′ on one end, and a plurality of cutters 100 secured on the opposite end. Bit body 10 ′ is substantially cylindrical in shape. As the drill string 30 ′ rotates, so does the drill bit 1 ′, disintegrating earthen formation with its cutters 100 . Drill bit 1 ′ may comprise other exemplary cutters 100 , 200 , 300 , or a combination thereof, as shown in FIGS. 3-6 .
FIG. 3 is an isometric view of one of the exemplary cutters 100 shown in FIG. 2 . Cutter 100 has a first body 110 that includes a first cutting element 112 and a first trailing end 114 . First body 110 is substantially cylindrical in shape and may be comprised of hard metals, such as tungsten carbide. First cutting element 112 is substantially cylindrical in shape and includes a first cutting face 118 and a first cutting edge 116 . First cutting face 118 is located on top of first cutting element 112 and may be substantially flat. First cutting edge 116 defines the perimeter of first cutting face 118 and may be comprised of superhard materials, such as polycrystalline diamond.
In FIG. 3 , between first cutting element 112 and first trailing end 114 of first body 110 , there is a second body 120 . Second body 120 is substantially cylindrical in shape and has a second cutting element 122 and a second trailing end 124 . Second cutting element 122 is substantially cylindrical in shape and has a second cutting face 128 and a second cutting edge 126 . Second cutting face 128 is located on top of second cutting element 122 and is substantially flat. Second cutting edge 126 defines the perimeter of second cutting face 128 and may be comprised of superhard materials, such as polycrystalline diamond. Second body 120 may be comprised of hard metals, such as tungsten carbide. Planes of cutting faces 118 , 128 may be parallel.
Second body 120 may be located anywhere between first cutting element 112 and first trailing end 114 . The axis (not numbered) of second body 120 may be parallel to the axis (not numbered) of first body 110 . A slot 140 (not shown) in first body 110 where second body 120 may be inserted may be formed using a cylindrical diamond grinder. Second body 120 may be bonded to slot 140 (not shown) by brazing or chemical adhesive.
In an alternative embodiment, first 110 and second 120 cutter bodies may be integrally formed during the sintering process. The size or diameter of slot 140 may vary by the size or diameter of the second body 120 . In the preferred embodiment, the diameter of first body 110 is greater than the diameter of second body 120 . In the more preferred embodiment, the diameter of second body 120 is between 80% and 50% of the diameter of first body 110 .
In an alternative embodiment, not shown, the orientation of first body 110 can be reversed in relationship to first cutting element 112 , such that trailing end 114 is adjacent first cutting element 112 . In this embodiment, first body 110 provides additional backing support to the forces acting on second cutting element 122 during drilling. This also permits a variable spacing as between first cutting element 112 and second cutting element 122 , by moving second cutting element 122 into closer proximity to first cutting element 112 .
Referring to FIGS. 4 and 5 , another embodiment of exemplary cutters 200 is illustrated. A substantially cylindrical first body 210 is made of a hard metal, such as tungsten carbide. A substantially cylindrical first cutting element 212 is attached to one end of first body 210 by brazing or other method. First cutting element 212 is made of a superhard material, such as polycrystalline diamond. A trailing end (not shown) defines the opposite end of first body 210 .
In a preferred embodiment, first cutting element 212 is substantially cylindrical in shape and includes a first cutting face 218 and a first cutting edge 216 . First cutting face 218 is located on top of first cutting element 212 and may be substantially flat. First cutting edge 216 defines the perimeter of first cutting face 218 .
A substantially cylindrical second body 230 is made of hard metal, such as tungsten carbide, and is attached in axial alignment to trailing end (not shown) of first body 210 . As seen in FIG. 5 , a cylindrical slot 240 is formed in second body 230 . A substantially cylindrical third body 220 is also made of hard metal, such as tungsten carbide. Third body 220 is located in slot 240 . A substantially cylindrical second cutting element 222 is attached to one end of third body 220 . Second cutting element 220 is made of a superhard material, such as polycrystalline diamond.
In a preferred embodiment, second cutting element 222 is substantially cylindrical in shape and includes a second cutting face 228 and a second cutting edge 226 . Second cutting face 228 is located on top of second cutting element 222 and may be substantially flat. Second cutting edge 226 defines the perimeter of second cutting face 228 . In a preferred embodiment, the planes of first 218 and second 228 cutting faces are substantially parallel.
Third body 220 may have the same length as second body 230 but may also be shorter. The axes (not numbered) of first body 210 , second body 230 and third body 220 may be parallel to the axis (not numbered) of first body 210 . Slot 240 in second body 230 , where third body 220 may be inserted, may be formed using a cylindrical diamond grinder. Third body 220 may be bonded to slot 240 by brazing. When inserted, second body 230 provides a carbide backing support to third body 220 . The size or diameter of slot 240 may vary by the size or diameter of third body 220 . Slot 240 may be partially formed in first body 210 . Alternatively, cutter bodies 230 and 220 may be integrally formed during the sintering process.
In an alternative embodiment (not shown), the orientation of second body 230 can be reversed in relationship to first cutting element 212 . The location of first body 210 is then relocated to behind second body 230 . In this embodiment, first body 210 provides additional backing support to the forces acting on second cutting element 222 during drilling. This also permits a variable spacing as between first cutting element 212 and second cutting element 222 by moving second cutting element 222 into closer proximity to first cutting element 212 .
FIG. 6 is an isometric view of one of the exemplary cutters 300 . Exemplary cutter 300 has a body 310 that includes a cutting element 312 and a trailing end 314 . Body 310 is generally cylindrical in shape. Between cutting element 312 and trailing end 314 , a spherical body 330 extends from body 310 . Spherical body 330 and body 310 may be comprised of hard metals, such as tungsten carbide. Spherical body 330 may be bonded by brazing to a slot (not numbered) formed in body 310 . The slot may be formed using a diamond grinder. Cutting element 312 is substantially cylindrical in shape and has a cutting face 318 and a cutting edge 316 . Cutting face 318 is located on top of cutting element 312 and is substantially flat. Cutting edge 316 defines the perimeter of cutting face 318 . Cutting element 312 may be comprised of superhard materials, such as polycrystalline diamond.
It will be readily apparent to those skilled in the art that the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present invention.
Having thus described the exemplary embodiments, it is noted that the embodiments disclosed are illustrative rather than limiting in nature and that a wide range of variations, modifications, changes, and substitutions are contemplated in the foregoing disclosure and, in some instances, some features of the present invention may be employed without a corresponding use of the other features. Many such variations and modifications may be considered desirable by those skilled in the art based upon a review of the foregoing description of preferred embodiments. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention. | The present invention relates to a drill bit having a bit body and a plurality of cutters, which are configured to disintegrate earthen formation as the bit body is rotated by a connected drill string. At least some of the cutters have a first and second body, first and second cutting faces and first and second cutting edges. The body is comprised of hard metal. The cutting elements are comprised of superhard material. The orientation of the first cutter body is reversible as to the other components to permit variation in the proximity of the first and second cutting elements. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of on board reactive component removal systems, and reaction systems and methods for the removal of reactive components from vapor phase fluid prior to introduction thereof into fuel- or liquid chemical-containing vessels (e.g., vessels employed for fuel, flammable liquid or reactive liquid storage and/or transport). In a particular aspect, the invention relates to systems and methods for the catalytic removal of reactive components from vapor phase fluid prior to introduction thereof into fuel-containing vessels, specifically oxygen and/or fuel vapors, thereby reducing the potential for fire and explosion in such vessels.
BACKGROUND OF THE INVENTION
[0002] In order to avoid the potential fire and explosion hazard in vessels containing fuel, flammable liquid or reactive liquid (e.g., ships carrying flammable fluids as cargo, and the like), it is necessary to reduce the concentration of reactive components (e.g., oxygen and/or fuel vapors) in the gas phase that may be brought into contact with liquid fuel. Many different approaches have been taken in efforts to address this problem. One such approach, for example, involves the use of a membrane based gas separator to remove a sufficient amount of oxygen from the fluid stream which is to be introduced into the fuel-containing vessel so as to reduce the oxygen concentration below 5%. This reduced oxygen content gas is then used as an inert gas blanket in the fuel storage vessel.
[0003] Another method employed in the art involves use of a pressure swing adsorption system to separate the oxygen from air to generate oxygen depleted inert gas for introduction into the fuel-containing vessel.
[0004] These, as well as other systems described in the prior art require elaborate setup and add significantly to the cost of operation. Accordingly, there is a need for improved systems and methods for removing reactive components (e.g., oxygen and/or fuel vapors), or reducing the levels thereof, from the vapor phase used to fill the void-space in fuel-containing vessels.
SUMMARY OF THE INVENTION
[0005] In accordance with the present invention, there are provided simplified systems and methods for reducing the concentration of one or more reactive component(s) in vapor phase fluids introduced into the void space of fuel-containing vessels. The simple apparatus described herein can be utilized to replace complex systems on the market. Simply stated, in one embodiment of the invention, the vapor phase fluid to be introduced into a fuel-containing vessel is passed through a reaction zone (e.g., a catalytic bed) operated under conditions suitable to allow the consumption and/or inactivation of reactive components therein (e.g., free oxygen or other reactive vapors), thus deactivating reactive components in the gas phase.
[0006] In another embodiment of the present invention, there are provided systems for deactivating, reducing the concentration of, or removing one or more reactive components (e.g., oxygen and/or fuel vapors) from the vapor phase which is to be introduced into a fuel-containing vessel. Invention systems include a fluid treating zone (typically comprising a reaction zone having an inlet and outlet, wherein the reaction zone provides conditions suitable to deactivate the reactive components). Optionally, inventive systems include the ability to remove heat and or water from the vapor phase.
BRIEF DESCRIPTION OF THE FIGURES
[0007] FIG. 1 is a schematic illustration of one embodiment of a reactive component reduction system according to the invention.
[0008] FIG. 2 is a schematic illustration of another embodiment of a reactive component reduction system according to the invention.
[0009] FIG. 3 is a schematic illustration of yet another embodiment of a reactive component reduction system according to the invention.
[0010] FIG. 4 is a schematic illustration of still another embodiment of a reactive component reduction system according to the invention.
[0011] FIG. 5 is a schematic illustration of a further embodiment of a reactive component reduction system according to the invention.
[0012] FIG. 6 is a schematic illustration of a still further embodiment of a reactive component reduction system according to the invention.
[0013] FIG. 7 is a schematic illustration of still another embodiment of a reactive component reduction system according to the invention.
[0014] FIG. 8 is a schematic illustration of yet another embodiment of a reactive component reduction system according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] In accordance with the present invention, there are provided systems for reducing the concentration of one or more reactive component(s) in a vapor phase fluid prior to introduction thereof into a container having fuel therein, thereby reducing the concentration of reactive component(s) in said vapor phase fluid below the concentration at which auto-ignition may occur when said vapor phase is introduced into said container. Invention systems comprise:
[0016] said container, and
[0017] a fluid treating zone comprising:
at least one inlet, at least one outlet, and a reaction zone, wherein said reaction zone provides conditions suitable to deactivate said one or more reactive component(s) when contacted therewith,
wherein only the outlet of said fluid treating zone is in fluid communication with the container, such that the inlet of said fluid treating zone has no communication with the container or contents thereof. Such systems are especially useful in applications where large quantities of volatile materials are being handled, e.g., in fuel transfer operations where large volumes of fuel are transferred from one vessel to another, such as occurs when the contents of fuel transport vessels are transferred from the transport vessel to a storage facility.
[0021] As readily recognized by those of skill in the art, there are a variety of reactive components which one may desirably wish to remove from vapor phase fluids (or reduce the concentration of in vapor phase fluids) when such fluids are brought into contact with fuel (such as fuel oil, diesel, jet fuel, marine fuel, and the like). One reactive component contemplated for treatment in accordance with the present invention is oxygen. Another reactive component contemplated for treatment in accordance with the present invention may also include fuel vapor, as well as a variety of additives and/or impurities commonly associated therewith. A particular advantage of the present invention relates to the fact that treatment of vapors as contemplated herein is accomplished via passage through the simple system described herein.
[0022] As employed herein, “deactivate” refers to the conversion of reactive components such as oxygen, fuel vapor, and the like, into substantially non-reactive species, i.e., species that are substantially inert under the conditions to which they are exposed. Preferably, deactivated species are non-flammable.
[0023] In one aspect of the present invention, reaction zones contemplated for use in the practice of the present invention comprise a catalyst which facilitates conversion of reactive component(s) to non-reactive component(s) when contacted therewith under suitable conditions. In one embodiment, catalyst can be contained within a vessel. When catalyst contemplated for use herein is contained in a vessel, the vessel can be equipped with an inlet end and an outlet end. In one aspect, the catalyst content can vary from the inlet end to the outlet end. In one aspect, the catalyst content can vary non-linearly from the inlet end to the outlet end, e.g., in one aspect, the catalyst content can increase from the inlet end to the outlet end. Alternatively, the catalyst content can decrease from the inlet end to the outlet end.
[0024] Alternatively, catalyst need not be contained within a vessel, instead existing in a form which allows passage of vapor phase fluid therethrough, or where the catalyst is supported in such a way that a separate vessel to contain the catalyst is not necessary.
[0025] Catalysts contemplated for use in the practice of the present invention include optionally supported metal catalysts, such as, for example, noble metals (e.g., platinum, palladium, gold, silver, and the like), precious metals, transition metals, metal oxides, rare earth oxides, nitrides, carbides, enzymes, and the like, as well as mixtures of any two or more thereof. “Catalytic” refers to facilitating a reaction or interaction involving one or more reactants. Catalytic materials may include noble metals, transition metals, metal oxides (e.g., transition metal oxides such as RuOx, LaMnOx and perovskites), and the like, as well as various combinations thereof.
[0026] Catalytic materials contemplated for use herein may optionally be supported on a variety of materials, such as for example, metallic supports, activated carbon, carbon black, and the like, as well as mixtures thereof. Inorganic oxides may also be employed as support materials, either alone or in combination, e.g., silica, alumina, silica-alumina, magnesia, titania, zirconia, montmorillonite, and the like, or combinations thereof, for example, silica-chromium, silica-titania, and the like.
[0027] When catalytic treatment of reactive components is employed, a wide variety of suitable conditions for contacting said catalyst with said one or more reactive component(s) are contemplated. Exemplary conditions comprise contacting the vapor phase materials with catalyst at a temperature in the range of about 25° C. up to about 1200° C. Presently preferred temperatures contemplated for use herein range from about 50° C. up to about 400° C. Even more preferred are temperatures ranging from about 100° C. up to about 350° C.
[0028] To facilitate control of the above-described catalytic process, invention systems can optionally further comprise a temperature modulator. Optionally, the temperature modulator can be a heat exchanger, which may include a heat exchange medium. The heat exchange medium can optionally include a liquid or external air. Optionally, heat exchange can be accomplished by evaporative cooling. As another alternative, heat exchange can be accomplished with a heat pump, an evaporative cooler, or the like.
[0029] The heat exchanger can be positioned in a variety of locations within the invention system, e.g. the heat exchanger can be associated with the catalyst containing vessel; or the heat exchanger can be positioned upstream or downstream from the catalyst containing vessel; or the heat exchanger may be integrated with the catalyst vessel.
[0030] When the temperature modulator is positioned upstream of the catalyst containing vessel, it is preferably used to pre-heat either the fuel vapor, air, or a mixture thereof. When the temperature modulator is positioned downstream of the catalyst containing vessel, it is preferably used to reduce the temperature of the vapor exiting the catalyst containing vessel. When the temperature modulator is associated with the catalyst containing vessel, it can be used to heat or cool the reaction vessel, as necessary, to provide conditions suitable for catalyzing reaction of oxygen with fuel vapor, thereby deactivating reactive components (e.g., oxygen and/or fuel vapor) in the fuel vapor and air mixture.
[0031] Alternative methods for treating reactive components in accordance with the present invention include employing a reaction zone which comprises a source of microwave energy sufficient to deactivate said one or more reactive component(s) when contacted therewith.
[0032] As yet another alternative method for treating reactive components in accordance with the present invention, a reaction zone can be employed which comprises a source of plasma energy sufficient to deactivate said one or more reactive component(s) when contacted therewith.
[0033] Optionally, invention systems may further comprise a flame arrestor between the fuel storage tank and the fluid treatment zone (e.g., a water lock) so as to prevent any possibility of combustion to communicate between the fuel storage tank and the fluid treatment zone. Alternatively, the fluid treatment zone can be designed so as to prevent any flame formation.
[0034] Additional optional features which may be included in invention systems include one or more sensors (e.g., oxygen sensors, chemical sensors, carbon dioxide sensors, nitrogen oxide (NO x ) sensors, and the like), which may be positioned upstream and/or downstream from the fluid treatment zone so as to monitor the levels of chemicals of interest (e.g., oxygen, hydrocarbons, CO 2 , NO x , and the like) in the inlet and/or outlet gas thereof. Additionally, a feedback loop could be provided so as to adjust the contacting conditions within the fluid treatment zone as a function of the chemical levels detected before and/or after the reaction zone.
[0035] Thus, in one aspect of the present invention, sensors contemplated for use herein can be in fluid communication with the inlet of the fluid treating zone, and such sensors can be employed to control the passage of vapor through the fluid treating zone in response to the reactive species content thereof For example, if the oxygen level of the vapor subject to treatment herein is below a target value, said vapor can be introduced directly into said container, without the need to pass through the fluid treating zone. Conversely, if the oxygen level of the vapor subject to treatment herein is above a target value, said vapor can be recycled through the fluid treating zone for further treatment before being introduced into said container.
[0036] As used herein, the term “upstream” refers to an element in a flow scheme which is located prior to or before a reference point or reference element. As used herein, the term “downstream” refers to an element in a flow scheme which is located after a reference point or reference element.
[0037] In certain embodiments of the invention, the system may also include a fluid purification module adapted to remove water from the treated air. For example, the fluid purification module may include a condenser to reduce the temperature of the treated vapor below the dew point, thereby facilitating removal of any excess water. In a particular embodiment, the fluid purification module may include a pressure swing adsorption module. In other embodiments, the purification module may include membranes. A recirculation line may be provided to transfer the fluid from the fluid purification module to the inlet to the reaction zone. The fluid purification module may be located upstream or downstream from the reaction zone. In other embodiments, water may be removed by a moisture trap.
[0038] As used herein, “purification” and “purifying” refer to the removal from a fluid of one or more components. The removal may be partial, complete or to a desired level and may include removal of only some or all components.
[0039] In one embodiment, the system may also include a recirculation line adapted to transfer the fluid from the separator to the inlet of the reaction zone.
[0040] In one embodiment, the system may also include a vapor trap adapted to separate vaporized liquid mixed with the fluid from the separator.
[0041] Containers contemplated for use herein are typically provided with at least one outlet for removal of fuel therefrom and at least one inlet for introduction of vapor thereto. Such containers may optionally contain a venting system in communication with the atmosphere to allow pressure equilibration. Such containers may further optionally contain one or more elements which monitor flow rate of the vapor phase, and/or the level of reactive component(s) in said vapor phase. The output of such elements can be communicated to one or more elements which control the flow rate of the vapor phase (e.g., in response to the level of reactive component(s) in said vapor phase).
[0042] In certain embodiments of the present invention, the fluid treating zone is external to said container. In such embodiments, invention systems may optionally further comprise one or more heat exchangers upstream and/or downstream of said reaction zone.
[0043] In other embodiments of the present invention, the fluid treating zone is within said container.
[0044] In certain embodiments of the present invention, invention systems may further comprise one or more elements suitable for equilibrating pressure within the system upon exposure to sub- or super-atmospheric conditions. Exemplary elements for equilibrating pressure include a source of make-up fluid to equilibrate pressure within the system upon exposure to sub-atmospheric conditions; a vent to equilibrate pressure within the system upon exposure to super-atmospheric conditions; one or more flexible members, thereby providing one or more elements suitable for equilibrating pressure within the system, and the like.
[0045] In additional embodiments of the present invention, invention systems further comprise an independent source of reactive material to facilitate deactivation of the reactive components within the reaction zone. Exemplary independent sources of such reactive materials include hydrogen, fuel, and the like.
[0046] In accordance with another aspect of the present invention, there are provided systems for introducing reactive component-depleted air into a container having fuel therein as fuel is withdrawn therefrom. Invention systems comprise:
[0047] a fluid treating zone comprising:
at least one inlet, at least one outlet, and a reaction zone, wherein said reaction zone provides conditions suitable to deactivate said one or more reactive component(s) when contacted therewith,
[0051] a source of air, wherein the source of air is in fluid communication with the inlet of the fluid treating zone,
[0052] a source of fuel, wherein the source of fuel is in fluid communication with the inlet of said fluid treating zone, and
[0053] optionally a filter/condenser, wherein when the filter/condenser is present, the fluid treating zone is in fluid communication with the inlet of the filter/condenser, and the outlet of the filter/condenser is in fluid communication with the container,
[0054] wherein said fluid treating zone operates under conditions suitable to remove or reduce the concentration of reactive component in the source of air when contacted therewith in the presence of fuel, and is in fluid communication with the container.
[0055] Systems as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0056] In accordance with the present invention, there are provided systems for displacing fuel in, or vapor in the vapor space of, a container having fuel therein with reactive component-depleted air. Invention systems comprise:
[0057] a fluid treating zone comprising:
at least one inlet, at least one outlet, and a reaction zone, wherein said reaction zone provides conditions suitable to deactivate said one or more reactive component(s) when contacted therewith,
[0061] a source of air, wherein the source of air is in fluid communication with the inlet of the fluid treating zone,
[0062] a source of fuel, wherein the source of fuel is in fluid communication with the inlet of said fluid treating zone, and
[0063] optionally a filter/condenser, wherein when the filter/condenser is present, the fluid treating zone is in fluid communication with the inlet of the filter/condenser, and the outlet of the filter/condenser is in fluid communication with the container,
[0064] wherein said reaction zone provides conditions suitable to remove or reduce the concentration of reactive component(s) in the source of air when contacted therewith in the presence of fuel vapor, wherein the reaction zone is in fluid communication with the container.
[0065] Systems as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0066] In accordance with the present invention, there are provided systems for reducing the concentration of one or more reactive component(s) in a vapor phase fluid prior to introduction thereof into a container having fuel therein, thereby reducing the concentration of reactive component(s) in said vapor phase fluid below the concentration at which auto-ignition may occur when said vapor phase fluid is introduced into said container. Invention systems comprise:
[0067] said container, and
[0068] a fluid treating zone comprising:
at least one inlet, at least one outlet, and a catalyst zone, said catalyst zone comprising an optionally supported metal catalyst, said catalyst being reactive with one or more reactive component(s) when contacted therewith under suitable conditions so as to deactivate said one or more reactive component(s),
wherein only the outlet of said fluid treating zone is in fluid communication with the container, such that the inlet of said fluid treating zone has no communication with the container or contents thereof.
[0072] Systems as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0073] In accordance with the present invention, there are provided fuel storage systems, said systems comprising:
[0074] a container having an outlet for removal of vapor therefrom, and an inlet for return of vapor thereto, and
[0075] a reaction zone which provides conditions suitable to deactivate one or more reactive component(s) in the vapor phase of said container when contacted therewith,
[0076] wherein said container and the reaction zone are in fluid communication with one another.
[0077] Systems as contemplated hereinabove are useful for a variety of applications, i.e., inerting the void-space in a fuel storage container so as to substantially reduce the risk of ignition thereof.
[0078] In accordance with the present invention, there are provided methods for displacing fuel in, or vapor in the vapor space of, a container having fuel therein with reactive component-depleted air as fuel is withdrawn from the container, said method comprising:
[0079] combining air with vaporized fuel,
[0080] passing the resulting combination through a fluid treating zone under conditions suitable to produce reactive component-depleted air,
[0081] optionally removing any water from the reactive component-depleted air to produce substantially water-free, reactive component-depleted air, and
[0082] introducing the resulting substantially water-free, reactive component-depleted air into said container as fuel is withdrawn therefrom.
[0083] Methods as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0084] In accordance with the present invention, there are provided methods for displacing the vapor in the vapor space of a container employed for the storage of fuel therein with reactive component-depleted air as fuel-containing vapor is withdrawn from the container, and prior to the introduction of fuel into said container, said method comprising:
[0085] introducing ambient air, optionally in combination with a fuel material, into a fluid treating zone under conditions suitable to produce reactive component-depleted air,
[0086] optionally removing any water from the reactive component-depleted air to produce substantially water-free, reactive component-depleted air, and
[0087] introducing the resulting substantially water-free, reactive component-depleted air into said container as fuel-containing vapor is withdrawn therefrom.
[0088] Methods as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0089] In accordance with the present invention, there are provided methods for inerting the vapor space of a container employed for the storage of fuel therein, said method comprising replacing the vapor in said container, prior to the introduction of fuel into said container, with reactive component-depleted air prepared as described herein. For example, said method can be accomplished by:
[0090] passing ambient air, optionally in combination with a fuel material, through a fluid treating zone under conditions suitable to produce reactive component-depleted air, and
[0091] optionally removing any water from the reactive component-depleted air to produce substantially water-free, reactive component-depleted air.
[0092] Methods as contemplated hereinabove are useful for a variety of applications, i.e., for filling the void created by withdrawal of fuel from a storage container with air which has been treated so as to substantially reduce the risk of ignition thereof.
[0093] The invention will now be described in greater detail with reference to the Figures, which are illustrative of various embodiments of the invention. While the exemplary embodiments illustrated in the Figures and described herein are presently preferred, it should be understood that these embodiments are offered by way of example only. Other embodiments may include, for example, different techniques for performing the same operations. The invention is not limited to a particular embodiment, but extends to various modifications, combinations, and permutations that nevertheless fall within the scope and spirit of the appended claims.
[0094] FIG. 1 is a schematic illustration of one embodiment of the present invention. Inerted air is introduced into fuel-containing vessel 1 via line 11 . Inerted air is prepared by introducing ambient air into reaction zone 3 via line 13 . Reaction zone 3 may optionally also be supplied with an auxiliary fuel source, such as from vessel 5 . The combination of ambient air and fuel passes through reaction zone 3 , and optionally through heat exchanger 7 before being introduced into fuel-containing vessel 1 via line 11 .
[0095] FIG. 2 is a schematic illustration of another embodiment of the present invention, which is a variant of the embodiment illustrated in FIG. 1 . Thus, in FIG. 2 ambient air (via line 13 and fuel from vessel 5 are pre-mixed prior to introduction into reaction zone 3 . While only illustrated herein with respect to the embodiment illustrated in FIG. 1 , those of skill in the art will recognize that pre-mixing of ambient air with fuel can be employed with any of the other embodiment of the invention, instead of the direct introduction of ambient air into the reaction zone, as illustrated herein (merely for convenience and clarity).
[0096] FIG. 3 is a schematic illustration of another embodiment of the invention reactive component reduction system shown in FIG. 1 , wherein water lock 9 is inserted in line 11 to prevent fluid vapors from fuel-containing vessel 1 backing up into reaction zone 3 .
[0097] FIG. 4 is a schematic illustration of yet another embodiment of a reactive component reduction system according to the invention, further provided with one or more sensor 15 (which sensor(s) are capable of monitoring the content of reactive material(s) in the fluids which have passed through reaction zone 3 ), and recycle/return line 17 (which allows fluid vapors to be recycled for further treatment as needed if the content of reactive materials therein is higher than acceptable, or bypass of reaction zone 3 if the content of reactive materials therein is acceptably below the flammability limit).
[0098] FIG. 5 is a schematic illustration of still another embodiment of a reactive component reduction system according to the invention, wherein the heat exchange function is integrated with the reaction zone, shown in the figure as reaction zone 3 ′.
[0099] FIG. 6 is a schematic illustration of a further embodiment of a reactive component reduction system according to the invention, further comprising an additional heat exchanger (i.e., heat exchanger 7 ′) to facilitate modulating the temperature of ambient air introduced into reaction zone 3 .
[0100] FIG. 7 is a schematic illustration of a still further embodiment of a reactive component reduction system according to the invention, further comprising by-pass line 21 which facilitates direct introduction of ambient air into fuel-containing vessel 1 in the event the content of reactive materials therein is acceptably below the flammability limit.
[0101] FIG. 8 is a schematic illustration of still another embodiment of a reactive component reduction system according to the invention, representing one of the possible combinations of features contemplated for use in the practice of the present invention.
[0102] While the exemplary embodiments illustrated in the Figures and described above are presently preferred, it should be understood that these embodiments are offered by way of example only. Other embodiments may include, for example, different techniques for performing the same operations. The invention is not limited to a particular embodiment, but extends to various modifications, combinations, and permutations that nevertheless fall within the scope and spirit of the appended claims. | In accordance with the present invention, there are provided simplified systems and methods for deactivating, removing, or reducing the levels of reactive component(s) from vapor phase fluids prior to introduction thereof into fuel storage tanks. The simple apparatus described herein can be utilized to replace complex systems on the market. Simply stated, in one embodiment of the invention, the vapor phase fluid contemplated for introduction into the fuel storage tank is passed through a reaction zone (e.g., a catalytic bed) operated at appropriate temperatures to allow the reaction between free reactive components therein (e.g., oxygen and hydrogen or other fuel vapor), thereby deactivating reactive component(s) in the gas phase. | 1 |
FIELD OF THE INVENTION
The present invention relates to a catheter, particularly intended for use with peritoneal dialysis. In particular, the invention relates to a peritoneal dialysis catheter suitable for high flow speeds while preventing significant catheter migration. The catheter according to the invention can also be used in other circumstances, such as with the connection to other cavities or vessels in the body, like the stomach, the intestine, the urine bladder, the heart, the brain etc., as well as for connection to blood vessels.
BACKGROUND ART
With peritoneal dialysis, a catheter is used for the supply and removal of dialysis liquid to/from the peritoneal cavity.
A commonly-used catheter is the so-called Tenckhoff-catheter which can be of the straight type or the spiral-shaped type. This catheter consists of a silicon tube, on to which are fastened two dacron pads, to which peritoneal fibres may grow attached, thereby fixing the catheter in position after surgical implantation.
The proximal end of the catheter is connected by means of a connector to a dialysis liquid supply arrangement. The distal end of the catheter is provided with a plurality of holes in its sidewall and generally ends in an opening.
One problem with this catheter is that the holes in the catheter can be blocked during the outward-feed phase, due to the effect of the suction pressure. During the inward-feed phase, too high flows can lead to the catheter moving into the peritoneal cavity. The force which occurs when the fluid flows out causes the tip of the catheter to lash about and to be displaced when the flow is initiated. This catheter migration is one of the reasons for a catheter having to be changed. This movement can also affect the peritoneal membrane's susceptibility to infection.
The liquid also flows out of the catheter through the side holes and, if the flow speed in the sideways direction is too high, discomfort to the patient may result. The flow speed in the forward direction may also cause the patient discomfort.
Catheters for different purposes are described in patent literature. For example, the patent document EP-A1-185 865 relates to an implantable intraperitoneal catheter provided with several spacers in the form of discs which protect the holes in the side of the catheter from becoming blocked by ingrowth. The spacers probably also have a protective effect on the peritoneal membrane which is kept away from the holes where the out-feed flow speed is at its largest. The distal end of the catheter is normally closed but may also be open.
The patent document EP-B1-381 062 describes a catheter for even distribution of therapeutic fluids and comprises a catheter with a plurality of holes along the catheter's sidewall. The diameter of the holes increases towards the distal end of the catheter which is closed. The very small holes are manufactured by laser technology and are rectangular or oblong.
The patent document WO 89/02290 describes a catheter for placement in the ventricular system in the brain. The catheter comprises many small holes which are drilled at an angle with respect to the normal, vis-a-vis the catheter wall.
The patent document U.S. Pat. No. 5,057,073 describes a double-lumen catheter for implanting into a patient's vein, for use with hemodialysis treatments. The catheter implanted with the help of a Seldinger thread and the catheter's distal end tip opening is formed with a restriction in order to fit around the Seldinger thread. The wall of the catheter is provided with a plurality of holes for the passage of blood into, and out of, the catheter.
The patent document EP-B1-191 234 discloses a process for providing a medical tube with grooves or slits.
With a straight catheter for peritoneal dialysis having an open distal end, a large part of the total flow, as much as two-thirds, will pass out through the tip opening. High outflow speeds thereby result, which could damage the fibres in the peritoneum. Additionally, the force which acts on the tip of the catheter due to the outflow of fluid in an axial direction becomes excessively high. It is this force which causes the catheter to lash about and be displaced when the flow is initiated. It is desirable to reduce this force, particularly at higher flows.
The problem is greater for shorter catheters with fewer side holes and with straight catheters. With higher mass flows, the proportion which flows out through the tip becomes larger when viewed as a percentage. If the flow is doubled, the outflow speed through the open tip is more than twice as high and the resulting force more than quadruples.
SUMMARY OF THE INVENTION
The object of the present invention is to achieve a catheter, particularly intended for peritoneal dialysis, which can be used for higher flows and have lower flow resistance.
Another object of the present invention is to achieve a catheter wherein the force which affects the tip due to the flow out from an opening in the tip of the catheter, is minimised.
An additional object of the present invention is to achieve a catheter where the outflow through the side holes is as equal as possible.
A simple way of minimising the catheter's flow resistance is to increase its diameter. This can however give rise to medical problems, like increased susceptibility to infection or a larger risk of leakage.
In order to minimise the flow resistance with an unchanged diameter, it is possible to increase the combined area of the holes in the catheter's sidewall and tip.
As described above, a large part of the liquid flows through the catheter's tip opening, which significantly effects the patient and the catheter. By minimising the flow through the tip opening it ought to be possible to divide the out-going flow over a larger area, which would be beneficial for the patient.
According to the present invention, the distal end of the catheter is therefore provided with a restriction, so that a smaller part of the total flow passes out through the tip opening. It is preferred that less than 50% of the total flow passes out through the tip opening and it is particularly preferred that between 20% and 25% of the total flow passes out though the tip opening. A smaller tip opening is also possible so that more than 5% to 10% of the total flow passes out through this opening.
If the catheter is provided with a restriction so that the flow through the tip opening is 20% to 25% of the total flow, the speed through the opening is however still so great that the problem of the force excerted on the tip of the catheter remains. In order to further reduce this force, without restricting the flow through the tip completely, the tip can be provided with both a restriction which reduces the flow and a conic diffusor which increases the flow diameter and thereby reduces both the speed and the force of the out-going flow.
As explained above, the diffusor's main task is to reduce flow speed rather than to recover pressure. The increase of the diameter for the flow should occur gradually such that the liquid will flow smoothly along the diffusor's internal surface and therefor without relief. A suitable tip angle (α) with respect to a longitudinal axis of the channel of the diffusor is between 3 and 30 degrees, preferably 5 to 15 degrees. Particularly preferred is about 8 to 10 degrees.
According to a preferred embodiment of the invention, the tip can be manufactured as a separate part, or tip insert, which is fixed to the otherwise tube-shaped catheter by means of welding or adhesive. The insert can be manufactured of the same material as the rest of the catheter, such as silicon or polyurethane.
According to a preferred embodiment of the invention, the insert is manufactured of a metal such as titanium or tungsten. In this way, the catheter's tip is somewhat heavier which may be an advantage in certain circumstances. Other metals may also be used if the insert is provided with a coating of a biocompatible material, i.e. the insert is cast in a plastic material. The insert may be cast in the catheter during its manufacture, which thus occurs in one single step.
In order to achieve an even distribution of the outflow through the holes in the catheter's sidewall, these holes are formed having different sizes so that the holes which are nearest to the distal end of the catheter have the smallest diameter. By forming the holes in this way, the first holes, where the flow speed is high and therefore the static pressure is low, have a flow which is the same as that in the smaller holes which are located more distal along the catheter towards the tip where the static pressure is higher and the flow speed is lower. Additionally, only a small part of the area of the first larger holes will be used for effective flow, due to the fact that the fluid in the catheter has a flow component towards the end of the catheter. In order to increase the effective area of the hole, these are, according to the present invention, formed ovally in the longitudinal direction of the catheter.
In order to reduce the flow speed out through the holes, a plurality of holes may be provided. If too many holes are provided, however, the catheter will be too soft or weak. The same occures if holes too large in diameter are used.
In accordance with a preferred embodiment of the invention, a restriction may be arranged along the catheter's length between the proximal holes and the distal holes. The restriction raises the static pressure for the proximal holes which can therefore be made smaller, while reducing the flow speed at the same time.
Holes of different size may thus be arranged along the length of the catheter so that the first holes, as seen from the proximal end, are large and oblong and thereafter diminish in size towards the restriction, while immediately after the restriction the holes may be larger again and diminish in size towards the catheter's distal end. In this way, a substantially equal outflow through all the holes is obtained.
If a restriction is introduced into the catheter, it can be expected that the catheter will have a higher total flow resistance. If, however, the restriction is placed further from the distal end, for instance two-thirds distance from the distal end calculated along the part of the catheter provided with holes, referred to as the vented catheter region, a somewhat reduced total flow resistance is obtained. It is therefore preferred that the restriction is placed at between about 50% and 80% distance from the distal end of the catheter, preferably at about 65% distance, of the vented catheter region as measured from the distal end.
Additional features, advantages and characteristics of the catheter according to the invention will be apparent from the following detailed description of preferred embodiments of the invention with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a catheter of the type CD-5001 and depicts a typical example of a catheter according to the state of the art.
FIG. 2 is an enlarged cross-sectional view through the catheter of FIG. 1.
FIG. 3 is an enlarged cross-sectional view similar to FIG. 2, but provided with a tip insert according to the present invention.
FIG. 4 is a schematic diagram of the pressure conditions inside the catheter.
FIG. 5 is a schematic flow diagram at a side hole in the catheter.
FIG. 6 is a cross-sectional view similar to FIG. 3, schematically showing the flow at a restriction in the part of the catheter provided with holes.
FIG. 7 is a cross-sectional view similar to FIG. 3, of one alternative embodiment of the invention.
FIG. 8 is a schematic diagram similar to FIG. 4, of the pressure conditions in a catheter provided with a restriction.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a side view of a catheter of known type. The catheter 1 consists of a flexible tube of silicon, which at its proximal end 2 is connected with an arrangement for the supply or removal of dialysis liquid, which is not shown on the drawing.
At the end 2, the catheter is provided with two dacron pads 3, 4. When the catheter is surgically implanted in the peritoneal cavity, the two pads 3 and 4 are at such positions in the insertion tunnel that peritneal fibres may grow attached to the pads 3, 4 and fix the position of the catheter, and thereby prevent infection through the insertion tunnel. The proximal end 2 of the catheter is located outside the skin.
The distal end 5 of the catheter is located inside the peritoneal cavity and is provided with a plurality of holes 6 along its sidewall and a tip opening 7. The catheter is shown in enlarged cross-section in FIG. 2.
In this embodiment, the outer diameter of the catheter d 1 is 5.0 mm and the inner diameter d 2 is 2.7 mm. There may be fifty-six holes with a respective spacing of 3.2 mm and with a hole diameter of about 0.7 mm positioned along the vented catheter region, which may have a length of 90 mm. The holes are approximately equal in size. These specifications may, however, vary considerably between different catheters and each manufacturer has its own constructions and preferences.
FIG. 3 shows a catheter according to a preferred embodiment of the present invention. The catheter 11 is provided with a plurality of holes 16 along the wall of the catheter defining the vented catheter region 28.
The catheter may comprise an insert 18, which further comprises a restriction 19, as well as an enlarging portion 20, for example in the form of a diffusor with even cross-sectional enlargement 23 (conical) and concludes in a tip opening 17. The inner diameter of the restriction may be 1.5 mm and the diffusor's conicity may be about 8° which, with a length of about 9 mm, results in a final opening diameter of about 2.7 mm, i.e. the same as the original inner diameter of the catheter.
The insert 18 can preferably be dimensioned so that the flow speed through the tip opening is approximately the same as the flow speed through the holes in the catheter's sidewall (see below for more detail).
With the aforementioned dimensions the flow through the tip opening is about 20% of the flow through the side holes, which has shown itself to be a suitable value. By means of this dimensioning, the advantage is obtained that the force which the flow exerts on the catheter tip is not too large and does not cause the catheter to move to too large a degree, i.e. catheter migration is avoided. Additionally, the flow speed through the tip opening is relatively slow, whereby the effect on the peritoneal cavity is minimised.
With certain types of catheter, it is suitable if the flow through the tip opening is less than that which is stated above, for example more than 5 or 10% of the total flow. This is true particularly for catheters with many holes in the sidewall. In certain cases, it can also be favourable if the tip opening is not present.
In other cases it may be better if a larger part of the total flow passes through the tip opening, such as up to 50% or more of the total flow. Normally however, it is preferred that about 20% to 25% of the total flow passes through the tip opening.
The insert 18 is preferably manufactured of the same material as the rest of the catheter, such as silicon. The whole catheter is preferably made in one single piece in the same manufacturing step. Alternatively, the insert 18 can be manufactured by itself in the same material, or in another material, and be fastened to the catheter tip by means of welding or adhesive, which is of course done in a biocompatible manner.
Alternatively, the insert can be manufactured of a biocompatible plastic material such as polyurethane or polycarbonate.
In a further alternative embodiment of the invention, the insert is made of metal such as titanium or tungsten and thereby has a somewhat larger weight than if it was made of plastics material. This is favourable since the tip of the catheter will thereby automatically be orientated downwardly in the peritoneal cavity, which is generally preferred.
The insert can be embedded in a plastic material which is biocompatible. Other metals can also be used such as silver which also has a certain bacteriostatic function.
In the preferred embodiment of the invention as shown in FIG. 3, the holes 16 are depicted as having different sizes. The object of using holes with different sizes is to obtain approximately the same flow speed out through the various holes.
FIG. 4 shows a schematic diagram of the pressure conditions within the vented catheter region as the liquid moves toward the catheter tip. The pressure in the catheter is made up of a dynamic pressure which corresponds to the movement energy of the fluid (see curve 31) and a static pressure which constitutes the fluid's pressure against the catheter wall (see curve 32). The sum of the dynamic pressure and the static pressure corresponds to the total pressure (see curve 33). For the sake of simplicity, no account is taken of the hydrostatic pressure.
As shown by curve 31, the dynamic pressure drops towards the catheter tip which is dependent on the fact that the fluid's flow speed is reduced due to what is given out through the side holes. At the same time, the static pressure rises as shown by curve 32. The total pressure reduces slightly due to, inter alia, the frictional effect against the catheter's sidewall.
The static pressure at each side hole 16 determines the flow speed through that hole. Thus, the side holes must have a lesser diameter nearer to the tip in order for the same flow speed to be obtained from all the holes, whereby the frictional losses against the sidewall of the hole as well as the losses due to the fluid's viscosity reduce the outflow speed. A reduction in the outflow speed can probably be obtained alternatively with conical holes where the diameter increases outwardly. Such holes can be manufactured with laser technology or in another way, such as by conical stamps.
In practice, the diameter of the holes does not have to be adapted accurately to the static pressure and it is normally sufficient if two or three different diameters are used. In FIG. 3, the holes 21 are shown with a small diameter close to the catheter tip and holes 22 with a larger diameter further away from the catheter's tip.
FIG. 5 schematically shows the flow picture for a circular, relatively small hole 21 in the catheter's sidewall. Along the flow lines 24 which lie closest to the sidewall, the fluid particles have a relatively low speed and can therefore, without any great difficulty, be diverted outwardly by the static pressure and pass out through the hole 21. Along the flow lines 25 which are further from the sidewall, the fluid particles are however more difficult to divert and do not manage to be adequately diverted before the hole 21 has been passed. The effective surface area of the hole 21 is therefore reduced. The effective surface area is dependent on the flow speed of the fluid at the hole. In order to obtain the same effective surface area, the hole's cross-sectional area therefore has to be increased further from the catheter tip.
There are thus two reasons for increasing the hole diameter further away from the catheter's tip. It is, however, not possible to increase the hole's diameter too much as the catheter becomes too weak and flexible.
Therefore, in accordance with the present invention, it is proposed to use oblong holes 22, such as are clearly shown in FIG. 3, for the holes which require a larger cross-sectional area. The advantage is thereby obtained that the effective surface area of the hole is used better than with completely circular holes. Additionally, oblong holes affect the integrity of the catheter less so that it does not become too flexible.
It can be difficult to manufacture holes with sufficiently large surface area, despite the measures which are indicated above. It is therefore proposed in accordance with the present invention, that a restriction 26 is arranged approximately in the middle of the vented catheter's region which is provided with holes, as shown in FIG. 3. However, the use of this restriction 26 is optional.
As shown schematically in FIG. 8, the restriction achieves a reduction 35 of the total pressure due to the frictional forces along, and the energy losses across, the restriction, which means that the static pressure is reduced over the restriction since the dynamic pressure is unchanged before and after the restriction (the same flow speed). The static pressure before the restriction is also somewhat higher than without the restriction.
It is therefore possible to use oblong holes 22 furthest away from the tip, followed by small circular holes 21 nearer to the tip and towards the restriction 26. After the restriction oblong holes 22 are first used again and then small circular holes 21 closest to the tip. In this way, approximately the same flow speed is obtained through the various holes.
It can be expected that the total flow resistance for a catheter with such a restriction 26 would be greater than without a restriction. However, it has discovered that, if the restriction is placed in a certain way, the total flow resistance of the catheter may be minimised. If the restriction is placed about two thirds distance from the tip along the portion of the catheter provided with holes, about the same or even a lower flow resistance is obtained compared to when no restriction is present. According to the invention, a restriction is arranged at a distance of between 50%-80% of the length of the vented catheter region, as measured from the tip. An explanation of this unexpected result may be that the holes before the restriction are used more effectively due to the increased static pressure in this portion.
In a preferred embodiment of the invention forty-eight holes are used, divided in the following way seen from the catheter's tip. First there are ten circular holes with a diameter of 0.8 mm, followed by eighteen oblong holes with the dimensions 0.9 mm×2.0 mm. Then there is a restriction, followed thereafter by ten small circular holes with a diameter of 0.8 mm, followed by 10 oblong holes having the dimensions 0.9 mm×2.0 mm. The distance between the holes is 5 mm.
The restriction is dimensioned so that the flow speed through the various holes is as similar as possible. A suitable dimension is an inner diameter of 2.0 mm with a length of about 4 mm. The size is also dependent on how the inner surface of the restriction looks and on the geometry of the restriction. If the surface is rough or edged, the restriction can be shortened.
As shown in more detail in FIG. 6, the restriction 26 induces eddies 27 in the fluid flow after the restriction. These eddies cause a loss of energy which reduces the total pressure and thus also the static pressure. Moreover, energy losses arise due to frictional forces against the wall of the restriction (increased flow speed) and due to the viscosity.
The pressure conditions before and after the restriction 26 are shown schematically in FIG. 8. The curve 34 for the total pressure shows a steep drop 35 at the restriction. The curve for the dynamic pressure 36 rises sharply at the restriction as shown by a hump 37, but returns thereafter to the same value as before the restriction, since the flow speeds are the same. The curve 38 gives the static pressure, which rises before the restriction but sinks to a lower value after the restriction, approximately corresponding to the starting value, and then rises. The two curve portions of the static pressure before and after the restriction are about the same. In this manner the two parts of the portion provided with holes are used in approximately the same way.
The aforementioned features can be combined in different ways to give the catheter desired characteristics. With catheters which are to be used for extra-sensitive patients, it may be possible to use a long portion provided with holes, which portion has many holes, and thereby use more than one restriction, such as two or three along the length of the portion having holes.
Referring to FIG. 7 it may be possible to replace the insert 18 with a restriction 42 which is relatively close to the catheter tip, but also sufficiently removed from the tip opening 17 in order that the jet which is obtained from the restriction will have collected into a homogeneous flow.
The restriction 42 is positioned about 20 mm from the tip opening 17, allowing the flow to collect and reduce in speed before the flow passes through the tip opening 17.
The restrictions 26 and 42 are preferably manufactured of the same material as the rest of the catheter, such as of silicon. The whole catheter is preferably produced in one single piece and in the same manufacturing step. Alternatively, the restrictions may be inserts which are introduced into the catheter and fixed in a suitable way such as by welding or adhesive. Alternatively, the restriction 26 can be mechanically fixed by being provided with projecting pins 43 which fit into holes 21 in the catheter's sidewall. The same materials can be used as for the insert (see above).
The length of, or the tip angle of, the conical portion 20 can be increased so that the orifice has a larger cross-section than the rest of the catheter. FIG. 6 shows an insert 48 with larger tip angle which results in a larger outlet area and lower outflow speed.
FIG. 7 shows further alternative embodiments of the restrictions and holes. A conical restriction 41 is thus shown which consists of a conically diminishing portion, followed by a relatively sharp edge. The fluid's flow speed increases in the conical portion, which results in a large eddy formation after the sharp edge. This eddy formation brings about energy losses which result in a drop of the total pressure and the static pressure. Additionally, energy losses arise in the form of friction losses against the walls as well as internally in the fluid due to the viscosity.
In order to avoid the effect which is shown in FIG. 5, where only a part of the hole's effective surface area is used, it is proposed that the holes 44 and 45 are arranged at a small angle relative to the normal to the sidewall, such as 10°. Such a slanted arrangement is most noticeable at the start of the portion provided with holes where the flow speed is at its largest.
It can be difficult to reduce the static pressure sufficiently, close to the tip of the catheter. Thus, the small holes at this end can be slightly conically widened, as shown by the hole 46. Since the wall thickness is relatively small, the speed reduction will of course be correspondingly small. This hole can also be arranged in a slanted manner as shown by the hole 47.
The flow conditions for flow of fluid into the peritoneal cavity have been described above. With outward flow, an underpressure is used which sucks the fluid out of the peritoneal cavity. For this, the proximal holes furthest from the tip are used mainly. The fluid passes to a very small extent through the tip opening and the distal holes as well as past the restriction. Only when the proximal holes become blocked due to the fluid at these holes being used up and the catheter sucking on to the peritoneal membrane, does flow occur through the distal holes. This has the beneficial effect that the restrictions do not become blocked by fibres or larger particles which may be present in the fluid in the peritoneal cavity.
The invention has been described above with reference to the embodiments shown in the drawings. The various components and characteristics can however be combined in different ways than have been shown in the drawings and other combinations are included within the scope of the invention. The invention is only limited by the appended claims. | Catheters are disclosed for insertion into a body cavity. The catheters include a region near the distal end of the catheter which includes a number of apertures as well as a reduced diameter portion which has a diameter less than the diameter of the rest of the catheter region so that the flow of a fluid through the reduced diameter portion is reduced thereby. | 0 |
BACKGROUND
[0001] This disclosure is related to the field of analysis of fluid production from subsurface wellbores to evaluate expected future fluid production and ultimate total fluid production therefrom. More specifically, the disclosure relates to methods for statistical analysis of time-dependent fluid production rate and cumulative produced fluid volume measurements to obtain improved estimates of future fluid production rate and ultimate cumulative production volumes.
[0002] Statistical prediction of well fluid production rates is known in the art for use in estimating wellbore reserves and wellbore economic value. Several methods known in the art are used to quantify the uncertainty in wellbore fluid production forecasts, which is useful for representing a range of reserves in accordance with United States Securities and Exchange Commission (SEC) reserves reporting rules, and estimating the chance of commercial success of oil and gas wells given the inherent uncertainty in forecasting.
[0003] Production forecasts are engineering interpretations of fluid production volumetric or mass rate data to predict the performance of hydrocarbon producing (oil and gas) wells. Data used for production forecasts may be obtained from disparate sources, but most often when a wellbore is already producing fluids (including oil and/or gas), the data used are typically solely measurements of production rates. The fluid production rate is often displayed on a Cartesian coordinate graph wherein the fluid production rate is shown on the y-axis, and the time of measurement shown on the x-axis. An example fluid production rate graph is shown in FIG. 1 . Many different versions of the same basic data display also known in the art to be used, such as log-log and semi-log axis display of the same fluid production rate data (shown in FIG. 2 and FIG. 3 ), as well as other transforms of the fluid production rate data. These manipulations and transforms may identify different trends used to characterize the change in fluid production rate over time, and to evaluate the quality of the fit of a model to the fluid production rate measurement data. A model may be a representation of inferred physical characteristics of a particular subsurface reservoir, such as fluid pressure, fractional volumes of pore space occupied by oil, gas and water, viscosities and composition of the reservoir fluids, geometry of the reservoir, and the drive mechanism by which fluid is moved from the reservoir to the Earth's surface.
[0004] Interpretation of the fluid production rate measurement data to generate a fluid production rate and/or cumulative produced fluid volume forecast is usually performed by analysis of the interpreter in a process of “tuning ” Estimates of the parameters used in the model used for forecasting may be obtained from interpretation or diagnosis of the fluid production rate measurement data, or, when the data displays no strong indications, from analogous data such as data from geodetically proximate (“offset”) wells or subsurface reservoirs having similar characteristics. For example, a wellbore having a well-defined fluid production rate measurement trend is shown in FIG. 4 , while a wellbore having fluid production rate measurement data that may be characterized as “noisy” is shown in FIG. 5 .
[0005] Interpretation of fluid production rate measurement data using known techniques such as curve fitting to generate fluid production rate forecasts and/or cumulative fluid production volume forecasts typically does not include a calculation of error between the forecast and the measurement data. Such forecasts are typically performed by a human interpreter and are based at least in part on informed but subjective judgment of the human interpreter. There are limitations associated with forecasting based on such human interpretation including, for example, difficulties associated with consistently reproducing interpretations among different human interpreters, non-uniqueness of interpretations among interpreters, the inability to rapidly make interpretations using computer algorithms, the inability to quantify the uncertainty inherent in any prediction of future well production, and the requirement that the interpreter be highly skilled in the art of fluid production rate measurement data interpretation so as to make subjective judgments well informed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 shows a graph of production data with production rate on the y-axis, and the time of measurement on the x-axis in Cartesian coordinates.
[0007] FIG. 2 shows a graph such as in FIG. 1 with a logarithmic scale on the y-axis.
[0008] FIG. 3 shows a graph such as in FIG. 1 with a logarithmic scale on both axes.
[0009] FIG. 4 shows a graph such as FIG. 1 for an example well having a well-defined production decline trend with respect to time.
[0010] FIG. 5 shows a graph such as FIG. 1 for an example well having what may be described as a “noisy” production rate with respect to time.
[0011] FIG. 6 shows a histogram of distribution of accepted model proposals ranked by estimated ultimate recovery (EUR).
[0012] FIG. 7 shows a cumulative distribution function of accepted model proposals ranked by EUR.
[0013] FIG. 8 shows P90, P50, & P10 percentile neighborhood production forecasts.
[0014] FIG. 9 shows mean percentile neighborhood production forecast.
[0015] FIGS. 10A, 10B and 10C show a flow chart of an example method according to the present disclosure.
[0016] FIG. 11 shows an example computer system for performing analysis according to the present disclosure.
DETAILED DESCRIPTION
[0017] In performing analysis methods according to the present disclosure, at selected times a rate of fluid production from a wellbore is measured. The fluid production rate measurements may include measurements of any or all of volumetric and/or mass flow rates of gas, water and oil. Gas production may be quantified volumetrically in units of thousands of standard cubic feet per day (wherein the volume of gas is corrected to the volume it would occupy at “standard’ conditions of 25 degrees C. and a pressure of 1 bar), Oil and water production may be quantified volumetrically in barrels per day (1 barrel is equal to 42 U.S. gallons). The fluid production rate measurements may be entered into a computer or computer system for processing as will be explained further with reference to FIGS. 10 and 11 .
[0018] In analysis methods according to the present disclosure, certain parameters and attributes may be defined. The first nine attributes listed below correspond to a specific production forecast model which may be used in some embodiments. In the present example embodiment the Transient Hyperbolic Model (described below) may be used. Different production forecast models may be used in other embodiments; such other production forecast models may require substitution of or modification of some or all of the below listed attributes for the respective production forecast model's specific parameters.
[0019] 1. Initial Rate Attribute: This attribute is the initial fluid production rate of the model, written as the parameter q 1 .
[0020] 2. Initial Decline Attribute: This attribute is the initial fluid production decline rate used for the production forecast model, expressed herein as the parameter D i .
[0021] 3. Initial Hyperbolic (b-) Parameter Attribute: This attribute is the initial hyperbolic parameter of the production forecast model, also referred to as the b-parameter, hyperbolic exponent, or n-exponent. It is expressed herein as the parameter b i .
[0022] 4. Final Hyperbolic Parameter Attribute: This attribute is the final hyperbolic parameter of the production forecast model, expressed herein as the parameter b f .
[0023] 5. Time to End of Linear Flow Attribute: This attribute is the time to the end of linear flow of the production forecast model, expressed herein as the parameter t etf .
[0024] 6. Distribution of Initial Decline Attribute: This attribute is an estimate of a range of possible values for the Initial Decline Attribute. This attribute constrains randomly generated production forecast models and production forecast model parameters to within boundaries determined, by, for example, expert opinion (i.e., informed, subjective human judgment), allowing for more accurate fluid production forecasts. Any type of distribution may be used. In some embodiments a uniform distribution is used.
[0025] 7. Distribution of final b-parameter Attribute: This attribute is an estimate of the range of possible values for the b-parameter. This attribute constrains randomly generated models and model parameters to within boundaries determined, by, for example, expert opinion (i.e., informed, subjective human judgment), allowing for more accurate fluid production forecasts. Any type of distribution may be used. In some embodiments a uniform distribution is used.
[0026] 8. Distribution of time to end of linear flow (0 Attribute: This attribute is an estimate of a range of possible values for the t eif parameter. This attribute constrains randomly generated models and model parameters to within boundaries determined, by, for example, expert opinion (i.e., informed, subjective human judgment), allowing for more accurate fluid production forecasts. Any type of distribution may be used. In some embodiments a log-normal distribution is used.
[0027] 9. Prior Likelihood of Model Parameter Attribute: This attribute is the likelihood of any model parameter represented by a probability distribution. This attribute is useful for measuring likelihood of any fluid production model parameter given an expert opinion (i.e., an informed, subjective human judgment) of the fluid production model parameter's distribution. For a uniform probability distribution, the likelihood is normalized by itself and therefore expresses no substantial indication of the likelihood of any parameter value within bounds of the distribution, but only that the fluid production model parameter must fall within the bounds expressed. This is referred to as an uninformative prior. For a parameter in which an informative prior is used as a distribution, such as the time to end of linear flow attribute, this attribute is defined as:
[0000]
π
(
θ
|
q
i
,
D
i
,
b
i
,
b
f
,
t
elf
)
=
1
2
π
t
elf
σ
t
elf
-
(
L
N
(
t
elf
)
-
μ
t
elf
)
2
2
σ
t
elf
2
*
…
etc
[0028] Using the likelihood of the time to end of linear flow parameter as an example for the prior likelihood, the prior likelihood may be substituted for any fluid production model parameter, as well as the product of likelihood of multiple fluid production model parameters.
[0029] The following attributes are general to the present disclosure and are not related to any specific production forecast model that may be used.
[0030] 10. Logarithm Residuals Attribute: This attribute evaluates the logarithm residuals between the input data (the fluid production rate measurements with respect to time) and the values of fluid production with respect to time calculated by a specific fluid production forecast model at corresponding values of time. The logarithm residuals may be evaluated for every fluid production rate input data point (i.e., the fluid production rate measurements and time at which the measurements were made), and may be expressed as:
[0000] ε=ln(data)−ln(model)
[0031] 11. Standard Deviation of Logarithm Residuals Attribute: This attribute is a measure of the standard deviation of the above described logarithm residuals, ε. This attribute is useful for measuring a difference in curvature between the input data and the forecast values for any particular fluid production forecast model. This attribute may be expressed as:
[0000]
σ
ɛ
=
1
n
-
1
∑
i
=
1
n
(
ɛ
i
-
ɛ
_
)
2
[0000] where n represents the number of input data points being evaluated, and ε is the logarithm residual. ε represents the average of all values of logarithm residuals.
[0032] 12. Minimum Standard Deviation of Logarithm Residuals Attribute: This attribute is the minimum standard deviation of logarithm residuals determined during the evaluation of any particular fluid production forecast model. This attribute may be determined by means of a genetic algorithm as each of a plurality of fluid production forecast models is randomly generated from a prior “accepted” (defined below) fluid production forecast model. The attribute may be expressed as:
[0000] σ ε min =min[σ ε ]
[0033] 13. Distribution of Standard Deviation of Logarithm Residuals Attribute: This attribute represents the distribution of the standard deviation of logarithm residuals between the input data and the values calculated by a particular fluid production forecast model. The distribution is assumed to be a normal distribution, with a standard deviation empirically tuned for an optimum rate of acceptance of fluid production forecast models generated, e.g., randomly. This attribute may be expressed as as:
[0000] θ ε ˜ (σ ε min , 0.01)
[0034] 14. Likelihood of Standard Deviation of Logarithm Residuals Attribute: This attribute evaluates the likelihood of the standard deviation of logarithm residuals as a function of the normal distribution with a mean of the minimum standard deviation of logarithm residuals, and standard deviation of 0.01. The attribute may be expressed as:
[0000]
f
(
θ
ɛ
|
σ
ɛ
)
=
1
2
π
-
1
2
(
(
σ
ɛ
-
σ
ɛ
min
)
2
0.01
2
)
[0035] 15. Magnitude of Logarithm Residuals Attribute: This attribute evaluates the magnitude of logarithm residuals between the input data and the values calculated by any particular fluid production forecast model. The magnitude of logarithm residuals may be evaluated for every input data point, and are defined as:
[0000] ε=abs[LN(data)−LN(model)]
[0036] 16. Mean of Magnitude of Logarithm Residuals Attribute: This attribute is a measure of the arithmetic mean of the logarithm residuals, ε. This attribute is useful for measuring the absolute error between the input data and the values calculated using an particular fluid production forecast model. The attribute may be expressed as:
[0000] μ ε = ε
[0000] where ε is the magnitude of the logarithm residual.
[0037] 17. Minimum Mean of Magnitude of Logarithm Residuals Attribute: This attribute is the minimum mean of logarithm residuals measured during the evaluation of any particular fluid production forecast model. This attribute may be determined by means of a genetic algorithm as each fluid production forecast model is randomly generated from a prior accepted fluid production forecast model. The attribute may be expressed as:
[0000] μ ε min [μ ε ]
[0038] 18. Distribution of Mean of Magnitude of Logarithm Residuals Attribute: This attribute describes the distribution of the mean of magnitude of logarithm residuals between the data and the model fluid production rate forecast. The distribution is assumed to follow a normal distribution, with a standard deviation empirically tuned for an optimum acceptance rate of possible fluid production forecast models, e.g., as generated randomly from a prior accepted fluid production forecast model. The attribute may be expressed as:
[0000] θ ε ˜ (μ ε min , 0.1)
[0039] 19. Likelihood of Mean of Magnitude of Logarithm Residuals Attribute: This attribute evaluates the likelihood of the mean of magnitude of logarithm residuals as a function of the normal distribution with a mean of the minimum mean of magnitude of logarithm residuals, and standard deviation of 0.1. The attribute may be expressed as:
[0000]
f
(
θ
ε
|
μ
ε
)
=
1
2
π
-
1
2
(
(
μ
ε
-
μ
ε
min
)
2
0.1
2
)
[0040] 20. Likelihood of Model Proposal Attribute: This attribute evaluates the likelihood that a particular fluid production forecast model is an acceptable description of the fluid production rate measurements (i.e., the input data). The attribute may be expressed as:
[0000]
f
(
θ
|
σ
ɛ
,
μ
ε
)
=
1
2
π
-
1
2
(
(
σ
ɛ
-
σ
ɛ
min
)
2
0.01
2
+
(
μ
ε
-
μ
ε
min
)
2
0.1
2
)
*
π
(
θ
|
q
i
,
D
i
,
b
i
,
b
f
,
t
elf
)
[0041] 21. Model Acceptance Attribute: This attribute uses the “Metropolis” algorithm to evaluate the acceptance probability of any particular fluid production forecast model. Each fluid production forecast model is accepted with probability normalized by the likelihood of the prior accepted fluid production forecast model. If the current fluid production forecast model is more likely, it is accepted. Otherwise the fluid production forecast model is accepted with a determinable or determined probability. The attribute may be expressed as:
[0000]
α
=
min
(
1
,
f
(
θ
)
π
(
θ
)
f
(
θ
i
-
1
)
π
(
θ
i
-
1
)
)
[0000] where α is the acceptance probability, θ is the current model proposal, and θ i−1 is the prior accepted fluid production forecast model.
[0042] 22. Distribution of Accepted Model Proposals Attribute: This attribute is the result of the evaluation and acceptance of fluid production forecast models from the fluid production forecast model acceptance attribute. This attribute is the set of possible forecasts, referred to as the statistical distribution of well performance.
[0043] 23. Histogram of Distribution of Accepted Model Proposals Attribute: A histogram or “density function” of the distribution of accepted fluid production forecast models, after ranking by expected ultimate recovery (EUR). This attribute is useful for illustrating the likelihood of the EUR from the accepted fluid production forecast models, and can be observed in FIG. 6 .
[0044] 24. Cumulative Distribution Function of Accepted Model Proposals Attribute:
[0045] The cumulative distribution function of the distribution of accepted fluid production forecast models, after ranking by EUR. This attribute is useful for illustrating the percentiles of the distribution of accepted fluid production forecast models, and can be seen in FIG. 7 .
[0046] 25. Production Forecast of Percentile Neighborhood Attribute: The forecast of a given percentile neighborhood represents features from a plurality accepted fluid production forecast model, as well as the possible accepted fluid production forecast models that are not generated due to limiting the number of iterations in the simulation for the purpose of reducing calculation time. At each percentile of interest, a production forecast representative of the features of a plurality of forecasts proximate the given percentile (hence “percentile neighborhood”) is created by averaging each parameter of the fluid production forecast model among all iterations in the neighborhood. A neighborhood size of +/−1 percentile is typically chosen. The 10 th , 50 th , and 90 th percentiles, referred to as P90, P50, and P10, respectively, are typically chosen for a simplified representation of the full distribution of production forecasts, although any percentile may be chosen. Examples of P90, P50, and P10 forecasts are shown in FIG. 8 . The mean forecast is determined as the percentile neighborhood's forecast which results in the mean EUR. An example of a mean forecast is shown in FIG. 9 .
[0047] Methods according to the present disclosure may use, without limitation, any of the following methods that may be advantageously applied for statistical prediction of fluid production rates, including but not limited to the attributes described above:
[0048] 26. Markov Chain Monte Carlo Method: This method utilizes a Markov chain to generate random model proposals for evaluation of likelihood of acceptance for the set of possible fluid production rate forecasts.
[0049] 27. Production Forecast Method: This method uses a production forecast to calculate an expected time-dependent array of fluid production rates. The results of any forecast are referred to as the “fluid production forecast model”. While any production forecast model may be used, in the present example implementation, the Transient Hyperbolic Model is used.
[0050] 28. Expected Ultimate Recovery Integral Method: This method evaluates the integral of the rate-time array of fluid production rates from a fluid production forecast model to forecast the EUR for such fluid production forecast model.
[0051] 29. Rank of Accepted Model Proposals Method: This method ranks the set of fluid production forecast models by the EUR to evaluate the chance that the EUR of the fluid production forecast models exceed a value of interest. This method is useful for reporting the confidence interval of EUR for the production data that has been analyzed.
[0052] Referring to FIGS. 10A, 10B and 10C , an example well fluid production rate analysis method according to the present disclosure will now be explained. In FIG. 10 A, at 10 , fluid production rate measurements with respect to time (i.e., the elapsed time since initiation of fluid production from a wellbore) may be input to a computer or computer system ( FIG. 11 ) programmed to perform a method as described herein. At 12, prior beliefs (e.g., subjective human interpretations) of fluid production forecast model parameters are input to the computer or computer system. The prior beliefs may be represented by attributes 6 through 8 listed above. At 14, random values of parameters for a fluid production rate forecast model for an initial simulation iteration (this is the initial fluid production forecast model and may be represented by parameters 1-5 above) are entered into the computer or computer system.
[0053] At 16, a fluid production rate forecast is generated by the computer or computer system. The fluid production rate forecast may be attribute 27 described above in the present implementation. At 18, differences (errors) between the fluid production rate forecast and the input data fluid production rate measurements (at the time(s) of the measurements) are calculated. The errors may be expressed by attributes 10, 11, 15 and 16 described above At 20, the errors may be stored in the computer or computer system as minimum errors, for example as attributes 12 and 17 set forth above. At 22, the likelihood of a fluid production forecast model relative to minimum errors may be determined by the computer or computer system. This may be performed by the computer or computer system using attributes 12-14 and 18-20 as set forth above.
[0054] In FIG. 10B , at 24, an iterative process, using, for example, the Markov Chain
[0055] Monte Carlo method (attribute 26 as set forth above) may be initiated. At 24A, parameters of a fluid production rate forecast generated using a random walk from a prior accepted fluid production rate forecast model are generated by the computer or computer system. At 24B, a fluid production rate forecast may be generated, e.g., using model attribute 27 as set forth above. At 24C, errors between the fluid production rate forecast and the input data are calculated by the computer or computer system as attributes 10, 11, 15 and 16 set forth above. At 24D, if the current iteration errors are smaller than the previous iteration errors, the current iteration errors are stored in the computer or computer system. At 24E, a likelihood of the fluid production rate forecast model relative to minimum error is calculated by the computer or computer system.
[0056] At 24F, acceptance probability as likelihood relative to the prior accepted fluid production rate forecast model is calculated in the computer or computer system This may be performed using attribute 21 set forth above. At 24G, the fluid production rate forecast model is accepted or rejected, which may be based on attribute 22 as set forth above. At 24J, if the fluid production rate forecast model is accepted, it becomes the “prior” accepted fluid production rate forecast mode in a subsequent iteration. If the fluid production rate forecast model is rejected, then the most recent accepted fluid production rate forecast model is retained as the “prior” accepted model proposal, e.g., as evaluated using attribute 22 given above.
[0057] In FIG. 10C , at 26, a selected number, n, of fluid production rate forecast models may be discarded during an initialization period in which convergence to a selected number of fluid production rate forecast models is obtained, which may be referred to as the “posterior distribution.” At 28, an EUR may be calculated for all iterations of all accepted fluid production rate forecast models. At 30, a fluid production rate forecast model distribution may be sorted by EUR. At 32, the percentiles of the fluid production rate forecasts may be generated in the computer or computer system using attribute 25 set forth above. At 34 and 36, respectively, a histogram and cumulative distribution plot sorted by EUR of the selected fluid production rate forecast models may be generated by the computer or computer system. At 38, fluid production rate forecasts from all iterations may be displayed, e.g. on a graphic computer user interface.
[0058] FIG. 11 shows an example computing system 100 in accordance with some embodiments. The computing system 100 may be an individual computer system 101 A or an arrangement of distributed computer systems. The individual computer system 101 A may include one or more analysis modules 102 that may be configured to perform various tasks according to some embodiments, such as the tasks explained with reference to FIG. 10 . To perform these various tasks, the analysis module 102 may operate independently or in coordination with one or more processors 104 , which may be connected to one or more storage media 106 . A display device 105 such as a graphic user interface of any known type may be in signal communication with the processor 104 to enable user entry of commands and/or data and to display results of execution of a set of instructions according to the present disclosure.
[0059] The processor(s) 104 may also be connected to a network interface 108 to allow the individual computer system 101 A to communicate over a data network 110 with one or more additional individual computer systems and/or computing systems, such as 101 B, 101 C, and/or 101 D (note that computer systems 101 B, 101 C and/or 101 D may or may not share the same architecture as computer system 101 A, and may be located in different physical locations, for example, computer systems 101 A and 101 B may be at a well drilling location, while in communication with one or more computer systems such as 101 C and/or 101 D that may be located in one or more data centers on shore, aboard ships, and/or located in varying countries on different continents).
[0060] A processor may include, without limitation, a microprocessor, microcontroller, processor module or subsystem, programmable integrated circuit, programmable gate array, or another control or computing device.
[0061] The storage media 106 may be implemented as one or more computer-readable or machine-readable storage media. Note that while in the example embodiment of FIG. the storage media 106 are shown as being disposed within the individual computer system 101 A, in some embodiments, the storage media 106 may be distributed within and/or across multiple internal and/or external enclosures of the individual computing system 101 A and/or additional computing systems, e.g., 101 B, 101 C, 101 D. Storage media 106 may include, without limitation, one or more different forms of memory including semiconductor memory devices such as dynamic or static random access memories (DRAMs or SRAMs), erasable and programmable read-only memories (EPROMs), electrically erasable and programmable read-only memories (EEPROMs) and flash memories; magnetic disks such as fixed, floppy and removable disks; other magnetic media including tape; optical media such as compact disks (CDs) or digital video disks (DVDs); or other types of storage devices. Note that computer instructions to cause any individual computer system or a computing system to perform the tasks described above may be provided on one computer-readable or machine-readable storage medium, or may be provided on multiple computer-readable or machine-readable storage media distributed in a multiple component computing system having one or more nodes. Such computer-readable or machine-readable storage medium or media may be considered to be part of an article (or article of manufacture). An article or article of manufacture can refer to any manufactured single component or multiple components. The storage medium or media can be located either in the machine running the machine-readable instructions, or located at a remote site from which machine-readable instructions can be downloaded over a network for execution.
[0062] It should be appreciated that computing system 100 is only one example of a computing system, and that any other embodiment of a computing system may have more or fewer components than shown, may combine additional components not shown in the example embodiment of FIG. 11 , and/or the computing system 100 may have a different configuration or arrangement of the components shown in FIG. 11 . The various components shown in FIG. 11 may be implemented in hardware, software, or a combination of both hardware and software, including one or more signal processing and/or application specific integrated circuits.
[0063] Further, the acts of the processing methods described above may be implemented by running one or more functional modules in information processing apparatus such as general purpose processors or application specific chips, such as ASICs, FPGAs, PLDs, or other appropriate devices. These modules, combinations of these modules, and/or their combination with general hardware are all included within the scope of the present disclosure.
[0064] While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims. | A method for optimizing a well production forecast includes a) inputting initial production rate measurements made at selected times, b) inputting probability distributions to estimate production forecast model parameters, c) generating an initial forecast of fluid production rates and total produced fluid volumes using a selected production forecast model, d) at a time after a last one of the selected times, comparing the initial forecast with actual production rate and total produced fluid volume measurements to generate an error measurement, e) adjusting parameters of the selected production forecast model to minimize the error measurement, thereby generating an adjusted production forecast model, f) repeating (d) and (e) for a plurality of iterations to generate a plurality of production forecast models each having a determined likelihood of an error measurement and displaying the plurality of production forecast models with respect to likelihood of error. | 4 |
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Certain of the research leading to the present invention was sponsored by the United States National Science Foundation under contract No. DMI-9713782. The United States Government may have rights in the invention.
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable.
BACKGROUND OF INVENTION
1. Field of Invention
The present invention relates generally to shape grammars and, more particularly, to shape grammar systems and methods having parametric shape recognition.
2. Description of the Background
A shape grammar is a set of rules, based on shape, that is used to generatedesigns through rule applications. Rules take the form of a→b, where a and b both denote shapes. A rule is applicable if the left-hand shape, a, can be found in the design shape, denoted c. If the rule is applied, the left hand shape is subtracted from the design and the right-hand shape is added to the design, denoted c−τ(a)+τ(b), where shapes a and b undergo a transformation τ according to the transformation required to make shape a a subshape of shape c.
Shape grammars, having their roots in architecture literature, have recently found application in engineering, such as in the design of coffeemakers, lathe process plans, roof trusses, and microelectromechanical systems (MEMS) resonators. Shape grammars may be conceptualized of as a type of expert system based on geometry. Shape grammars, however, have succeeded in engineering applications where traditional expert systems have failed because of: (i) their direct handing of reasoning about geometry; (ii) their ability to operate on a parametric geometric representation; and (iii) their ability to support emergence of shape. These advantages presage a future in which shape grammars play an increasingly larger role in engineering design in comparison with the traditional expert systems.
In the past, however, shape grammars have been limited by the difficulty and time intensity in their implementations. Implementations have not allowed for general parametric shape recognition. Engineering shape grammars in particular have been restricted to limited, non-parametric shape recognition and often are hard-coded. These drawbacks minimize much of the beneficial potential of shape grammars.
Accordingly, there exists a need for a shape grammar system that uses shape recognition to provide, for example, an automated approach to product generation. There further exists a need for a shape grammar system in which engineering knowledge (geometry-based and otherwise) may be incorporated into implementation design rules in order to drive design exploration and the generation of designs toward a desired end.
BRIEF SUMMARY OF INVENTION
The present invention is directed to a method of recognizing a first shape in a second shape. According to one embodiment, the method includes decomposing the first shape into at least one subshape belonging to one of a plurality of subshape groups, and searching the second shape for a parametric transformation of the subshape.
According to another embodiment, the present invention is directed to a shape grammar interpreter, including a shape decomposition module, and a shape recognition module in communication with the shape decomposition module.
The present invention allows for shape grammars, including engineering shape grammars, to be implemented in a fraction of the time that it currently takes to hard code them. Consequently, the present invention allows shape grammars to be adjusted, fine tuned, and adapted to the changing design scenario presented to the rule writer. The shape grammar interpreter of the present invention therefore possesses the features desired in an engineering grammar implementation, including general parametric shape recognition, providing designers with the possibility of exploring the promising potential of engineering shape grammar systems. These and other benefits of the present invention will be apparent from the detailed description hereinbelow.
DESCRIPTION OF THE FIGURES
For the present invention to be clearly understood and readily practiced, the present invention will be described in conjunction with the following figures, wherein:
FIG. 1 is a block diagram of a shape grammar system according to one embodiment of the present invention;
FIGS. 2 and 3 are diagrams of examples of line segments belonging to subshape groups according a default hierarchy of subshape groups according to one embodiment of the present invention;
FIG. 4 is a block diagram of the process flow through the parametric shape grammar interpreter of the shape grammar system of FIG. 1 according to one embodiment of the present invention;
FIGS. 5-11 are diagrams illustrating a method of shape decomposition according to one embodiment of the present invention;
FIGS. 12-19 are diagrams illustrating a method of parametric shape recognition according to one embodiment of the present invention;
FIGS. 20-23 are diagrams illustrating a method of using parametric shape recognition to apply a given shape grammar rule to a given initial design shape according to one embodiment of the present invention; and
FIGS. 24-27 are diagrams illustrating a method of using parametric shape recognition to apply a set of shape grammar rules to a given initial design shape according to another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a block diagram of a shape grammar system 10 according to one embodiment of the present invention. The shape grammar system 10 includes a parametric shape grammar interpreter 12 , including a shape decomposition module 14 and a shape recognition module 16 . The shape grammar system 10 also includes a rule application module 18 and an intelligent rule selection module 20 , which are in communication with the parametric shape grammar interpreter 12 . The shape grammar system 10 may also include an input/output (I/O) interface module 22 , as illustrated in FIG. 1 . The shape grammar system 10 , as described hereinbelow, may be used to implement, for example, architectural shape grammars, engineering shape grammars, and industrial design shape grammars, with parametric shape recognition. The parametric shape grammar interpreter 12 will be described herein as being used to recognize the left-hand shape of a shape grammar rule in the initial design shape(s) through the steps of decomposing the shape into subshapes and progressively searching for parametric transformations of those subshapes, however, it should be recognized that the benefits of the present invention may be realized in any application requiring parametric shape recognition, and is not limited to shape grammar applications.
The system 10 may be implemented using, for example, a computer, such as a workstation or a personal computer, a microprocessor, or an application specific integrated circuit (ASIC). The modules 14 , 16 , 18 , 20 , and 22 may be implemented as software code to be executed by the system 10 using any type of computer instruction type suitable such as, for example, microcode, and can be stored in, for example, an electrically erasable programmable read only memory (EEPROM), or can be configured into the logic of the system 10 . According to another embodiment, the modules 14 , 16 , 18 , 20 , and 22 may be implemented as software code to be executed by the system 10 using any suitable computer language such as, for example, C or C++ using, for example, conventional or object-oriented techniques. The software code may be stored as a series of instructions or commands on a computer readable medium, such as a random access memory (RAM), a read only memory (ROM), a magnetic medium such as a hard-drive or a floppy disk, or an optical medium such as a CD-ROM.
The parametric shape grammar interpreter 12 may perform the operations necessary to determine whether any of a predefined set of shape grammar rules may be applied to a particular shape (or set of shapes). In addition, the interpreter 12 may determine how a particular rule may be applied to the shape(s). As described hereinbelow, the interpreter 12 may perform these operations by decomposing, for example, the left-hand shape of a shape grammar rule into a group of subshapes, thereby allowing for any part of the shape to be transformed with any possible transformation, although, as discussed hereinbefore, it is not limited to such shapes. The interpreter 12 may perform these operations with respect to, for example, a left-hand shape of a rule having one-dimensional, two-dimensional or three-dimensional shapes. In addition, the left-hand shape may include, for example, straight line segments, curved line segments, planes, or three-dimensional objects. Once the interpreter 12 determines whether a rule may be applied and how to apply the rule, whether the rule should be applied to the shape may be determined, for example, by a user of the system 10 or the intelligent rule selection module 20 . The rule application module 18 may then apply the rule to the shape if so determined.
The shape decomposition module 14 decomposes a shape such as, for example, the left-hand shape of a rule (the shape a in the rule a→b ) into a group of subshapes contained in the shape. The groups may be defined such that subshapes belonging to different groups do not share, for example, line segments for two-dimensional shapes. The group of shapes may be ordered according to a hierarchy of, for example, decreasing restrictions or constraints for more efficient searching, as described hereinbelow, although it is not necessary for the subshape groups to be so ordered.
For an embodiment in which the subshape groups are ordered according to a hierarchy of decreasing constraints, the basis of the hierarchy of constraints may be, for example, defined by the designer or it may be a default hierarchy. A default hierarchy may be designed, for example, to interpret the designer's intentions and preferences through particular features present in a shape which defines part of a shape grammar rule. For example, the default hierarchy may be intended to separate the parts of the left-hand shape of the rule that the designer specified exactly from the parts of the shape that were intended as a general scheme.
For example, in defining a default hierarchy for an embodiment in which the left-hand shapes of the predefined shape grammar rules include shapes having straight lines in a single plane, it is recognized that there is a limited set of transformations that can be applied to the shapes, such as translation, rotation, scaling (isotropic and anisotropic), and shearing. Of the possible transformations, some will destroy certain features of the shape and some will not. For example, no amount of translation or rotation will destroy a specific feature such as, for example, a right angle, a square, or an equilateral triangle. Shearing, however, will eliminate perpendicular intersections and symmetry in a two-dimensional shape. In addition, anisotropic scaling will also destroy symmetry unless the scaling is along or perpendicular to the line of symmetry. Isotropic scaling, on the other hand, does not affect the symmetry of a shape.
In view of the properties of these transformations, an example of a default hierarchy of subshapes may be defined as follows:
TABLE 1
Subshape Group
Features
Transformations
s 1
1) lines that intersect
translation, rotation,
perpendicularly and are
isotropic scaling
the same length
2) lines that are symmetric
to more than one lines that
are not parallel
s 2
1) lines that intersect
translation, rotation,
perpendicularly
anisotropic scaling
2) lines that are symmetric
to one line or
3) more than one lines that
are parallel
s 3
intersecting lines
translation, rotation,
anisotropic scaling,
shearing
s 4
none
all
According to such a default hierarchy, subshape group s 1 consists of the most constrained lines. Group s 1 contains the line segments that intersect perpendicularly and are the same length. Additionally, the s 1 group also contains any line segment that is symmetric to two or more other line segments which are not parallel. Two examples of lines that meet the symmetry criteria of group s 1 are the sides of a square and the legs of an equilateral triangle.
Group s 2 consists of the next most constrained lines, containing line segments that intersect perpendicularly. Any line segment that is symmetric to another line segment is also included in group s 2 . Accordingly, group s 1 is a subset of group s 2 . Some examples of s 2 lines that are not also in group s 1 include the sides of a rectangle and the two equal legs of an isosceles triangle.
Group s 3 contains the line segments that intersect. Thus, subshape groups s 1 and s 2 are subsets of s 3 . An example of three lines that are in group s 3 and not s 1 or s 2 are the three line segments that make up the triangle illustrated in FIG. 2 .
The line segments in group s 4 have no discernible spatial relationship to any other line segments. Thus, the line segments in group s 4 are essentially those not found in s 1 , s 2 , and s 3 . An example of line segments that may be found in group s 4 are illustrated in FIG. 3 .
The above-described default hierarchy is but one example of a hierarchy of subshapes ordered by decreasing constraints. According to other embodiments of the present invention, the shape decomposition module 14 may search the left-hand shape of a rule according to such other subshape hierarchies. Such other hierarchies, as described hereinbefore, may be defined by a user of the system 10 , or may be a default hierarchy making different assumptions about the intent of the designer through particular features present in a shape which defines part of a shape grammar rule. For example, according to one embodiment, the hierarchy may be based on an assumption that the intersection of line segments at, for example, a right angle, is intended to represent a specific design choice, and the intersection of line segments at an angle other than a right angle is intended to represent a general scheme. According to other embodiments, the hierarchy may be based on an assumption that the intersection of line segments at, for example, sixty degrees, is intended to represent a specific design choice, and the intersection of line segments at an angle other than sixty degrees is intended to represent a general scheme.
The shape recognition module 16 searches a shape, or a set of shapes, for the subshapes belonging to the subshape groups according to the transformations appropriate for that group. According to one embodiment, parametric shape recognition may be accomplished by the shape recognition module 16 by repeating a three-step process for each of the subshape groups of the decomposed left-hand shape of a rule. The three steps of the process may include: 1) finding subshapes in the design shape, 2) subtracting the subshapes from the design shape, and 3) identifying the connectivity between the subshape and the design shape and between the subshapes of successive subshape groups by, for example, marking points of intersection with labels or weights to a) the overlapping points of the decomposed left-hand shapes and also to b) points in the design equal in location to the transformed, identified points in the decomposed left-hand side shape. The process is begun with a first of the subshape groups, and progressively repeated for the others. According to one embodiment, the subshape groups are of a hierarchical order of decreasing constraints, and the process is started with the most constrained group and progressively repeated with the next most constrained subshape group. Such an embodiment generally yields more efficient searching.
For example, according to such an embodiment the initial design shape is first searched for subshapes belonging to the most constrained group. The subshape matches, found by applying the transformations appropriate for that group, are defined as a set S. The subshapes in the set S are each subtracted from the initial design shape, producing another set of shapes, denoted as the set C. According to one embodiment, the subshapes of a decomposed shape will overlap each other, if at all, only at points because the definition of the hierarchical groups may require that the subshapes share no line segments. Thus, in order to maintain the connectivity, and hence orientation, of the subshapes, the connectivity between the shapes of sets S and C is identified and maintained. The connectivity may be maintained, for example, by identifying with labels or weights the overlapping points of the decomposed left-hand shapes and the points in the initial design corresponding to the location of the transformed, identified points in the decomposed left-hand shape.
The shape recognition module 16 may repeat this process for all of the subshape groups. The shape recognition process may end when all of the decomposed parts of the left-hand shape have been found or when one of the shape searches finds no subshapes. The shape recognition module 16 may then add each of the shapes, maintaining the connectivity between the shapes, for each of the subshape groups found in the original shape to recognize the occurrences of the left-hand shape of the rule in the original design shape. Once the shape recognition process is completed, as described hereinbelow, the rule may then be applied.
FIG. 4 is a block diagram of the process flow through the parametric shape grammar interpreter 12 according to one embodiment of the present invention. The process begins at block 30 with a determination of whether a rule remains in a set of shape grammar rules for which the left-hand shape of the rule has not been searched in the set of shapes C 0 . The set of shape grammar rules may be defined and input to the system 10 by a user of the system 10 and may be, for example, architectural shape grammar rules, engineering shape grammar rules, or industrial design shape grammar rules. The set of rules may include one or a multitude of rules. In addition, the set of shapes C 0 may include one shape or a multitude of shapes. If the set does not contain any such rules, the process flow continues to block 32 , and the operation of the shape grammar interpreter 12 is terminated.
Conversely, if the set does contain such a rule, the process flow continues to block 34 , where the rule is selected to be applied, if applicable as determined by the parametric shape grammar interpreter 12 , to the set of shapes C 0 . From block 34 , the process flow advances to block 36 , where a counter, denoted as i, is set to a value of one. In addition, at block 36 , the set of shapes S 0 , as discussed hereinbelow, is set to null.
From block 36 , the process advances to block 38 , where the left-hand shape of the rule is decomposed into a number, denoted N, of subshape groups, denoted s i . . . N . The subshape groups may be defined such that no subshapes of the decomposed left-hand shape share, for example, the same line segment. According to one embodiment, the subshape groups s i . . . N may be of a hierarchical order of decreasing constraints, such as the default hierarchy described hereinbefore with respect to Table 1, or the hierarchy may be defined by a user of the system 10 . According to other embodiments, the subshape groups are not ordered according to a hierarchical order.
From block 38 , the process continues to block 40 , where it is determined whether the subshape group s i is null. This corresponds to a determination of whether the left-hand shape of the rule includes a subshape belonging to the s i subshape group. For example, where i=1, it is determined whether the left-hand rule includes a subshape of the s 1 group. If the group s i is null, the process advances to block 42 , where the set of shapes S i , as described further hereinbelow, is set to null. In addition, at block 42 , the set of shapes C i , as described hereinbelow, is set to the same as the set C i−1 .
From block 42 , the process flow advances to block 43 , where it is determined whether i=N. If i does not equal N, then the process flow continues to block 44 , where the counter (i) is incremented by one, and the process flow returns to block 40 such that it may be determined whether the subshape group s i+1 is null. Conversely, if it is determined that i equals N, then the process flow advances to block 59 .
If at block 40 it is determined that the s i subshape group is not null, the process flow continues to block 46 , where the set of shapes C i−1 is searched for subshapes belonging to the subshape group s i . For example, where i=1, the set of shapes C 0 is searched for subshapes belonging to the subshape group s 1 . Accordingly, as the counter i is incremented during the process flow, as described hereinbelow, the set of shapes to be searched (C 0 . . . N−1 ) will be progressively searched for subshapes belonging to the other subshape groups until all the subshape groups are exhausted.
The set of shapes C i−1 is searched for subshapes belonging to the group s i using the parametric transformations appropriate for that group. For example, for the default subshape group described hereinbefore with respect to Table 1 where i=1, the set of shapes C 0 is searched for subshapes of the group s i using translation, rotation, and isotropic scaling. Accordingly, where i=2, the set of shapes C 1 is searched for subshapes of the group s 2 using translation, rotation, and anisotropic scaling, and so on for the remaining subshape groups s 3 and s 4 .
From block 46 , the process continues to block 48 , where it is determined whether a parametric transformation of a subshape belonging to the group s i is found in the set of shapes C i−2 . For example, where i=1, it is determined whether a parametric transformation of a subshape belonging to the group s 1 is found in the set of shapes C 0 . If a subshape belonging to the group s i is not found in the set of shapes C i−1 , the process flow returns to block 32 , where the operation of the parametric shape grammar interpreter 12 is terminated. The process flow is terminated at this point because a subshape belonging to the group s i is not found in the set of shape C i−1 , and if the subshape group s i is not null, then the left-hand shape of the selected rule cannot be found in the set of shapes C 0 . Conversely, if at block 48 a parametric transformation of a subshape belonging to the group s i is found, then the process continues to block 50 .
At block 50 , a set of shapes S i is generated. The set of shapes S i includes the parametric transformations of the subshapes of the group s i found in the set of shapes C i−1 using the transformations appropriate for that subshape group. For example, where i=1, a set of shapes S 1 is generated which includes the parametric transformations of the subshapes of the group s 1 found in the set of shapes C 0 . For subshape groups that are null, the set S i is set to be a null, as described hereinbefore with respect to block 42 .
Continuing to block 52 , a set of shapes C i is generated which corresponds to the subtraction of the set of shapes S i from the set of shapes C i−1 . Thus, for example, where i=1, at block 52 the set of shapes C 1 is generated which corresponds to the subtraction of the set of shapes S 1 from the set of shapes C 0 . For subshape groups that are null, the set C i is set to be the same as C i−1 , as described hereinbefore with respect to block 42 .
From block 52 , the process continues to block 54 , where the set of shapes S i are added to the sum of sets S i−1, . . . , 0 . The set of shapes S i is added to the previous sum such that the connectivity of the decomposed left-hand shapes is maintained using, for example, the connectivity technique described herein. Thus, for example, where i=1, the set of shapes S 1 is added to the set of shapes S 0 , which was set to null as described hereinbefore with respect to block 36 . Accordingly, the sum of the sets S 1 and S 0 will be the same as S 1 . The set S 1 will also be null if the group s 1 is null. Conversely, if s 1 is not null and if at block 48 parametric transformations of the subshapes belonging to the group s 1 are found in the set C 0 , then the set S 1 will include those shapes corresponding to those parametric transformations. Accordingly, where i=2, the sum of sets S 2,1,0 will correspond to the sum of sets S 2 and S 1 .
From block 54 , the process flow continues to block 56 , where it is determined whether i=N. This determination corresponds to a check of whether parametric transformations of the subshapes of each of the subshape groups S i . . . N that are not null have been searched for.
If i does not equal N, then the process flow advances to block 58 , where the connectivity of the subshapes of set S i relative to the set of shapes C i , as well as the relative connectivity between the other parts of the decomposed left-hand shape, are determined. The relative connectivity of the parts of the left-hand shape may be determined by, for example, identifying with labels or weights the overlapping points of the subshapes of groups s 1 , s 2 , . . . , s i , and the subshape of the next group that is not null. In addition, the points in the shapes of set C i corresponding in location to the transformed, identified points in the groups s 1 , s 2 , . . . , s i , may also be identified with, for example, labels or weights. From block 58 , the process flow returns to block 44 , where the counter (i) is incremented such that the shape recognition function may resume with the subshapes of the next subshape group.
It should be recognized that prior to advancement of the process flow to decision block 56 , the set of shapes C i has been generated at either block 42 or 52 , as described hereinbefore. At block 42 , the set C i is set to be the set C i−1 because the set s i is null. Accordingly, when the process flow returns to block 46 (assuming the group s i+1 is not null), in essence the set of shapes C i−1 will be searched for the subshapes of group s i+1 . Conversely, if at block 48 , a parametric transformation of a subshape of the group s i was found in the set of shapes C i−1 , then the set of shapes C i is generated at block 52 , as described hereinbefore, as the set of shapes S i subtracted from the set of shapes C i−1 . Accordingly, when the process flow continues to block 46 , the set of shapes S i subtracted from the set of shapes C i−1 (i.e., the set of shapes C i ) will be searched for subshapes of the group s i+1 (again, assuming the group s i+1 is not null).
If at block 56 it is determined that i=N, which corresponds to a determination that the presence of parametric transformations of subshapes belonging to each of the subshape groups S i . . . N which are not null have been searched for, then the process flow proceeds to block 59 , where the sum of sets S i . . . N , as determined at block 54 , corresponds to the parametric transformations of the left-hand shape of the selected rule found in the set of shapes C 0 .
According to other embodiments of the present invention, the interpreter 12 may recognize parametric transformations of the left-hand shape of a selected rule according to process flows different than that illustrated in FIG. 4 . For example, according to another embodiment, rather than adding the set of shapes S i to the sum of S i−1 . . . 0 at block 54 prior to the determination of whether i=N at block 56 , the sets S i . . . N may be summed together in one step after the determination of whether i=N to recognize the parametric transformations of the left-hand shape of the rule in the set of shapes C 0 .
Once the parametric transformations of the left-hand shape of a selected rule is recognized in the set of shapes C 0 by the parametric shape grammar interpreter 12 , as described hereinbefore with reference to FIG. 4 , it may be determined whether the rule is to be applied to the set of shapes C 0 . This determination may be made, for example, by an operator of the system 10 or the intelligent rule selection module 20 . If a particular application of the rule is selected, the rule application module 18 may then apply the rule by subtracting the transformation of the left-hand shape of the rule from the initial shape and adding a transformation of the right-hand shape. After the rule is applied, the process flow illustrated in FIG. 4 may be repeated with the selection of a different rule from the set of predefined rules to be applied to the resulting shape (or shapes) from the application of the prior rule. If it is determined that the rule is not to be applied, the process flow illustrated in FIG. 4 may also be repeated with the selection of a new rule from the set of predefined rules to be applied to the original shape or shapes (C 0 ). According to another embodiment, the rule application module 18 may apply the rule for all transformations of the left-hand shape found in the set of shapes C 0 , and the process may be repeated for all of the resulting shapes, thus producing all possible permutations resulting from application of the predefined set of rules in the initial design shape(s).
The I/O interface module 22 may be used to input data, such as the shape grammar rules, and to output data, such as the set of rules, the transformations of the left-hand shape of a particular rule found in a shape, and the shapes resulting from the application from a particular rule. The I/O interface module 22 may input and output the data, for example, in text and/or graphical form. The I/O interface module 22 may display data via a display device (not shown) in communication with the I/O interface module 22 .
Thus, the parametric shape grammar interpreter 12 of the present invention permits parametric shape recognition of the left-hand shape of a shape grammar rule in an initial design shape(s). Unlike previous interpreters that are limited to Euclidean transformations (translation, rotation, and scaling) that can only be applied to whole shapes, the parametric shape grammar interpreter 12 can search for general parametric features of a subshape generated through decomposition of a shape, thus allowing for separate treatment of each subshape.
FIGS. 5-11 provide a shape decomposition example using the example default hierarchy of subshape groups defined hereinbefore with respect to Table 1. Consider the shape to be decomposed (such as the shape a in the rule a→b) to be that illustrated in FIG. 5 . To recognize the transformations of the subshapes of the groups s 1−4 , as defined hereinbefore, the lines of symmetry in the shape of FIG. 5 may first be determined. These lines of symmetry are illustrated in FIG. 6 as dashed lines. As illustrated in FIG. 6 , each line of the square 60 is symmetric with the two lines of the square 60 that it intersects. In addition, each of the lines of the triangle 62 is symmetric with more than one line. Accordingly, these subshapes satisfy the requirements of the subshape group s 1 , and can be subtracted from the example shape, resulting in the shape shown in FIG. 7 , for which the subshapes of group s 2 may be searched.
The resulting shape, shown in FIG. 7 , contains two lines that are symmetric to only one other line. Additionally, there are two perpendicular intersections, comprised of three line segments, that satisfy the requirements of s 2 , as illustrated in FIG. 8 . Accordingly, this shape may be subtracted from the shape shown in FIG. 7 , resulting in the shape shown in FIG. 9 , which may be searched for subshapes of the group s 3 .
The s 3 subshape illustrated in FIG. 10 is present in the shape of FIG. 9 . As illustrated, the s 3 subshape is simply the intersecting line segments. Accordingly, this subshape may be subtracted from the shape of FIG. 9 , resulting in the shape shown in FIG. 11 , which corresponds to the subshapes comprising the s 4 group.
FIGS. 12-19 provide an example of parametric shape recognition, using the example default hierarchy defined hereinbefore with respect to Table 1, to recognize the presence of parametric transformations of the left-hand shape (a) of the rule (a→b) in a design shape (C 0 ). Consider the rule to be the rule a→b illustrated in FIG. 12 , and consider the initial design shape (C 0 ) to which the rule is to be applied to be the shape illustrated in FIG. 13 . As described hereinbefore, in order to apply the rule a→b to the design shape C 0 , the left hand shape (a) of the rule must be found to be a parametric subshape under various transformations (τ) of the shape C 0 . Using the default hierarchy defined hereinbefore with respect to Table 1, the shape a may be decomposed into the four subshapes where a=s 1 +s 2 +s 3 +s 4 .
For the shape a shown in FIG. 12 , using the default hierarchy defined hereinbefore with respect to Table 1, the subshapes comprising groups s 1 and s 2 are shown in FIG. 14 , and the groups s 3 , s 4 are null. The shape recognition process, as described hereinbefore, may begin with the most constrained subshape group that is not null and skipped any less constrained groups that are null. Such an embodiment produces a more efficient shape recognition process because the more highly constrained shapes have fewer possible transformations. Thus, for the rule shown in FIG. 12 , the s 1 subshape is searched first, and then the s 2 subshape is searched.
Permissible transformations of the s 1 subshape may be found multiple times in the shape a, resulting in four instances of s 1 subshapes in this example. These transformations, as described hereinbefore, are defined as the set S 1 , and are shown in FIG. 15 . The four shapes of S 1 are equal but are found differently within the initial design shape by the rotation of s 1 subshape four different ways (0°, 90°, 180°, and 270°). The dots in FIG. 15 are to show the various transformations of the s 1 subshape found in the shape a. Having found the set of shapes S 1 , the set of shapes C 1 is generated, which is the result of the set of shapes S 1 subtracted from C 0 . The set of shapes C 1 is shown in FIG. 16 .
By definition of the subshape groups s 1 , s 2 , s 3 , and s 4 , it can been seen that no two groups will share any common line segments. They will, however, share common line segment end points. Accordingly, the relative connectivity of the shapes of groups s 1 and s 2 , as well as the relative connectivity of the transformed instance of s 1 and the set of C 1 shapes may be identified, as illustrated in FIG. 17 .
Next, as described hereinbefore, the set of shapes C 1 is searched for the next most constrained subshape group, which for this example, is the s 2 group. As can be appreciated, two permissible transformations of the s 2 subshape may be found in each of the shapes of C 1 . The set of the subshapes thus define the set S 2 . Next, as described hereinbefore, the set of shapes S 2 is subtracted from the set of shapes C 1 to define the set of shapes C 2 . Next, the intersection points between the marked shapes S 2 and the corresponding shapes C 2 are identified.
The sets S 1 and S 2 are then added such that their connectivity is maintained to produce the subshapes illustrated in FIG. 18 . Because the groups s 3 and s 4 are null, as described hereinbefore, the shapes illustrated in FIG. 18 represent the parametric transformations of the left-hand shape a of the rule a→b (illustrated in FIG. 12 ) found in the initial design shape C 0 (illustrated in FIG. 13 ). The two possible applications of the rule may then be applied to the shape C 0 to produce the shapes illustrated in FIG. 19 .
FIGS. 20-23 provide an example of parametric rule application. Consider the rule to be applied as the rule a→b illustrated in FIG. 20 , and the initial design shape C 0 , to which the rule is to be applied, as the shape illustrated in FIG. 21 . Using the default hierarchical subshape groups described hereinbefore with respect to Table 1, it can be recognized that the left-hand shape (a) of the rule has constraints that limit the parametric shape search to perpendicular intersections. This corresponds to group s 2 . Twelve permissible transformations of the s 2 shape may be found in the shape C 0 , three of which are shown in bold in FIG. 22 . Because the subshape groups s 1 , s 3 , and s 4 are null for this example, the sum of sets S 1-4 includes only the twelve transformations of the s 2 subshape found in the shape C 0 . Accordingly, the shape a may be recognized twelve times in the shape C 0 , with application of the rule for each of the transformations resulting in the shapes illustrated in FIG. 23 .
FIGS. 24-27 provide another example of a parametric shape grammar application using the default hierarchy of subshape groups described hereinbefore with respect to Table 1. For the example, the set of rules illustrated in FIG. 24 comprise the predefined shape grammar rules, and the initial design shape is the shape illustrated in FIG. 25 . Upon examining each of the rules, it can be recognized that the left-hand shapes of each rule fall into the s 3 group because of the lack of symmetry and perpendicular intersections. Therefore, in general, each of the rules may be applied if a shape corresponding to a permissible parametric transformation of the left-hand shape of any of the rules is recognized in the initial design shape. For example, rule 1 is applicable if any triangle can be recognized, and rule 4 may be applied if any five-sided polygon can be recognized. The progression of shapes illustrated in FIG. 26 depict the application of a series of these rules using the parametric shape grammar interpreter 12 for shape recognition. For the shapes illustrated in FIG. 26 , the subshape to which the indicated rule is to be applied is highlighted in bold. The progression of rule application may continue, such as by randomly choosing the applicable rules as well as the parameters, producing final design shapes such as those illustrated in FIG. 27 .
Those of ordinary skill in the art will recognize that many modifications and variations of the present invention may be implemented. The foregoing description and the following claims are intended to cover all such modifications and variations. | A method of recognizing a first shape in a second shape. The method includes decomposing the first shape into at least one subshape belonging to one of a plurality of subshape groups, and searching the second shape for a parametric transformation of the subshape. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application relates to the following co-pending applications, each of which is incorporated herein by reference: U.S. patent application Ser. No. 10/424,419, filed Apr. 28, 2003, by Huitao Luo et al., and entitled “DETECTING AND CORRECTING RED-EYE IN A DIGITAL IMAGE;” U.S. patent application Ser. No. 10/653,019, filed on Aug. 29, 2003, by Huitao Luo et al., and entitled “DETECTING AND CORRECTING RED-EYE IN AN IMAGE;” and U.S. patent application Ser. No. 10/653,021, filed on Aug. 29, 2003, by Huitao Luo et al., and entitled “SYSTEMS AND METHODS OF DETECTING AND CORRECTING REDEYE IN AN IMAGE SUITABLE FOR EMBEDDED APPLICATIONS.”
BACKGROUND
Redeye is the appearance of an unnatural reddish coloration in the pupils of a person appearing in an image captured by a camera with flash illumination. Peteye is the appearance of an unnatural coloration (not necessarily red) of the pupils in an animal appearing in an image captured by a camera with flash illumination. Redeye and peteye are caused by light from the flash illumination reflecting off the retina and returning to the camera. Redeye typically results from light reflecting off blood vessels in the retina, whereas peteye typically results from light reflecting off a reflective layer of the retina.
Image processing techniques have been proposed for detecting and correcting redeye in color images of humans. These techniques typically are semi-automatic or automatic. Semi-automatic redeye detection techniques rely on human input. For example, in some semi-automatic redeye reduction systems, a user must manually identify to the system the areas of an image containing redeye before the defects can be corrected. Many automatic human redeye reduction systems rely on a preliminary face detection step before redeye areas are detected. A common automatic approach involves detecting human faces in an image and, subsequently, detecting eyes within each detected face. After the eyes are located, redeye is identified based on shape, coloration, and brightness of image areas corresponding to the detected eye locations.
Detecting and correcting peteye are significantly more difficult than detecting and correcting redeye because peteye may be any of a variety of colors and face detection cannot be used to localize peteyes in an image. In addition, the reflective retinal layer that is present in the eyes of many animals, such as dogs and cats, can cause a variety of peteye colors as well as brightly glowing large white peteyes. Although techniques for detecting and correcting redeye in images may be used to correct some peteyes, such systems and methods cannot satisfactorily detect and correct the majority of peteyes that appear in images. What are needed are systems and methods that are designed specifically to detect and correct peteyes in images.
SUMMARY
In one aspect of the invention, a classification map segmenting pixels in the input image into peteye pixels and non-peteye pixels is generated based on a respective segmentation condition on values of the pixels. Candidate peteye pixel areas are identified in the classification map. The generating and the identifying processes are repeated with the respective condition replaced by a different respective segmentation condition on the pixel values.
In another aspect of the invention, pixels in the input image are segmented into an animal-fur color class and a non-animal-fur color class. Candidate peteye pixel areas corresponding to respective clusters of pixels in the non-animal-fur color class are identified in the input image. Ones of the identified candidate peteye pixel areas are selected as detected peteye pixel areas. Ones of the pixels in the detected peteye pixel areas are recolored.
In another aspect of the invention, pixels in the input image are segmented into peteye pixels and non-peteye pixels based on a mapping of the input image pixels into a one-dimensional luminance space. Candidate peteye pixel areas are identified in the input image based on the segmented peteye pixels. Ones of the identified candidate peteye pixel areas are selected as detected peteye pixel areas. Ones of the pixels in the detected peteye pixel areas are recolored.
Other features and advantages of the invention will become apparent from the following description, including the drawings and the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 is a block diagram of an embodiment of a system for detecting and correcting peteye in an image.
FIG. 2 is a block diagram of components of an embodiment of a peteye detection module.
FIG. 3 is a block diagram of components of an embodiment of an initial candidate peteye detection module.
FIG. 4 shows the various maps that are generated in an embodiment of a method of identifying initial candidate peteye pixel areas in an input image.
FIG. 5 is a histogram of animal fur colors obtained from a set of images and quantized into a set of predefined color ranges.
FIG. 6 is an image of a classification map that is derived by segmenting pixels in an image of a dog into an animal-fur color class and a non-animal-fur color class.
FIG. 7 is a block diagram of an embodiment of a single peteye verification classifier selecting candidate peteye pixel areas from a set of initial candidate peteye pixel areas.
FIG. 8A is a diagrammatic view of an embodiment of a graphical user interface presenting an image of a dog and a user-controlled pointer overlayed on the image.
FIG. 8B is a diagrammatic view of the graphical user interface shown in FIG. 8A after a user has moved the pointer over a candidate peteye pixel area.
FIG. 9 is a flow diagram of an embodiment of a method of correcting detected peteye pixels.
FIG. 10 shows a detected peteye pixel area and cropping lines for corner regions.
FIG. 11 is a flow diagram of an embodiment of a method of correcting redeye pixels in an image.
FIG. 12A is an exemplary grayscale iris area surrounded by a neighborhood area.
FIG. 12B is another exemplary grayscale iris area surrounded by a set of eight neighborhood areas.
FIG. 13A shows inner and outer bounding regions derived from a peteye pixel area and a corresponding grayscale iris pixel area.
FIG. 13B shows inner and outer peteye pixel corrections regions used in an embodiment of a method of correcting peteye in an image.
FIG. 14 is a flow diagram of an embodiment of a method of recoloring peteye pixels in detected peteye pixel areas.
FIG. 15 is a graph of darkening factors plotted as a function of a green color component value of a pixel of an input image.
FIG. 16 is a flow diagram of an embodiment of a method of correcting peteye pixel areas containing large glowing glint.
FIG. 17 is a diagrammatic view of a glint correction region inscribed in a peteye pixel area.
DETAILED DESCRIPTION
In the following description, like reference numbers are used to identify like elements. Furthermore, the drawings are intended to illustrate major features of exemplary embodiments in a diagrammatic manner. The drawings are not intended to depict every feature of actual embodiments nor relative dimensions of the depicted elements, and are not drawn to scale.
I. System Overview
The embodiments that are described in detail below are designed specifically to detect and correct peteyes in images. As a result, these embodiments are capable of satisfactorily detecting and correcting the majority of peteyes that appear in images. Some of these embodiments are able to detect a wide variety of different peteyes using multiple classification maps that segment pixels into peteye pixels and non-peteye pixels. Each of the classification maps is generated based on a different respective segmentation condition on the values of the pixels, where each segmentation condition is selected to increase the contrast between the pixels typically contained in a respective type of peteye area and surrounding non-peteye pixels. In some embodiments, the contrast between peteye pixels and non-peteye pixels is increased by segmenting pixels into a specified animal-fur color class and a non-animal-fur color class. In addition, some of these embodiments apply type-specific peteye color correction processes to the peteye pixels in the detected peteye pixel areas to generate a corrected image.
FIG. 1 shows an embodiment of a system 10 for detecting and correcting peteye pixels in an input image 12 that includes a peteye detection module 14 and a peteye correction module 16 . The input image 12 may correspond to any type of image, including an original image that was captured by an image sensor (e.g., a video camera, a still image, or an optical scanner) or a processed (e.g., sub-sampled, filtered, reformatted, enhanced or otherwise modified) version of such an original image.
The peteye detection module 14 semi-automatically detects areas 18 in input image 12 likely to contain peteye. In particular, the peteye detection module 14 automatically detects candidate peteye pixel areas in the input image 12 and selects ones of the candidate peteye pixel areas as the detected peteye pixel areas 18 based on the user's selection of areas of the input image 12 coincident with respective ones of the candidate peteye pixel areas. The peteye correction module 16 automatically corrects the detected peteye areas 18 by applying type-specific peteye color correction processes to the peteye pixels in the detected peteye pixel areas 18 to generate a corrected image 20 . In some cases, multiple type-specific color correction processes will apply to a detected peteye area 18 . In these cases, the user may have the peteye correction module 16 apply multiple ones of the applicable type-specific color correction processes to the peteye pixels in the corrected ones of detected peteye pixel areas 18 .
In some embodiments, the peteye detection module 14 and the peteye correction module sequentially process the input image 12 with respect to each peteye type. In other embodiments, the peteye detection module 14 detects all peteye types in the input image 12 and then the peteye correction module 16 corrects the detected peteyes that are selected by the user.
In general, the peteye detection module 14 and the peteye correction module 16 are not limited to any particular hardware or software configuration, but rather they may be implemented in any computing or processing environment, including in digital electronic circuitry or in computer hardware, firmware, device driver, or software. The peteye detection module 14 and the peteye correction module 16 may be incorporated into any system or method in which such functionality is desired, including embedded environments, which typically have limited processing and memory resources. For example, the peteye detection module 14 and the peteye correction module 16 may be embedded in the hardware of any one of a wide variety of electronic devices, including digital cameras, printers, and portable electronic devices (e.g., mobile phones and personal digital assistants).
II. Detecting Peteye Pixel Areas
A. Peteye Detection Module Overview
Referring to FIG. 2 , in some embodiments, the peteye detection module 14 includes an initial candidate detection module 22 , a candidate peteye verification module 24 , and a detected peteye pixel area selection module 25 . The initial candidate detection module 22 identifies a set of initial candidate peteye pixel areas 26 in the input image 12 , and the candidate peteye verification module 24 filters false alarms (i.e., candidate peteye pixel areas with a low likelihood of corresponding to actual peteyes in input image 12 ) from the set of initial candidate peteye pixel areas 26 to produce a set of candidate peteye pixel areas 27 . The detected peteye pixel area selection module 25 selects the set of detected peteye areas 18 from the set of candidate peteye pixel areas based on user input.
B. Initial Candidate Detection Module
1. Overview
As explained in detail below, in some embodiments, initial candidate detection module 22 identifies candidate peteye pixel areas using multiple classification maps that segment pixels into peteye pixels and non-peteye pixels based on different respective segmentation conditions. In this way, initial candidate detection module 22 ensures that there is a high likelihood that all of the actual peteyes in the input image 12 are included in the set of initial candidate peteye pixel areas 26 .
Referring to FIG. 3 , in some embodiments, the initial candidate detection module 22 includes a classification map generation module 28 and a segmentation module 30 . The classification map generation module 28 generates multiple classification maps 32 , each of which segments pixels in the input image 12 into peteye pixels and non-peteye pixels. The segmentation module 30 segments the peteye pixels in the classification maps 32 into the initial candidate peteye pixel areas 26 .
The classification map generation module 28 generates each of the classification maps 32 based on a different respective segmentation condition on the values of the pixels. Each of the segmentation conditions is selected to increase the contrast between the pixels that typically are contained in a respective type of peteye area and surrounding non-peteye pixels. In the illustrated embodiments, the segmentation conditions are selected to increase the likelihood of identifying the following common types of peteyes: red peteyes (designated Type I); bright peteyes (designed Type II); non-pet-fur-color peteyes (designated Type III); very bright peteyes (designated Type IV); and bright peteyes with bright surroundings (designated Type V). In an exemplary sample of 227 images containing 402 peteyes, it was observed that Type I peteyes composed approximately 23% of the sample, Type II peteyes composed approximately 33% of the sample, Type III peteyes composed approximately 26% of the sample, Type IV peteyes composed approximately 12% of the sample, and Type V peteyes composed approximately 3% of the sample.
In the embodiments that are described in detail below: the segmentation condition for Type I peteyes is a threshold level of red contrast between red peteyes and their non-red neighbors; the segmentation condition for Type II peteyes is a first threshold level of luminance contrast between bright peteyes and their less bright neighbors; the segmentation condition for Type III peteyes is contrast between non-pet-fur color peteye pixels and their pet-fur colored neighbors, where white is a pet-fur color; the segmentation condition for Type IV peteyes is a second threshold level of luminance contrast between bright peteyes and their less bright neighbors, where the second threshold level of luminance contrast is higher than the first threshold level of luminance contrast used in the segmentation condition for Type II peteyes; the segmentation condition for Type V peteyes is contrast between non-pet-fur color peteye pixels and their pet-fur colored neighbors, where white is a non-pet-fur color.
2. Generating Classification Maps
FIG. 4 shows a set of classification maps 34 , 36 , 38 , 40 , 42 that are generated in an embodiment of a method of identifying the initial candidate peteye pixel areas 26 in the input image 12 . The classification maps 34 - 42 may be generated sequentially or in parallel. The classification map 34 segments pixels in the input image 12 into Type I peteye pixels and non-peteye pixels. The classification map 36 segments pixels in the input image 12 into Type II peteye pixels and non-peteye pixels. The classification map 38 segments pixels in the input image 12 into Type III peteye pixels and non-peteye pixels. The classification map 40 segments pixels in the input image 12 into Type IV peteye pixels and non-peteye pixels. The classification map 42 segments pixels in the input image 12 into Type V peteye pixels and non-peteye pixels.
a. Generating Classification Maps for Type I Peteyes
The classification map 34 for Type I peteyes is generated by producing a redness map 44 from the input image 12 and applying to the redness map 44 a redness threshold that segments the pixels of the input image 12 into Type I peteye pixels and non-peteye pixels. The redness map 44 may be produced by mapping the values of the pixels of the input image 12 into a one-dimensional redness color space.
In accordance with one redness color space model, the classification map generation module 28 converts the input image 12 into the CIE L*a*b* color space. The classification map generation module 28 then binarizes the L*a*b* color space representation of the input image 12 based on one or more of the contrast threshold curves that are described in U.S. patent application Ser. No. 10/653,019, filed on Aug. 29, 2003, by Huitao Luo et al., and entitled “DETECTING AND CORRECTING RED-EYE IN AN IMAGE,” to produce the classification map 34 for Type I peteyes.
In accordance with another redness color space model, the classification map generation module 28 initially computes measures of pixel redness in the input image 12 to generate the redness map 44 . Any one of a variety of different measures of pixel redness may be used to generate the redness map 44 from input image 12 . In some embodiments, the pixel redness measures are computed based on a ratio of a measure of a red component of pixel energy to a measure of total pixel energy. For example, in one implementation, pixel redness measures (R 0 ) are computed as follows:
R 0 = α · r + β · g + γ · b r + g + b + d ( 1 )
where r, g, and b are red, green, and blue component pixel values of input image 12 , respectively, α, β and γ are weighting factors, and d is a prescribed constant with a value selected to avoid singularities and to give higher weights to bright pixels. In one exemplary implementation in which each of r, g, and b have values in the range of [0,255], α=204, β=−153, and γ=51, and d has a value of 1. Based on the mapping of equation (1), the redness of each pixel of input image 12 is mapped to a corresponding pixel of the redness map 44 having a redness value given by equation (1).
In other embodiments, the redness map 44 is computed using different respective measures of redness. For example, in one exemplary implementation, pixel redness measures (R 0 ) for the redness map 44 are computed as follows: R 0 =(255·r)/(r+g+b+d) when r>g, r>b; otherwise R 0 =0. Other representative redness measures (R 1 , R 2 , R 3 , R 4 ) that may be used to compute the redness map 44 are expressed in equations (2)-(5) below:
R 1 = r 2 ( r + g + b + 1 ) 2 ( 2 ) R 2 = r 2 ( g + b ) 2 ( 3 ) R 3 = r + b ( r + g + b + 1 ) ( 4 ) R 4 = Cr ( Cb + 1 ) 2 ( 5 )
where r, g, and b are red, green, and blue component pixel values of input image 12 , respectively, and Cr and Cb are the red and blue chrominance component pixel values of the input image 12 in the YCbCr color space.
Next, the classification map generation module 28 binarizes the redness map 44 to produce the classification map 34 . In some implementations, the redness map 44 is binarized by applying a linear adaptive threshold filter to the redness map 44 . In one exemplary implementation of a linear adaptive threshold filter, the value of each pixel in the redness map 44 is compared with the average of its neighboring pixels, where the neighborhood is defined as a square d×d pixel window, centered at the current pixel. The window size d is defined with respect to the original image size (h×w) as follows:
d =min( h, w )/13 (6)
where h and w are the height and width of the original input image. If the current pixel has a higher redness value than its neighborhood average, the filter output is one; otherwise the output is zero.
b. Generating Classification Maps for Type II Peteyes
The classification map 36 for Type II peteyes is generated by producing a luminance map 46 from the input image 12 and applying to the luminance map 46 a luminance threshold that segments the pixels of the input image 12 into Type II peteye pixels and non-peteye pixels. The luminance map 46 may be produced by mapping the values of the pixels of the input image 12 into a one-dimensional luminance color space.
In accordance with one luminance color space model, the classification map generation module 28 initially computes measures of pixel luminance in the input image 12 to generate the luminance map 46 . Any one of a variety of different measures of pixel luminance may be used to generate the luminance map 46 from input image 12 . In some embodiments, the pixel luminance measures L are computed as follows:
L = u · r + v · g + w · b x ( 7 )
where r, g, and b are red, green, and blue component pixel values of input image 12 , respectively, u, v, and w are weighting factors, and x is a prescribed constant.
In one exemplary implementation in which each of r, g, and b have values in the range of [0,255], u=77, v=150, w=29, and x=256. Based on the mapping of equation (7), the luminance of each pixel of the input image 12 is mapped to a corresponding pixel of the luminance map 46 having a luminance value given by equation (7).
Next, the classification map generation module 28 binarizes the luminance map 46 to produce the classification map 36 . In some implementations, the luminance map 46 is binarized by applying a linear adaptive threshold filter to the luminance map 46 . In one exemplary implementation, the value of each pixel in the luminance map 46 is compared with the average of its neighboring pixels, where the neighborhood is defined as a square d×d pixel window, which is centered at the current pixel, and the window size d is defined with respect to the is original image size (h×w) in accordance with equation (6) above. If the current pixel has a higher luminance value than its neighborhood average, the filter output is one; otherwise the output is zero.
c. Generating Classification Maps for Type III Peteyes
The classification map 38 for Type III peteyes is generated by producing an animal-fur color map 48 from the input image 12 and labeling pixels in the animal-fur color map 48 classified in a specified animal-fur color class as non-peteye pixels and pixels in the animal-fur color map 48 classified in a specified non-animal-fur color class as Type III peteye pixels. The animal-fur color map 48 may be produced by mapping the values of the pixels of the input image 12 into a quantized color space having a finite set of specified colors each of which is defined by a respective color range. In some embodiments, the animal-fur color map 48 is produced by mapping the pixels in the input image 12 into a quantized color space consisting of a set of twenty-seven non-overlapping quantized color bins.
It has been discovered from an analysis of a sample of images of animals that animal-fur colors typically can be classified into a small class of possible animal fur colors. In particular, each image in the sample was cropped to remove non-fur-coated areas and the resulting cropped images were mapped to a quantized color space defined by a set of twenty-seven color names (or bins). FIG. 5 shows a histogram of the number of pixels in a sample of sixty-two cropped images classified into respective ones of the twenty-seven color bins. As shown by the histogram, most of the animal-fur color images were classified into a small set of the possible color bins: brown, flesh, and five levels of gray, including white (which corresponds to bin number 0 ). Equations (13)-(15) below provide an exemplary definition of these animal-fur colors in which the five levels of gray are defined in terms of a single luminance range. The remaining animal-fur colors that were observed (i.e., olive, maroon, cyan, and pale yellow) were found to correspond to specular reflections from animal fur, reflections from other parts of the image (e.g., sky or grass) near the animals, and image artifacts or compression artifacts.
Next, the classification map generation module 28 binarizes the animal-fur color map 48 to produce the classification map 38 . In this process, pixels classified in one of the seven possible animal-fur color bins are segmented into a non-peteye class and pixels classified in any of the other (non-animal-fur) color bins are segmented into a Type III peteye class.
In some embodiments, the classification map generation module 28 produces the classification map 38 directly from the input image without producing the animal-fur color map 48 in accordance with the following process:
1. Convert the input image 12 into the YCrCb color space. For example, in some embodiments, if the input image 12 originally is specified in the RGB color space, the input image pixels are mapped into the YCrCb color space as follows:
Y= 0.299 ·r+ 0.587 ·g+ 0.112 ·b (8)
Cr= 0.713266·( r−Y )+128 (9)
Cb= 0.564334·( b−Y )+128 (10)
where r, g, and b are red, green, and blue component pixel values of input image 12 , respectively, and Y, Cr, and Cb are the component pixel values in the YCrCb color space.
2. Calculate the chroma and hue for each of the input image pixels as follows:
Chroma
=
1.88085
·
Cr
·
Cb
+
Cb
·
Cb
(
11
)
Hue
=
0.708333
·
Arc
Tangent
(
Cr
Cb
)
(
12
)
3. Segment pixels of the input image 12 into the non-peteye class if one of the following conditions is true:
a. the pixel is in a gray color range defined by:
Chroma<25; or (13)
b. the pixel is in a brown color range defined by:
(Chroma<120) AND (Y<120) AND (Hue≧254 OR Hue≦45); or (14)
c. the pixel is in a flesh color range defined by:
(Chroma<115) AND (Y≧120) AND (10≦Hue≧45). (15)
FIG. 6 shows a classification map 38 that is derived by segmenting pixels in an image of a dog exhibiting a pair of Type III peteyes 50 , 52 into an animal-fur color class (shown by the gray pixels) and a non-animal-fur color class (shown by the white pixels). As shown in the figure, at least for Type III peteyes, there is high contrast between the white pixels in the classification map 38 that correspond to the non-animal-fur color peteyes 50 , 52 and the surrounding gray pixels that correspond to animal-fur color pixels.
d. Generating Classification Maps for Type IV Peteyes
The classification map 40 for Type IV peteyes is generated in the same way that the classification map 36 for Type II peteye is generated, except that the luminance threshold used to binarize the luminance map is increased to a higher empirically determined threshold value. For example, in some implementations, if the luminance value of a current pixel is higher than the average neighborhood luminance by an empirically determined additive or multiplicative scale factor, the current pixel is classified as a potential Type IV peteye pixel and set to one in the classification map 40 ; otherwise the current pixel is classified as a non-Type IV peteye pixel and set to zero in the classification map 40 .
e. Generating Classification Maps for Type V Peteyes
The classification map 42 for Type V peteyes is generated in the same way that the classification map 38 for Type III peteye is generated, except that white pixels (e.g., pixels with red, green, and blue component values all equal to 255 in an 8-bit RGB color space representation) are classified as non-animal-fur color pixels.
3. Identifying Initial Candidate Peteye Pixel Areas
In the illustrated embodiment, the classification maps 34 - 42 are passed to the segmentation module 30 , which generates the set of initial candidate peteye pixel areas 26 by generating objects for all the pixels set to one in the classification maps. The segmentation module 30 segments the candidate peteye pixels into peteye and non-peteye classes based on pixel connectivity using any one of a wide variety of pixel connectivity algorithms. Each pixel area that is segmented into the peteye class is labeled as a candidate peteye area. In the embodiments illustrated herein, each candidate peteye area is represented by a boundary rectangle (or box). In other embodiments, the candidate peteye pixel areas may be represented by non-rectangular shapes.
C. Candidate Peteye Verification Module
As explained in detail below, the candidate peteye verification module 24 ( FIG. 2 ) classifies the candidate peteye pixel areas based on consideration of multiple features in parallel using a machine learning framework to verify that candidate peteye pixel areas correspond to actual peteyes in input image 12 with greater accuracy and greater efficiency.
FIG. 7 shows an implementation of the candidate peteye verification module 24 that is implemented by a single peteye verification classifier 54 . The single peteye verification classifier filters candidate peteye pixels from the initial set 26 based on a projection of input image data into a feature space spanned by multiple features to generate feature vectors respectively representing the candidate peteye pixel areas 26 in the feature space. Candidate peteye pixel areas in the initial set 26 are filtered out based on the generated feature vectors. In particular, the single peteye verification classifier 54 classifies the candidate peteye pixel area into the set of candidate peteye pixel areas 27 or a set of false alarms 56 .
Additional details regarding the structure and operation of the single peteye verification classifier 54 , as well as a description of the feature vectors that are used by the single peteye verification classifier 54 to classify the initial candidate peteye pixel areas 26 , can be obtained from the description of the single-eye verification classifier contained in U.S. patent application Ser. No. 10/653,019, filed on Aug. 29, 2003, by Huitao Luo et al., and entitled “DETECTING AND CORRECTING RED-EYE IN AN IMAGE.”
D. Selecting Ones of the Candidate Peteye Pixel Areas as Detected Pixel Areas
As explained above, the detected peteye pixel area selection module 25 selects the set of detected peteye areas 18 from the set of candidate peteye pixel areas 27 based on user input. In particular, the detected peteye pixel area selection module 25 selects ones of the candidate peteye pixel areas 27 as the detected peteye pixel areas 18 based on the user's selection of areas of the input image 12 that are coincident with respective ones of the candidate peteye pixel areas 27 .
FIG. 8A shows an embodiment of a graphical user interface 58 presenting an image 60 of a dog and a user-controlled pointer 62 overlayed on the image. FIG. 8A also shows a bounding box 64 that is superimposed on a portion of the eye of the dog shown in the image 60 . The bounding box 64 contains one of the candidate peteye pixel areas 27 that were verified by the candidate peteye verification module 24 . In some embodiments, the bounding box 64 is hidden from the user. In other embodiments, the bounding box 64 is visible to the user.
FIG. 8B shows the graphical user interface 58 after a user has moved the pointer 62 into an area of the image 60 that coincides with the candidate peteye pixel area defined by the bounding box 64 . In response to the user's selection of the area of the image 60 specified by the pointer 62 (e.g., by pressing a button on an input device, such as a computer mouse), the detected peteye pixel area selection module 25 selects the candidate peteye pixel area 27 corresponding to the bounding box 64 as one of the detected peteye areas 18 .
III. Peteye Correction
Referring to FIG. 9 , after the detected peteye pixel areas 18 have been selected, the pixels within the detected peteye pixel areas 18 are classified as peteye pixels and non-peteye pixels (block 66 ). The pixels within each of the detected peteye pixel areas 18 that are classified as peteye pixels are then recolored (block 68 ).
Referring to FIG. 10 , in some embodiments, before the detected peteye pixel areas 18 are classified, the corners of the detected redeye pixel areas 18 are cropped to form an octagonal shape that approximates the shape typical of animal eye pupils. The amount by which the corners are cropped is empirically determined. In one exemplary illustration, the side dimension of each corner region corresponds to 15% of the corresponding side (horizontal or vertical) dimension of the detected redeye pixel areas 18 .
A. Classifying Peteye Pixels
FIG. 11 shows an embodiment of a process of classifying peteye pixels in the detected peteye pixel areas 18 . In some embodiments, the pixels within each of the detected peteye pixel areas 18 are classified independently of the other peteye pixel areas. In these embodiments, pixel classification also is performed per pixel and per pixel line without any reference to (or coherence with) adjacent (above or below) pixel lines.
In some embodiments, a number of fast heuristics are applied to the candidate peteye areas to eliminate false alarms (i.e., candidate peteye pixel areas that are not likely to correspond to actual peteye areas), including aspect ratio inspection and shape analysis techniques. For example, in some implementations, atypically elongated candidate peteye areas are removed.
In the embodiment shown in FIG. 11 , the detected peteye pixel area 18 is skipped and the next detected peteye pixel area 18 is processed ( FIG. 11 , block 70 ), if the detected peteye pixel area 18 is atypically large ( FIG. 11 , block 72 ). In some implementations, a detected peteye pixel area 18 is considered to be atypically large if any dimension (e.g., width or height) is larger than an empirically determined number of pixels.
The detected peteye pixel area 18 also is skipped if the aspect ratio of the detected peteye pixel area 18 is outside of an empirically determined valid range of aspect ratio values (block 74 ). The aspect ratio includes the ratio of width-to-height of the corresponding bounding box and the ratio of height-to-width of the corresponding bounding box. In some implementations, the valid range of aspect ratio values is from 1:2 to 2:1.
The pixels in the detected peteye pixel areas that are not too large and that have an aspect ratio within the specified valid range, are classified as candidate peteye pixels and non-candidate peteye pixels line-by-line based on horizontal coherence ( FIG. 11 , block 76 ). In some implementations, if a given peteye pixel is located adjacent to a pixel previously classified as a candidate peteye pixel and has a value (i.e., a redness value for Type I peteyes or a luminance value for Type II and Type IV peteyes) that is greater than an empirically determined, type-specific threshold value, then the given pixel also is classified as a candidate peteye pixel. In these implementations, the pixels of Type III peteyes are not classified by horizontal coherence.
Referring to FIGS. 11 and 12A , the pixels in the current detected peteye pixel area 18 are classified as candidate peteye pixels and non-candidate peteye pixels based on regions that are derived from a detected peteye pixel area 18 and a corresponding grayscale iris pixel area ( FIG. 11 , block 78 ). In some embodiments, a detected peteye pixel area 18 is represented by a rectangle 80 and the associated iris is represented as a square 82 . The iris is assumed to share the same center with the detected peteye pixel area 80 . Note that each of the detected peteye area 80 is not necessarily identical to its associated grayscale iris area 82 . In some embodiments, the square grayscale iris area 82 is computed over a grayscale plane using the following search algorithm.
Initially, a grayscale map is computed by mapping the pixels of input image 12 in accordance with a grayscale mapping G, given by G=MIN(G 1 , G 2 ), where MIN is a function that outputs the minimum of G 1 and G 2 , which are given by:
G 1=0.299 ×r+ 0.587 ×g+ 0.114 ×b (13)
G 2=0.299×(255 −r )+0.587 ×g+ 0.114 ×b (14)
where r, g and b are red, green and blue values for each pixel within the region and the grayscale values are obtained for each pixel and averaged over the region. In this grayscale mapping, G 1 is a standard grayscale mapping computed from (r, g, b), whereas G 2 is the grayscale mapping computed from (255-r, g, b). The grayscale mapping G 2 handles instances of “glowing” peteyes (i.e., when a peteye appears much brighter than its surroundings). In accordance with the above approach, such atypical “glowing” peteyes are mapped to a grayscale channel that allows them to be treated in the same way as typical peteyes.
Next, a search is performed over the computed grayscale map to locate one or more areas corresponding to irises. In this search, it is assumed that the iris area 82 shares the same center with its detected peteye area 80 . The size of the iris area 82 is determined based on a comparison of a candidate square box (box 8 in FIG. 12B ) with each of its eight nearest neighbors (boxes 0 - 7 in FIG. 12B ). In one implementation, an initial area that encompasses the surrounding areas 0 - 7 is partitioned into nine equal-sized nearest neighbor boxes (numbered 0 - 8 ). The size of the final optimal grayscale box 82 (or square) is determined by selecting a size that maximizes the grayscale contrast between the center box (box 8 ) and its surrounding neighbors (boxes 0 - 7 ). In this search process, only one variable is involved: the side length of the center box. In one implementation, a brute force search technique is used to determine the final size of grayscale iris area 82 .
Referring to FIGS. 11 and 13A , the peteye pixel areas are classified with respect to an inner bounding region 84 and an outer bounding region 86 , which are derived from the grayscale iris area 82 . The inner bounding region 84 is centered at the center of the detected peteye pixel area 18 being processed and has dimensions (e.g., width and height) that correspond to the average of the dimensions of the detected peteye pixel area 18 and its corresponding grayscale iris area 82 . The outer bounding region 86 also is centered at the center of the detected peteye pixel area 18 . In one implementation, the dimensions of the outer bounding region 86 are 50% larger than the corresponding dimensions of the inner bounding region 84 if the inner bounding region 84 is larger than two pixels; otherwise, the dimensions of the outer bounding region 86 are 200% larger than the corresponding dimensions of the inner bounding region 84 .
The pixels between the inner and outer bounding regions 84 , 86 are classified as either candidate peteye pixels or non-candidate peteye pixels based on application of a grayscale threshold to the computed grayscale values of the pixels as follows. In some implementations the green channel in RGB color space is used to approximate the grayscale values of pixels. In one implementation, the applied grayscale threshold corresponds to the average of (1) the average of the grayscale values within the inner bounding region 84 and (2) the average of the grayscale values between the inner and outer bounding regions 84 , 86 . For example, if the average of the gray values within the inner bounding region 84 is 90 and the average of the gray values outside the inner bounding region 84 but within the outer bounding region 86 is 120, then the average gray value, which is (90+120)/2=105, is the grayscale threshold used to segment the pixels between the inner and outer bounding regions 84 , 86 . Pixels between the inner and outer bounding regions 84 , 86 having grayscale values below the computed grayscale threshold are classified as candidate peteye pixels.
All of the pixels within the outer bounding region 86 shown in FIG. 13A that have been classified as candidate peteye pixels in the process blocks 76 and 78 of FIG. 11 are classified as peteye pixels based on connectivity, with stringent requirements to remove fragments, outliers, and noise.
Referring to FIGS. 11 and 13B , a peteye pixel correction region 88 that encompasses (or encircles) all pixels within the outer bounding region 86 that are classified as peteye pixels is identified ( FIG. 11 , step 90 ). In some implementations, the peteye pixel correction region 88 has an elliptical shape. In the illustrated example, the peteye pixel correction region 88 has a circular shape. In addition to the peteye pixel correction region 88 , a peteye pixel smoothing region 92 surrounding the peteye pixel correction region 88 is computed. In the example illustrated in FIG. 13B , the peteye pixel smoothing region 92 is defined by a circular boundary 94 that is concentric with the peteye pixel correction region 88 and has a radius that is 50% larger than the radius of the peteye pixel correction region 88 .
Referring back to FIG. 11 , after the classified peteye pixels have been classified ( FIG. 11 , blocks 76 , 78 ) and the peteye pixel correction and smoothing regions 88 , 92 have been identified ( FIG. 11 , block 90 ), the pixels in the detected peteye pixel areas 18 that have been classified as peteye pixels are recolored ( FIG. 11 , block 96 ). The process is repeated until all the detected peteye pixel areas have been corrected ( FIG. 11 , block 98 ).
B. Recoloring Peteye Pixels
The peteye pixels are corrected in accordance with a Type-specified pixel correction process shown in FIG. 14 .
1. Recoloring Peteye Pixels in Type I Pixel Areas
If the detected peteye pixel area 18 is a Type I peteye pixel area ( FIG. 14 , block 100 ), the peteye pixels in the peteye pixel correction region 88 are corrected as follows.
Color values of the peteye pixels are corrected by desaturating ( FIG. 14 , block 102 ) and darkening ( FIG. 14 , block 104 ) original color values in accordance with color correction darkening factors and weights that are computed for the peteye pixels to be corrected in accordance with the process described below. The darkening factors and weights indicate how strongly original color values of the peteye pixels are to be desaturated (i.e., pushed towards neutral or gray values). As explained in detail below, these two factors vary with pixel location relative to the center of the peteye pixel correction region 88 to give a smooth transition between the pixels in the input image 12 that are changed and those that are not to avoid artifacts.
The darkening factors are computed based on luminance (or gray) values of the input image pixels. In one implementation, the darkening factors are computed based on the graph shown in FIG. 15 , where the luminance (or gray) level of each peteye pixel is assumed to vary over a range of [lum min , lum max ]=[0, 1]. In one implementation, the green color channel is used to estimate luminance values. Other implementations may use different estimates or measures of luminance values. In the illustrated implementation, the minimum darkening factor (m i ) is set to 0.6 and the maximum darkening factor (m f ) is set to 1.0. These parameters may be set to different values in other implementations. In this formulation, the darkening factor values decrease with the darkness levels of the pixels. That is, lower (i.e., darker) luminance (or gray) values are associated with lower darkening factors. Since the darkening factors influence pixel values in a multiplicative way in the implementation described below, darker pixels (i.e., pixels with lower luminance values) identified as peteye pixels are darkened more than lighter pixels (i.e., pixels with higher luminance values).
The weights (wt) are set for a given peteye pixel based on the number of peteye pixels that neighbor the given pixel. For example, in one implementation, the weights may be set as follows:
wt = { 0 peteye neighbors = 0 .33 peteye neighbors = 1 , 2 , 3 .67 peteye neighbors = 4 , 5 , 6 1 peteye neighbors = 7 , 8 ( 15 )
where “peteye neighbors” corresponds to the number of peteye pixels that neighbor the given pixel being assigned a weighting factor. In this formulation, peteye pixels near the center of the peteye pixel correction region 88 are assigned higher weights than peteye pixels near the boundaries of the peteye pixel correction region 88 .
In some RGB color space implementations, the color values (red, green, blue) of each input image pixel identified as a peteye pixel are corrected to the final color values (R 1 , G 1 , B 1 ) as follows:
If (mask=1), tmp=dark[green−grn min ]
Else tmp=1
R 1 =( wt*tmp *green+(1 −wt )*red)
G 1 =( wt*tmp *green+(1 −wt )*green)
B 1 =( wt*tmp *green+(1 −wt )*blue)
In these embodiments, it is assumed that the color components of the input image pixels are defined with respect to the RGB color space. These embodiments readily may be extended to other color space representations. It is noted that if wt=1, pixel values are pushed all the way to neutral (i.e., the pixel values are set to the same shade of gray). If wt=0, none of the color component values of the corresponding pixel are changed. In this implementation, lower luminance pixels (i.e., smaller green values) generally are pushed darker than higher luminance pixels, which have their luminance unchanged.
The original color values of peteye pixels in the peteye pixel smoothing region 92 are corrected in a similar way as the peteye pixels in the pixel correction region 88 , except that the relative amount of correction varies from 90% at the boundary with the peteye pixel correction region 88 to 20% at the boundary 94 of the peteye pixel smoothing region 92 . This smoothing or feathering process reduces the formation of disjoint edges in the vicinity of the corrected peteyes in the corrected image.
Referring back to FIG. 14 , if the user is satisfied with the results of the desaturating and darkening recoloring processes ( FIG. 14 , block 106 ), the peteye pixel correction process is terminated ( FIG. 14 , block 108 ). If the user is not satisfied with the results ( FIG. 14 , block 106 ), the user may have the peteye pixel detection and correction system 10 re-perform the peteye detection process described above on the corrected image 20 . The user may then re-select the previously selected peteye pixel area 64 ( FIGS. 8A and 8B ) using, for example, the user interface shown in FIGS. 8A and 8B . If the selected area corresponds to a detected peteye pixel area 18 , the peteye correction module 16 will recolor the peteye pixels in the detected peteye pixel area 18 in accordance with the process shown in FIG. 11 . Since Type I peteye pixel areas have already been corrected, the newly detected peteye pixel areas should correspond to one or more of the other types of peteye pixel areas (i.e., peteye Types II-V).
In some embodiments, a user who is not satisfied with the peteye pixel correction results may select an undo command to return the image to its previous state.
2. Recoloring Peteye Pixels in Type II or Type IV Pixel Areas
Referring to FIG. 14 , if the detected peteye pixel area 18 is a Type II peteye pixel area or a Type IV peteye pixel area ( FIG. 14 , block 110 ), the peteye pixels in the peteye pixel correction region 88 are corrected as follows.
Initially, the color values of the peteye pixels in Type II and Type IV peteye pixel areas are corrected by desaturating ( FIG. 14 , block 112 ) and darkening ( FIG. 14 , block 114 ) the original color values in accordance with the processes described above in connection with peteye pixels in Type I peteye pixel areas.
Referring to FIGS. 14 , 16 , and 17 , After the desaturating and darkening the peteye pixel areas ( FIG. 14 , blocks 112 , 114 ), the peteye correction module 16 processes the detected peteye pixel areas as follows to correct large glowing glint.
In this process, the pixels in the detected peteye pixel area are classified based on glint (block 116 ). In one implementation, peteye pixel areas are classified as containing large glowing glint if the percentage of the non-peteye pixels in an oval glint correction region 118 inscribed in a boundary box 80 corresponding to the detected peteye pixel area 18 is greater than a heuristically determined threshold (see FIG. 17 ). In another implementation, peteye pixel areas are classified as containing large glowing glint if the average luminance value computed over the oval glint correction region 118 is greater than a heuristically determined threshold. In another implementation, peteye pixel areas are classified as containing large glowing glint if the average luminance value computed over the oval glint correction region 118 is greater than the average luminance value computed over the regions of the boundary box 80 surrounding the oval glint correction region 118 by a heuristically determined threshold.
If a detected peteye pixel area is classified as containing large glowing glint ( FIG. 14 , block 120 ), the peteye correction module 16 performs glint correction as follows ( FIG. 14 , block 122 ).
Referring to FIG. 16 , initially, the center (C i ,C j ) of the glint correction region 118 is computed ( FIG. 16 , block 124 ; FIG. 17 ). In one implementations, the center (C i C j ,) of the glint correction region 118 is the location of the pixel with the maximal luminance value. In instances in which there are multiple pixels with the maximal luminance value, the pixel location that is closest to the average of the locations of the pixels with the maximal luminance value is selected as the center (C i ,C j ) of the glint correction region 118 . For each pixel (i,j) within the oval glint correction region 118 , the distance D 1 to the center (C i ,C j ) of the glint correction region 118 is determined. The darkening factor a for each pixel is computed as follows ( FIG. 16 , block 126 ):
α = 1.0 - 0.3 ( D 1 D 2 ) 0.005 ( 16 )
where D 2 =(A 2 +B 2 ) 1/2 , and A and B correspond to one-half of the lengths the semiminor and semimajor axes of the oval glint correction region 118 , respectively. The pixels within the glint correction region 118 are darkened in accordance with the computed darkening factors as follows ( FIG. 16 , block 128 ):
Red FINAL =α·Red INITIAL (17) Green FINAL =α·Green INITIAL (18) Blue FINAL =α·Blue INITIAL (19)
where Red FINAL , Green FINAL , and Blue FINAL are the final darkened red, green, and blue color values for the glint corrected pixel, and Red INITIAL , Green INITIAL , and Blue INITIAL are the initial red, green, and blue color values of the pixel after the desaturating and darkening recoloring processes shown in blocks 112 , 114 of FIG. 14 .
The original color values of peteye pixels in the peteye pixel smoothing region 92 are corrected in a similar way as the peteye pixels in the pixel correction region 88 , except that the relative amount of correction varies from 90% at the boundary with the peteye pixel correction region 88 to 20% at the boundary 94 of the peteye pixel smoothing region 92 . This smoothing or feathering process reduces the formation of disjoint edges in the vicinity of the corrected peteyes in the corrected image.
Referring back to FIG. 14 , if the user is satisfied with the results of the desaturating and darkening recoloring processes ( FIG. 14 , block 130 ), the peteye pixel correction process is terminated ( FIG. 14 , block 108 ). If the user is not satisfied with the results ( FIG. 14 , block 130 ), the user may have the peteye pixel detection and correction system 10 re-perform the peteye detection process described above on the corrected image 20 . The user may then re-select the previously selected peteye pixel area 64 ( FIGS. 8A and 8B ) using, for example, the user interface shown in FIGS. 8A and 8B . If the selected area corresponds to a detected peteye pixel area 18 , the peteye correction module 16 will recolor the peteye pixels in the detected peteye pixel area 18 in accordance with the process shown in FIG. 11 . Since Type I, II, and IV peteye pixel areas have already been corrected, the newly detected peteye pixel areas should correspond to one or more of the other types of peteye pixel areas (i.e., peteye Types III and V).
In some embodiments, a user who is not satisfied with the peteye pixel correction results may select an undo command to return the image to its previous state.
3. Recoloring Peteye Pixels in Type III or Type V Pixel Areas
Referring to FIG. 14 , if the detected peteye pixel area 18 is a Type III pixel area or a Type V peteye pixel area ( FIG. 14 , block 132 ), the peteye pixels in the peteye pixel correction region 88 are corrected as follows.
Initially, the color values of the peteye pixels in Type III and Type V peteye pixel areas are corrected by desaturating ( FIG. 14 , block 134 ) the original color values in accordance with the desaturation process described above in connection with peteye pixels in Type I peteye pixel areas.
If the proportion of non-pet-fur color pixels in the detected peteye pixel area constitutes less than an empirically determined threshold (e.g., 40%) (FIG. 14 , block 136 ), the peteye pixel correction process is terminated ( FIG. 14 , block 108 ). If the proportion of non-pet-fur color pixels in the detected peteye pixel area is greater than the threshold ( FIG. 14 , block 136 ), the peteye pixels are darkened ( FIG. 14 , block 138 ) in accordance with the darkening process described above in connection with peteye pixels in Type I peteye pixel areas. In addition, the pixels in the detected peteye pixel area are classified based on glint ( FIG. 14 , block 140 ) and if a detected peteye pixel area is classified as containing large glowing glint ( FIG. 14 , block 142 ), the peteye correction module 16 performs glint correction ( FIG. 14 , block 144 ) in accordance with the glint correction process described above in connection with peteye pixels in Type III and Type V peteye pixel areas.
The original color values of peteye pixels in the peteye pixel smoothing region 92 are corrected in a similar way as the peteye pixels in the pixel correction region 88 , except that the relative amount of correction varies from 90% at the boundary with the peteye pixel correction region 88 to 20% at the boundary 94 of the peteye pixel smoothing region 92 . This smoothing or feathering process reduces the formation of disjoint edges in the vicinity of the corrected peteyes in the corrected image.
IV. CONCLUSION
The embodiments that are described in detail herein are designed specifically to detect and correct peteyes in images. As a result, these embodiments are capable of satisfactorily detecting and correcting the majority of peteyes that appear in images. Some of these embodiments are able to detect a wide variety of different peteyes using multiple classification maps that segment pixels into peteye pixels and non-peteye pixels. Each of the classification maps is generated based on a different respective segmentation condition on the values of the pixels, where each segmentation condition is selected to increase the contrast between the pixels typically contained in a respective type of peteye area and surrounding non-peteye pixels. In some embodiments, the contrast between peteye pixels and non-peteye pixels is increased by segmenting pixels into a specified animal-fur color class and a non-animal-fur color class. In addition, some of these embodiments apply type-specific peteye color correction processes to the peteye pixels in the detected peteye pixel areas to generate a corrected image.
Other embodiments are within the scope of the claims. | Peteye is the appearance of an unnatural coloration (not necessarily red) of the pupils in an animal appearing in an image captured by a camera with flash illumination. Systems and methods of detecting and correcting peteye are described. In one aspect a classification map segmenting pixels in the input image into peteye pixels and non-peteye pixels is generated based on a respective segmentation condition on values of the pixels. Candidate peteye pixel areas are identified in the classification map. The generating and the identifying processes are repeated with the respective condition replaced by a different respective segmentation condition on the pixel values. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a 35 U.S. §371 national stage filing of International Application No. PCT/IB2010/053269, filed Jul. 19, 2010, the entire contents of which are incorporated by reference herein, which claims priority to Japanese Patent Application No. 2009-173693, filed Jul. 24, 2009, the entire contents of which are incorporated by reference herein.
TECHNICAL FIELD
[0002] The present invention relates to a power converter that receives a plurality of substantially same potentials and supplies power to a plurality of loads, and a vehicle lighting device, a vehicle headlight and a vehicle using the power converter.
BACKGROUND
[0003] Existing power converters receive a single input and output a single output. However, as power sources or loads become more diverse, the need to generate a plurality of outputs in response to a plurality of inputs (which are input at various times) is becoming desirable. Particularly, in the field of a power converters mounted in vehicles, various control units have been integrated, and multi-input multi-output devices are becoming more desirable.
[0004] FIG. 18 illustrates a power converter that controls loads of two systems as an example of a vehicle lighting device having a plurality of light sources. The power converter receives a power 1 directly connected to a vehicle battery BT. A controller area network (CAN) communication 2 which is a vehicle communication controller, controls a light emitting diode (LED) 3 (reading light) and an LED 4 (foot light) of two systems. The respective inputs are received by an input connection unit 10 , and an output is output to the LEDs 3 and 4 of two systems via an output connection unit 11 . The power converter is configured to include first and second power converting units 8 and 9 for converting a voltage of the battery directly-connected power 1 into a certain current required by the LEDs 3 and 4 , a control unit 7 for controlling the first and second power converting units 8 and 9 , a control power supply unit 5 that receives the battery directly-connected power 1 and outputs the power 1 to the control unit 7 , and a transceiver 6 that receives the CAN communication 2 notifying lighting timing of the LEDs 3 and 4 . The control unit 7 controls the LEDs 3 and 4 by receiving detection signals corresponding to output current values from the first and second power converting units 8 and 9 and outputting driving signals to the first and second power converting units 8 and 9 .
[0005] FIGS. 19 and 20 illustrate the first power converting unit 8 and the second power converting unit 9 , respectively. FIG. 19 illustrates a configuration of a flyback circuit which is an example of the power converting unit. A direct current (DC) power (a voltage between +B and GND) is received by a condenser C 1 , and a series circuit of a primary side winding TP 1 of a transformer T 1 and a switch element SW 1 is connected in parallel to the condenser C 1 . A driving signal of the switch element SW 1 is input to the power converting unit. A series circuit of a secondary side winding TS 1 of the transformer T 1 and a diode D 1 are connected in parallel to a condenser C 2 . An output unit is installed to connect a series circuit of a load and a resistor R 1 in parallel to the condenser C 2 . An output current is detected by the resistor R 1 and output as the detection signal.
[0006] A description will be made below in connection with a circuit operation. A current flows from the condenser C 1 to the primary side winding TP 1 of the transformer T 1 and the switch element SW 1 at ON timing of the switch element SW 1 . A direction of the diode D 1 at the secondary side is set to a direction in which a secondary side current does not flow when the switch element SW 1 is turned on, so that energy is accumulated in the transformer T 1 . The energy accumulated in the transformer T 1 moves from the secondary side winding TS 1 of the transformer T 1 to the condenser C 2 via the diode D 1 at OFF timing of the switch element SW 1 . Power is supplied from the condenser C 2 to the load via the resistor R 1 . An output current is detected by the resistor R 1 , and the control unit 7 adjusts an ON/OFF time of the driving signal of the switch element SW 1 . Thus, the output current can be constantly controlled.
[0007] FIG. 20 illustrates a configuration of a boosting circuit using an auto transformer which is an example of the power converting unit. A DC power (a voltage between +B and GND) is received by a condenser C 3 , and a series circuit of a primary side winding TP 2 of a coil T 2 and a switch element SW 2 is connected in parallel to the condenser C 3 . A driving signal of the switch element SW 2 is input to the power converting unit. A secondary side winding TS 2 of the transformer T 2 , a diode D 2 , and a condenser C 4 are connected in series to one another and in parallel to the switch element SW 2 . The primary side winding TP 2 and the secondary side winding TS 2 of the coil T 2 are wounded to have an additive polarity, and the diode D 2 is installed in a direction in which a current flows from the power to the output side. An output unit is installed to connect a series circuit of a load and a resistor R 2 in parallel to the condenser C 4 . An output current is detected by the resistor R 2 , and the detected output signal is output as a detection signal.
[0008] A description will be made below in connection with a circuit operation. A current flows from the condenser C 3 to the primary side winding TP 2 of the coil T 2 and the switch element SW 2 at ON timing of the switch element SW 2 , and energy is accumulated in the coil T 2 . The energy accumulated in the coil T 2 moves to the condenser C 4 via the condenser C 3 , the coil T 2 , and the diode D 2 at OFF timing of the switch element SW 2 . Power is supplied from the condenser C 4 to the load via the resistor R 2 . An output current is detected by the resistor R 2 , and the control unit 7 adjusts an ON/OFF time of the driving signal of the switch element SW 2 . Thus, the output current can be constantly controlled.
[0009] FIG. 21 illustrates a power converter having a different configuration for controlling loads of two systems. What is different from FIG. 18 in the aspect of input and output is that DC power as an input includes Acc power 12 linked with an accessory Acc of a vehicle and IGN power source 13 linked with the ignition (IGN) of the vehicle. For this reason, the Acc power 12 and the IGN power source 13 are input to a control power supply unit 5 via diodes D 4 and D 3 , respectively. Further, a power converting unit includes a predetermined current circuit (which has a current value obtained by dividing a voltage value, obtained by subtracting a forward voltage drop Vf of a load 3 from the IGN power source 13 , by resistance of the resistor R 3 ) configured with a resistor R 3 and a switch element SW 3 and a constant current circuit configured with a coil L 1 , a diode D 5 , a switch element SW 4 , a current detecting resistor R 4 , and a detecting unit 14 .
[0010] FIG. 22 illustrates an operation of the constant current circuit. When the switch element SW 4 is turned on, a current from the Acc power 12 flows through the coil L 1 , the LED 4 , the current detecting resistor R 4 , and the switch element SW 4 . When the current value becomes a predetermined current Imax, the switch element SW 4 is turned off. When the switch element SW 4 is turned off, a current of the coil L 1 flows through the LED 4 , the current detecting resistor R 4 and the diode D 5 . When the current value becomes a predetermined current value Imin, the switch element SW 4 is turned on. This operation is repeated, so that constant current control is implemented.
[0011] The control unit 7 that controls a plurality of loads usually controls the switch elements SW 3 and SW 4 according to the CAN communication 2 or other communications and supplies power to the loads 3 and 4 (for example, the LEDs 3 and 4 ).
SUMMARY
[0012] The power converter that controls the plurality of loads 3 and 4 can be implemented by the configurations of the conventional example illustrated in FIGS. 18 and 21 . However, the power converting unit 8 and 9 or at least the switch element is necessary for the respective loads 3 , 4 , and thus it is difficult to reduce the size and the cost of the lighting device. Further, a signal such as the CAN communication 2 is necessary for load control, and thus it is difficult to reduce the cost.
[0013] According to an embodiment of the present disclosure, a power converter receives a plurality of direct current (DC) powers, which are received in different modes, have a common ground, and have substantially the same potential and operates a plurality of loads. The power converter operates the loads according to input states of the plurality of DC powers and supplies the plurality of loads with power via at least a common switch element or a common coil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a circuit diagram according to Embodiment 1 of the present invention.
[0015] FIG. 2 is an operation waveform diagram according to Embodiment 1 of the present invention.
[0016] FIG. 3 is an operation waveform diagram according to a modification of Embodiment 1 of the present invention.
[0017] FIG. 4 is an operation waveform diagram according to another modification of Embodiment 1 of the present invention.
[0018] FIG. 5 is a circuit diagram according to another modification of Embodiment 1 of the present invention.
[0019] FIG. 6 is a circuit diagram according to Embodiment 2 of the present invention.
[0020] FIG. 7 is an operation waveform diagram according to Embodiment 2 of the present invention.
[0021] FIG. 8 is a circuit diagram illustrating a modification of a power converting unit according to Embodiment 2 of the present invention.
[0022] FIG. 9 is a circuit diagram according to Embodiment 3 of the present invention.
[0023] FIG. 10 is an operation waveform diagram according to Embodiment 3 of the present invention.
[0024] FIG. 11 is a circuit diagram according to Embodiment 4 of the present invention.
[0025] FIG. 12 is a circuit diagram according to Embodiment 5 of the present invention.
[0026] FIG. 13 is a circuit diagram according to a modification of Embodiment 5 of the present invention.
[0027] FIG. 14 is a perspective diagram illustrating a circuit substrate in which an LED lighting device according to Embodiment 2 of the present invention is mounted.
[0028] FIG. 15 is a perspective diagram illustrating a circuit substrate in which LEDs which are loads are simultaneously mounted on a substrate on which an LED lighting device according to Embodiment 2 of the present invention is mounted.
[0029] FIG. 16 is a schematic cross-sectional diagram of a vehicle headlight having a lighting device of the present invention.
[0030] FIG. 17 is an explanatory diagram illustrating a vehicle in which a lighting device or a headlight of the present invention is mounted.
[0031] FIG. 18 is a circuit diagram of Conventional example 1.
[0032] FIG. 19 is a circuit diagram illustrating an example of a power converting unit of Conventional example 1.
[0033] FIG. 20 is a circuit diagram illustrating another example of the power converting unit of Conventional example 1.
[0034] FIG. 21 is a circuit diagram of Conventional example 2.
[0035] FIG. 22 is an operation waveform diagram of Conventional example 2.
DETAILED DESCRIPTION
Embodiment 1
[0036] FIG. 1 illustrates a circuit configuration of a power converter according to Embodiment 1 of the present invention. Headlight 26 which generates a passing beam is a load of power source 21 which is linked with a headlight switch. Power is supplied from the power source 21 , which is linked with the headlight switch, to the headlight 26 (e.g., LED) through a coil L 1 , a current detecting resistor R 4 , and a switch element SW 4 . A diode D 5 is connected in a direction in which a current by the coil L 1 is regenerated when the switch element SW 4 is turned off. A current flowing through the headlight 26 is detected by the current detecting resistor R 4 and a detecting unit 14 , and a detection signal s 1 is input to the control unit 7 .
[0037] A day time running light (DTRL) provides a load across power source 13 which is linked with an ignition (IGN). The day time running light (DTRL) 25 is turned on during the daytime to inform another vehicle of its presence. Power is supplied from the power source 13 linked with the ignition (IGN) to the DTRL 25 through a high side switch 22 , a resistor R 3 , and the switch element SW 4 . Detecting units 23 and 24 detect a state of the power source 13 linked with the ignition (IGN) and a state of the power source 21 linked with the headlight switch. The detection results are input to the control unit 7 . The control unit 7 detects the state of the power source 21 linked with the headlight switch and the state of the power source 13 linked with the ignition (IGN) and controls the turning ON/OFF of both loads as shown in Table 1.
[0000]
TABLE 1
IGN power source 13
OFF
ON
OFF
ON
Headlight SW power source 21
OFF
OFF
ON
ON
Load 25
OFF
ON
OFF
OFF
Load 26
OFF
OFF
ON
ON
[0038] FIG. 2 illustrates a timing chart of lighting control of both loads by an input change of both powers. The operation is described below.
[0039] When both the IGN power source 13 and the headlight switch power source 21 are turned off, nothing is input to the control power supply unit 5 , and both loads 25 and 26 are in an OFF state. When the IGN power source 13 is turned on when both loads 25 and 26 are in the OFF state, the high side switch 22 and the switch element SW 4 are turned on by driving signals d 1 and d 2 , and the LED 25 is turned on through the resistor R 3 . In this case, the resistor R 3 is supposed to output a predetermined current limited to several milliamperes (mA) to tens of milliamperes (mA) and thus has a resistance in the tens of ohms (Ω) to thousands of ohms (Ω) (for example, 680 Ω).
[0040] Thereafter, when the headlight switch power source 21 is turned on, the driving signal d 1 of the high side switch 22 is turned off, so that the power supply to the LED 25 is cut off. Further, a constant current is supplied to the LED 26 by turning on/off the switch element SW 4 through the driving signal d 2 (for example, by driving at tens of kHz to hundreds of kHz). When the switch element SW 4 is turned on, a current is supplied from the power source 21 linked with the headlight switch to the LED 26 while flowing through the coil L 1 , the LED 26 , the resistor R 4 , and the switch element SW 4 . When the switch element SW 4 is turned off, a regeneration current flows through the coil L 1 , the LED 26 , the resistor R 4 , and the diode D 5 . A change in the current is detected by the resistor R 4 , and turning on/off of the switch element SW 4 is controlled according to the detection signal s 1 , so that the constant current is implemented. In this case, the resistor R 4 is used for current detection and has a resistance in the tens of milliohm (mΩ) to several ohm (Ω) to reduce a loss in the resistor R 4 (in the case of a current of 1A, a loss is 10 mW to 1 W).
[0041] When the power source 21 linked with the headlight is turned on in the OFF state of both loads 25 and 26 , the constant current is supplied to the LED 26 by turning on/off the switch element SW 4 in a state in which the high side switch 22 remains turned off
[0042] According to the present embodiment, lighting of the plurality of loads 25 and 26 can be controlled by the common switch element SW 4 , and on/off of the load is judged by the power state. Thus, communication including timing for turning on/off the load is unnecessary. Thus, the size and the cost can be reduced compared to the conventional circuit.
Embodiment 1a
[0043] When only the power source 13 linked with the IGN is turned on, the driving signal d 2 is always in the ON state in Embodiment 1. However, by turning on/off lighting at a frequency (for example, 10 Hz) less than 50 Hz, blinking can be recognized by the human eye, and a glittering feeling can be improved, so that a recognition degree of a driver's vehicle during daylight hours can be improved (there is influence of the afterglow or the like, but when the LED blinks at 60 Hz or more, it looks like a dimming state of DC lighting. If a deviation of a control system or the like is considered, a glittering feeling can be implemented by performing lighting at 50 Hz or less).
[0044] A timing chart at this time is illustrated in FIG. 3 . Thus, it is understood that both visibility improvement by blinking control of the LED 25 and predetermined current control of the LED 26 can be implemented by the switch element SW 4 , and the size and the cost can be reduced compared to the case in which control is performed by the individual switch elements. It is understood that when only the IGN power source 13 is turned on, the same effect can be obtained even though the driving signal d 1 and the driving signal d 2 are switched.
Embodiment 1b
[0045] Further, when only the IGN power source 13 is turned on, by increasing the frequency of the driving signal d 2 to 60 Hz, blinking is not seen by the human eye, so that dimming lighting can be implemented. When a predetermined current is supplied to the LED 25 via the resistor R 3 , the current value depends on the magnitude of the power voltage, but by varying an On duty of a pulse width modulation (PWM) according to the power voltage, it is possible to have substantially the same current during a predetermined time and make a light flux of the LED 25 substantially the same. In an example of FIG. 4 , as the power voltage decreases, the On duty increases. In this disclosure, a circuit that applies a predetermined current using a resistor also includes the above described control.
Embodiment 1c
[0046] In Embodiment 1, the LED is described as the load, but it is understood that the same effect can be obtained even when a halogen lamp 27 is used as the load instead of the LED 25 as illustrated in FIG. 5 . In this case, the resistor R 3 may be removed.
[0047] Further, in Embodiment 1, the high side switch 22 is involved in supplying the power from the power source 13 linked with the IGN to the LED 25 , but the current may be supplied without the high side switch 22 as illustrated in FIG. 5 . In this case, when both the power source 21 linked with the headlight and the power source 13 linked with the IGN are turned on, the switch element SW 4 is turned on/off to apply constant current to the LED 26 . Thus, the halogen lamp 27 is turned on/off at a high frequency (tens of kHz or more), so that the halogen lamp 27 can be turned on in the dimming lighting state.
[0048] Further, when the halogen lamp 27 is used as a width indicator, the power source 31 linked with the IGN functions as a power source linked with a width indicator switch, and when the headlight switch is turned on, the power from the power source linked with the width indicator switch is not input. Using this system, a state in which both power sources are turned on does not occur, and the high side switch can be removed. Accordingly, the size and the cost can be reduced.
Embodiment 2
[0049] FIG. 6 illustrates a circuit configuration of a power converter according to Embodiment 2 of the present invention. The same components as in Embodiment 1 are denoted by the same reference numerals, and a description thereof will be omitted. A description will be made below in connection with different points from Embodiment 1.
[0050] In the present embodiment, the flyback circuit illustrated in the conventional example of FIG. 19 is used as the power converting unit for the LED 26 . The power converting unit for the LED 26 illustrated in Embodiment 1 is used as the power converting unit for the LED 25 , and a resistor RO is connected in series with a diode D 5 . A coil and a switch element of the power converting unit that supplies power to the LED 25 are configured with a primary side winding TP 1 and a switch element SW 1 of a flyback circuit that supplies to power to the LED 26 . A control unit 7 outputs a driving signal d 3 for driving the switch element SW 1 . The control unit 7 detects an output current to the LED 25 and an output current to the LED 26 by a resistor R 4 and a resistor R 1 as a detection signal s 1 and a detection signal s 2 , respectively.
[0051] Operation of the control unit 7 is illustrated in FIG. 7 . When a power source 13 linked with an IGN is input, the control unit 7 detects the turning on of the power source 13 through the detecting unit 23 and outputs a PWM signal for driving the switch element SW 1 from the driving signal d 3 . Thus, the constant current is output to the LED 25 . The output current is detected by the resistor R 4 as the detection signal s 1 , and an ON time and an OFF time of the PWM signal are controlled, so that the constant current control is implemented. Further, blinking lighting of the LED 25 is performed by repetitively performing the constant current control at a certain frequency (for example, 10 Hz), a glittering feeling of the LED 25 is improved, and the recognition degree of a driver's vehicle is improved. Thereafter, when the power source 21 linked with the headlight switch is input, voltages of both terminals of the LED 25 have the same potential, so that the LED 25 is turned off. The input of the power source 21 linked with the headlight switch is detected by the detecting unit 24 , and the PWM signal for driving the switch element SW 1 from the driving signal d 3 is output. Thus, the constant current is output to the LED 26 .
[0052] The output current is detected using the resistor R 1 as the detection signal s 2 , and the ON time and the OFF time of the PWM signal are controlled, so that the constant current control is implemented. Thereafter, the PWM signal of the driving signal d 3 is switched in tandem while turning on/off of the headlight switch. When the IGN power source 13 is turned off in a state in which both the IGN power source 13 and the power source 21 linked with the headlight switch are turned on, a reverse voltage is applied to the LED 25 , but the LED 25 remains turned off. When the power source 21 linked with the headlight switch is turned on in a state in which both the IGN power source 13 and the power linked with the headlight switch are turned off, the LED 26 is subjected to the constant current control by the driving signal d 3 .
[0053] Through the above described circuit configuration and control, it is possible to share the switch element and the coil which are relatively large-scale components in the power converting unit for controlling the outputs to the LED 25 and the LED 26 . Thus, both loads can be controlled by the same switch element and coil, and thus the size and the cost of the lighting device can be reduced.
[0054] Typically, the power source 21 linked with the headlight switch is turned on in a state in which the IGN power source 13 is turned on. In this case, both an anode side and a cathode side of the LED 25 are connected to the power sources, and potentials of both sides become equal at a vehicle battery voltage (several voltages to a score of voltages), so that a voltage applied to the LED 25 becomes zero. Thus, the LED 25 can be automatically turned off without depending on the state of the switch element SW 1 , and the communication function or the power monitoring function can be removed, so that the size and the cost can be further reduced.
[0055] Power of the headlight is about 35 W, and power of the DTRL is about 5 W. The flyback circuit having a boosting capability is suitable for outputting power higher than a power converting circuit having no boosting capability. Thus, the LED 26 is used as the headlight, and the LED 25 is used as the DTRL.
[0056] In the present embodiment, the IGN power source 13 and the power source 21 linked with the headlight switch are used as the input. However, it is understood that even when any other power source (a power source directly connected to a battery or linked with an accessory) is added to supply power to another load, or communication such as LIN/CAN is used for load control, the same effect can be obtained. Further, it is understood that even when a power source is not added but switched (a power source linked with the IGN becomes a power directly connected to a battery or a power source linked with an accessory), the same effect can be obtained.
[0057] In the present embodiment, it is understood that the LED is used as the load, but even when a light source such as a halogen lamp or a high-intensity discharge (HID) lamp is used as the load, the same effect can be obtained. It is understood that even when the power converter is for power supply to other electronic units, not the light source, the same effect can be obtained. For example, the power converter has a function as a power source for a DC/AC converter enabling an alternating current (AC) powered device to be used within a vehicle or for an engine control unit (ECU) having a higher voltage as an input.
[0058] In an embodiment, the constant current control is performed as a control for the LED. Even when control such as constant voltage control or constant power control is performed instead of the constant current control, the same effect can be obtained.
[0059] Further, it is understood that even when a circuit of the resistor R 4 , the transformer T 1 , the switch element SW 1 , the diode D 1 , and the condenser C 2 constitute a circuit illustrated in FIG. 6 , an effect which is the same as that of the circuit of FIG. 8 can be obtained. In FIG. 8 , a coil TP 1 ′ is used which is further wound in the same direction as the primary side winding TP 1 . Thus, it is possible to easily increase an inductance value of the coil when the LED 25 is turned on and to facilitate predetermined current control.
Embodiment 3
[0060] FIG. 9 illustrates a circuit diagram of Embodiment 3 of the present invention. The same components as in Embodiment 2 are denoted by the same reference numerals, and thus a description thereof will be omitted. A description is made below in connection with different points from Embodiment 2 ( FIG. 6 ).
[0061] The LED 26 is replaced with a HID lamp 33 . In order to turn on the HID lamp 33 , an igniter 32 for applying a high voltage pulse is installed ahead of the HID lamp 33 . In order to turn on the HID lamp 33 by a rectangular wave, a full bridge inverter 31 for converting an output of the flyback circuit into the rectangular wave is installed behind the flyback circuit. A detection signal s 3 for detecting a lamp voltage is input to the control unit 7 . Driving signals d 5 and d 6 for controlling the full bridge inverter 31 are output from the control unit 7 .
[0062] A circuit for applying a predetermined current to the LED 25 includes three components, a resistor R 5 , a coil TP 1 , and a switch element SW 1 which are installed in series with the LED 25 . In this case, a resistance value is in a range of hundreds of ohms (Ω) to several kilohm (kΩ) since a current has a predetermined value (a voltage value of the IGN power source 13 - a forward voltage drop Vf of the LED 25 )/(a resistance value of the resistor R 5 ). Since control for causing a predetermined current to flow in the resistor R 5 is realized by the resistor R 5 , the detection signal s 1 for the LED current, the detecting unit 14 , and the current detecting resistor R 4 are not provided, unlike other embodiments.
[0063] An operation of the control unit 7 is illustrated in FIG. 10 . When the power source 13 linked with the IGN is input, the control unit 7 detects turning on of the IGN power source 13 through the detecting unit 23 and outputs the PWM signal for driving the switch element SW 1 by the driving signal d 3 . At this time, the PWM signal is an ON/OFF signal of tens of Hz (for example, 10 Hz) so that the driver's vehicle is made more visible by highlighting the glittering feeling by blinking the LED 25 . Thus, a predetermined current is supplied to the LED 25
[0064] Thereafter, when the power source 21 linked with the headlight switch is input, voltages of both terminals of the LED 25 have the same potential, and thus the LED 25 is turned off. The input of the power source 21 linked with the headlight switch is detected by the detecting unit 24 , and the PWM signal for driving the switch element SW 1 by the driving signal d 3 is output (when the HID lamp 33 is turned on, driving is performed at tens of kHz to hundreds of kHz). By varying on/off of the PWM signal by the values of the detected lamp voltage and lamp current, constant power is supplied to the HID lamp 33 . Another control such as a pulse output at the start time is necessary for turning on the HID lamp 33 , but a description thereof will be here omitted.
[0065] Thereafter, the PWM signal of the driving signal d 3 is switched in tandem with turning on/off of the headlight switch. When the IGN power source 13 is turned off in a state in which both the IGN power source 13 and the power source 21 linked with the headlight switch are turned on, a reverse voltage is applied to the LED 25 , but the LED 25 remains off. When the headlight switch is turned on in a state in which both the IGN power source 13 and the power source 21 linked with the headlight switch are turned off, only the HID lamp 33 is controlled by the driving signal d 3 .
[0066] Through the above described circuit configuration and control, it is possible to share the switch element and the coil which are relatively large-scale components in the power converting unit for controlling the outputs to the LED 25 and the HID lamp 33 . Thus, both loads can be controlled by the same switch element and coil, and thus the size and the cost of the lighting device can be reduced.
[0067] Typically, the headlight switch is turned on in a state in which the IGN power source is turned on. In this case, both an anode side and a cathode side of the LED 25 are connected to the power, and potentials of both sides become equal at a vehicle battery voltage (several voltages to a score of volts), so that a voltage applied to the LED 25 becomes zero. Thus, turning off can be automatically performed without depending on the state of the switch element SW 1 , and the communication function or the power monitoring function can be removed, so that the size and the cost can be further reduced.
[0068] Further, the circuit for turning on the LED 25 can be simplified compared to Embodiment 2, and thus the size and the cost can be further reduced.
[0069] In the present embodiment, when the LED 25 is turned on, blinking lighting is performed in order to improve the recognition degree of the driver's vehicle. However, it is understood that when only the power source 13 linked with the IGN is input, even though lighting is constantly performed or dimming lighting is performed at a higher frequency, the same effect can be obtained.
Embodiment 4
[0070] FIG. 11 illustrates a circuit diagram of Embodiment 4 of the present invention. The same components as in Embodiment 2 are denoted by the same reference numerals, and thus a description thereof will be omitted. A description will be made below in connection with different points from Embodiment 2 ( FIG. 6 ).
[0071] In the present embodiment, the flyback circuit of Embodiment 2 (illustrated in FIG. 19 ) is replaced with a boosting circuit using an auto transformer illustrated in FIG. 20 . A lighting circuit of the LED 25 has the circuit configuration of Embodiment 3.
[0072] Through the above configuration, it is possible to share the switch element SW 2 and the coil T 2 which are relatively large-scale components in the power converting unit for controlling the outputs to the LED 25 and the LED 26 . Thus, both loads 25 and 26 can be controlled by the same switch element SW 2 and coil T 2 , and thus the size and the cost of the lighting device can be reduced.
[0073] Typically, the headlight switch is turned on in a state in which the IGN power is turned on. In this case, both an anode side and a cathode side of the LED 25 are connected to the power, and potentials of both sides become equal at a vehicle battery voltage (several volts to a score of volts), so that a voltage applied to the LED 25 becomes zero. Thus, turning off can be automatically performed without depending on the state of the switch element SW 2 , and the communication function or the power monitoring function can be removed, so that the size and the cost can be further reduced.
[0074] Further, the circuit for turning on the LED 25 can be simplified compared to Embodiment 2, and thus the size and the cost can be further reduced.
[0075] In the present embodiment, the boosting circuit using the auto transformer is used. However, it is understood that even when any other converter circuit such as a boost chopper circuit having no secondary side winding TS 2 , a forward type converter, a choke circuit, or a SEPIC (single-ended primary inductance converter) circuit is used, the same effect can be obtained.
Embodiment 5
[0076] FIG. 12 illustrates a circuit diagram of Embodiment 5 of the present invention. The same components as in Embodiment 2 are denoted by the same reference numerals, and thus a description thereof will be omitted. A description will be made below in connection with different points from Embodiment 2 ( FIG. 6 ).
[0077] In the embodiment, the diode D 1 is removed from the flyback circuit that supplies power to the LED 26 , and a switch element SW 7 is added. A body diode of the added switch element SW 7 is added to have the same effect as the removed diode D 1 .
[0078] A circuit for applying a predetermined current to the LED 25 includes four components, a resistor R 5 , a diode D 6 , a coil TS 1 , and a switch element SW 7 . In this case, a resistance value is in a range of hundreds of ohm (Ω) to several kilohm (kΩ) to limit a current.
[0079] The diode D 6 is connected in series with the LED 25 , and the resistor R 6 is connected in parallel with the LED 25 , so that a large reverse voltage is not applied to the LED 25 when the output voltage of the flyback circuit increases.
[0080] By employing this configuration, when the LED 26 is turned on, the switch element SW 7 is turned off, and the flyback circuit is configured using the body diode of the switch element SW 7 . Thus, the LED 26 is turned on by the constant current. When the LED 25 is turned on, the switch element SW 7 is turned on, and a predetermined current is applied to the LED 25 via the resistor R 5 . Further, blinking of the LED 25 is performed (at the frequency of 10 Hz) by applying or not applying the predetermined current by the coil TS 1 and the switch element SW 7 .
[0081] Further, when the LED 26 is turned on by the flyback circuit, the switch element SW 7 is not constantly turned off, but when the switch element SW 1 is turned off, the switch element SW 7 is turned on, so that synchronization rectification of the flyback circuit can be performed. As a result, efficiency can be further improved compared to the case in which only the body diode is used.
[0082] Through the above configuration, it is possible to share the switch element and the coil which are relatively large-scale components in the power converting unit for controlling the outputs to the LED 25 and the LED 26 . Thus, both loads can be controlled by the same switch element and coil, and thus the size and the cost of the lighting device can be reduced.
[0083] In the present embodiment, the flyback circuit is used, but it is understood that even when any other converter circuit such as an auto transformer circuit ( FIG. 13 ) is used, the same effect can be obtained.
Embodiment 6
[0084] FIG. 14 illustrates a circuit substrate in which an LED lighting device as illustrated in Embodiment 2 of the present invention is used. Power is received from an input connection unit 10 , and power is output to an output connection unit 11 . In the present embodiment, since power supply units for two loads are present, a power supply to the LED 25 is separated from a power supply to the LED 26 , and the control unit 7 is installed therebetween, so that noises of the power supply units are reduced.
[0085] By using the circuit configuration illustrated in FIG. 6 , the size and the cost of the substrate can be reduced.
[0086] FIG. 15 illustrates a circuit substrate in which the LEDs 25 and 26 which are the loads are simultaneously mounted on the substrate on which the power supply unit is mounted. In this circuit substrate, an output connection unit is configured with a pattern, and the LEDs 25 and 26 can be mounted on the same substrate as the loads. Thus, the size and the cost can be further reduced.
Embodiment 7
[0087] FIG. 16 illustrates a schematic cross-sectional structure of a vehicle headlight having a lighting device of the present invention. A front opening of a case 40 in which the LEDs 25 and 26 are mounted as the loads is covered with a transparent cover 41 , and a lighting device 20 of the present invention is mounted on the bottom of the case 40 . By mounting the lighting device 20 of the present invention, the size and the cost of the vehicle headlight can be reduced.
[0088] Further, since the single lighting device 20 can have a plurality of functions, an input connector (the input connection unit 10 ) for the vehicle headlight can be put together.
Embodiment 8
[0089] FIG. 17 illustrates a vehicle in which a lighting device or a headlight of the present invention is mounted. A power source 21 linked with a headlight switch and an IGN power source 13 are received, and lighting of an LED 25 as a DTRL and an LED 26 as a passing beam is controlled.
[0090] By mounting the lighting device or the headlight of the present invention, the size and the cost of the vehicle can be reduced.
[0091] While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosures. Indeed, the novel organic light-emitting devices described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the disclosures. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosures. | A power converter that receives a plurality of direct current (DC) powers, which are received in different modes and have a common ground and substantially the same potential, and operates a plurality of loads, wherein the power converter operates the respective loads according to input states of the plurality of DC powers and supplies the plurality of loads with power via at least a common switch element or a common coil. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an improved pivot pin and saddle assembly for a side-dump trailer or truck. More particularly, a plurality of the saddle assemblies are secured to the frame of the truck or trailer upon which the side-dump body is movably positioned with the saddle assemblies receiving pivot pins secured to the side-dump body. Even more particularly, the saddle assemblies of this invention pivotally support the pivot pins of the side-dump body upon a Nylon® or composite bearing block. The design of the pivot pins and saddle assemblies prevents longitudinal movement of the side-dump body with respect to the truck or trailer frame.
2. Description of the Related Art
In recent years, side-dump bodies mounted on trailers or trucks have become extremely popular. The assignee of the instant invention has obtained many patents on side-dump bodies with one of the first patents being U.S. Pat. No. 5,480,214 to Ralph Rogers.
In most of Applicants' prior art patents relating to side-dump trailers and in most of the side-dump bodies of the competitors of assignee, the side-dump bodies are pivotally mounted on a truck or trailer frame in a manner so that they may be dumped to either side of the truck or trailer frame. In most cases, pivot pins are secured to the sides of the side-dump body with the pivot pins being received in saddle assemblies mounted on the trailer or truck frame. To the best of Applicants' knowledge, no one working in the side-dump body industry has provided pivot pin and saddle assemblies which adequately limit the longitudinal movement of the side-dump body with respect to the truck or trailer frame. Further, to the best of Applicants' knowledge, all the prior art side-dump bodies have metal-to-metal contact between the pivot pins and the saddle assemblies. In that situation, the pivot pins and saddle assemblies may become worn which will eventually effect the operation of the side-dump body with respect to those saddle assemblies which will then require repair or replacement of the pivot pins and saddle assemblies.
SUMMARY OF THE INVENTION
This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key aspects or essential aspects of the claimed subject matter. Moreover, this Summary is not intended for use as an aid in determining the scope of the claimed subject matter.
A pivot pin and saddle assembly is disclosed for use with a side-dump trailer or truck. The side-dump trailer or truck includes a wheeled frame having a forward end, a rearward end, a first side and a second side. An elongated side-dump body is movably positioned on the wheeled frame and has a forward end, a rearward end, a first side and a second side. The side-dump body also includes an upstanding front bulkhead with upper and lower ends, an upstanding back bulkhead with upper and lower ends, a first side wall having forward and rearward ends, a second side wall having forward and rearward ends, a bottom wall having forward and rearward ends, and an open upper end for receiving materials therein to be transported. A first diagonally extending pivot tube, having upper and lower ends, is secured to the front bulkhead. The upper end of the first pivot tube is positioned adjacent the upper end of the front bulkhead with the first pivot tube extending downwardly and outwardly from its upper end to its lower end. A second diagonally extending pivot tube, having upper and lower ends, is secured to the front bulkhead with the upper end of the second pivot tube being positioned adjacent the upper end of the front bulkhead. The second pivot tube extends downwardly and outwardly from its upper end to its lower end. A third diagonally extending pivot tube, having upper and lower ends, is secured to the back bulkhead. The upper end of the third pivot tube is positioned adjacent the upper end of the back bulkhead with the third pivot tube extending downwardly and outwardly from its upper end to its lower end. A fourth diagonally extending pivot tube, having upper and lower ends, is secured to the back bulkhead with the upper end of the fourth pivot tube being positioned adjacent the upper end of the back bulkhead. The fourth pivot tube extends downwardly and outwardly from its upper end to its lower end.
A first horizontally disposed pivot pin, having forward and rearward ends, is secured to the lower end of the first diagonally extending pivot tube with the first pivot pin having a first disc-shaped ring member mounted thereon rearwardly of its forward end and a second disc-shaped ring member mounted thereon forwardly of its rearward end. The first and second disc-shaped ring members are horizontally spaced-apart on the first pivot pin.
A second horizontally disposed pivot pin, having forward and rearward ends, is secured to the lower end of the second diagonally extending pivot tube with the second pivot pin having a first disc-shaped ring member mounted thereon rearwardly of its forward end and a second pivot pin having a disc-shaped ring member mounted thereon forwardly of its rearward end. The first and second disc-shaped ring members are horizontally spaced-apart on the second pivot pin.
A third horizontally disposed pivot pin, having forward and rearward ends, is secured to the lower end of the third diagonally extending pivot tube with the third pivot pin having a first disc-shaped ring member mounted thereon rearwardly of its forward end and a second disc-shaped ring member mounted thereon forwardly of its rearward end. The first and second disc-shaped ring members are horizontally spaced-apart on the third pivot pin.
A fourth horizontally disposed pivot pin, having forward and rearward ends, is secured to the lower end of the fourth diagonally extending pivot tube with the fourth pivot pin having a first disc-shaped ring member mounted thereon rearwardly of its forward end and having a second disc-shaped ring member mounted thereon forwardly of its rearward end. The first and second disc-shaped ring members are horizontally spaced-apart on the fourth pivot pin.
A first saddle assembly is secured to the wheeled frame adjacent the lower end of the first pivot tube and a second saddle assembly is secured to the wheeled frame adjacent the lower end of the second pivot tube. A third saddle assembly is secured to the wheeled frame adjacent the lower end of the third pivot tube. A fourth saddle assembly is secured to the wheeled frame adjacent the lower end of the fourth pivot tube. The first, second, third and fourth pivot pins are selectively pivotally received by the first, second third and fourth saddle assemblies respectively. A locking device is associated with each of the saddle assemblies to selectively lock the pivot pin in the saddle assembly. Each of the first, second, third and fourth pivot pins and the first, second, third and fourth saddle assemblies include means thereon for limiting the longitudinal movement of the side-dump body with respect to the saddle assembly and the wheeled frame. Further, the pivot pins of the side-dump body are supported upon Nylon® bearing blocks positioned on the saddle assemblies with each of the bearing blocks having a semi-circular recess formed therein which partially receives the associated pivot pin. The side-dump body may be pivotally movable between a transport position to a dumping position at either side of the truck or trailer.
It is therefore a principal object of the invention to provide an improved pivot pin/saddle assembly for a side-dump trailer or truck.
A further object of the invention is to provide a pivot pin/saddle assembly for a side-dump trailer or truck which limits the longitudinal movement of the side-dump body with respect to the trailer or truck frame.
A further object of the invention is to provide a saddle assembly for a side-dump trailer or truck which includes a Nylon® or composite bearing block which supports the associated pivot pin thereon.
A further object of the invention is to provide a pivot pin/saddle assembly for a side-dump trailer which prevents the metal-to-metal contact normally associated with the pivot pins and saddle assemblies of conventional side-dump trailers or trucks.
These and other objects will be apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
Non-limiting and non-exhaustive embodiments of The present invention are described with reference to the following figures, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified.
FIG. 1 is a rear perspective view of a side-dump trailer having a plurality of pivot pin/saddle assemblies of this invention secured thereto;
FIG. 2 is a front view of the side-dump body of FIG. 1 ;
FIG. 3 is an exploded front perspective view of the saddle assembly, two of which are secured to the left side of the trailer or truck frame;
FIG. 4 is a perspective view illustrating a pivot pin being lowered into the saddle assembly of FIG. 3 ;
FIG. 5 is a perspective view similar to FIG. 4 except that the pivot pin is locked into the saddle assembly;
FIG. 6 is a partial sectional view of the pivot pin/saddle assembly of FIG. 3 with the pivot pin being locked into the saddle assembly; and
FIG. 7 is an exploded front perspective view of one of the saddle assemblies which are secured to the right side of the truck or trailer frame.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Embodiments are described more fully below with reference to the accompanying figures, which form a part hereof and show, by way of illustration, specific exemplary embodiments. These embodiments are disclosed in sufficient detail to enable those skilled in the art to practice the invention. However, embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein. The following detailed description is, therefore, not to be taken in a limiting sense in that the scope of the present invention is defined only by the appended claims.
In FIGS. 1 , 2 , 4 - 6 , the numeral 10 refers generally to a wheeled frame which may be part of a truck or trailer. For purposes of description, the wheeled frame 10 will be described as having a left side 12 , a right side 14 , a forward end 16 , and a rearward end 18 . A conventional side-dump body such as disclosed in U.S. Pat. No. 5,480,214 is illustrated in FIGS. 1 and 2 and is referred to generally by the reference numeral 20 . For purposes of description, side-dump body 20 will be described as having a forward end wall or bulkhead 22 , a rearward end wall or bulkhead 24 , a first side wall 26 , a second side wall 28 , and a bottom wall 30 which may be curved or flat. Bottom wall 30 may be integrally formed with side walls 26 and 28 .
A pair of diagonally extending pivot tubes 32 and 34 are secured to the forward side of forward bulkhead 22 and have longitudinally extending pivot pins 36 and 38 secured to the lower ends respectively. A pair of diagonally extending pivot tubes 40 and 42 are secured to the rearward side of rearward bulkhead 24 and have longitudinally extending pivot pins 44 and 46 secured thereto respectively. Inasmuch as the pivot pins 36 , 38 , 44 and 46 are identical, only pivot pin 36 will be described in detail. Pivot pin 36 has a pair of spaced-apart, disc-shaped ring members 48 and 50 secured thereto by welding or the like.
A saddle assembly 52 is secured to the web of frame member 10 L as seen in FIG. 2 by bolts or the like so as to be positioned below the lower end of pivot tube 32 . Saddle assembly 54 is secured to the web of frame member 10 R as seen in FIG. 2 by bolts or the like so as to be positioned below the lower end of pivot tube 34 . Saddle assembly 56 is secured to the web of frame member 10 L as seen in FIG. 1 by bolts or the like so as to be positioned below the lower end of pivot tube 40 . Saddle assembly 58 is secured to the web of frame member 10 R so as to be positioned below the lower end of pivot tube 42 .
Inasmuch as saddle assemblies 52 and 56 are identical, only saddle member 52 will be described in detail. Inasmuch as saddle assemblies 54 and 58 are identical, only saddle assembly 54 will be described in detail. The only difference between saddle assemblies 52 and 54 is the location of the locking devices as will be described in more detail hereinafter. All of the saddle assemblies described above could be constructed identical to saddle assembly 52 if so desired as will be explained hereinafter.
Saddle assembly 52 includes a vertically disposed mounting plate 60 having bolt openings 62 formed therein. Mounting plate 60 is bolted to the web of frame member 10 L by bolt 64 extending through opening 62 and through registering bolt openings in frame member 10 L. Horizontally spaced-apart front and back side plates 66 and 68 are welded to mounting plate 60 and extend outwardly therefrom as seen in the drawings. Front side plate 66 has a generally U-shaped pivot pin receiving opening 70 formed therein which has a generally semi-circular lower end 72 . Front side plate 66 has a pair of spaced-apart ears 74 and 76 at its upper end which are bent forwardly as seen in FIG. 3 . The forward side of side plate 66 has a pair of spaced-apart collars or bushings 78 and 80 welded thereto. The numeral 82 refers to a locking plate which has a tube or sleeve 84 at its lower end. Locking plate 82 includes an opening 86 formed therein. Sleeve 84 is positioned between bushings 78 and 80 and is held therebetween in a pivotal manner by means of pin 88 extending through bushing 80 , sleeve 84 and bushing 78 . Pin 88 is held in place by any suitable means such as by a cotter key or the like extending through bore 90 in pin 88 .
The numeral 92 refers to a spring-lock assembly which is mounted on the front side of front side plate 66 . Assembly 92 includes a box-like bracket 94 which is welded to side plate 66 . A pin 96 extends through bracket 94 and has a spring 98 embracing it to yieldably urge the pin 96 towards mounting plate 60 beyond the outer side of opening 70 . Assembly 92 includes means to maintain pin 96 in a retracted non-locking position in conventional fashion. Back side plate 68 includes rearwardly bent ears 100 and 102 and a U-shaped opening 104 having a semi-circular lower end 106 .
A bearing block mounting plate 108 is positioned between side plates 66 and 68 adjacent the lower ends thereof and is welded thereto and to the mounting plate 62 . the outer end of mounting plate 108 is provided with an upturned lip 110 . The forward and rearward side edges of mounting plate 108 are provided with notches 112 and 114 formed therein which receive the lower ends of ring members 48 and 50 when pivot pin 36 is received by the saddle assembly 52 . The numeral 116 refers to a bearing block which is comprised of Nylon®, plastic or a composite material. The upper surface of bearing block 116 has an elongated recessed area 118 formed therein which has a generally semi-circular cross-section. Bearing block 116 is positioned on mounting plate 108 between side plates 66 and 68 and is secured to mounting plate 108 by bolts 120 and 122 which extend downwardly through bolt openings 124 and 126 respectively in baring block 116 . When bearing block 116 is positioned on mounting plate 108 , the lower end 128 of the recessed area 118 dwells in a plane above the lower ends 72 and 106 of U-shaped openings 70 and 104 in side plates 66 and 68 respectively so that pivot pin 36 is held in a plane above the lower ends 72 and 106 by openings 70 and 104 . The bearing block 116 prevents pivot pin 36 from engaging the lower ends 72 and 106 of openings 70 and 104 . If bearing block 116 becomes worn, it is easily replaced or vertically adjusted.
As previously stated, saddle assemblies 52 and 56 are identical. Saddle assemblies 52 and 56 are positioned on the left side of the wheeled frame 10 , as viewed from the rear thereof, so that the locking plates 82 will be at the forward sides of the saddle assemblies 52 and 56 and will be readily visible to the driver of the vehicle. If the saddle assembly 52 was used on the right side of the wheeled frame 10 , the locking plates would be at the rearward side of the saddle assembly and would not be clearly visible from the front of the vehicle. Thus, a slight modification is made to a saddle assembly 52 so that it may be used on the right side of the vehicle. It should be noted that while it is preferred that the locking plate 82 be positioned at the forward side of the saddle assembly for observation purposes, it is not necessary.
The saddle assembly 54 illustrated in FIG. 7 is different from saddle assembly in only two respects. First, the locking plate 82 on saddle assembly 54 is positioned on the forward side of side plate 68 rather than on side plate 66 . Secondly, the spring-lock assembly 92 is also located on the front side of side plate 68 so as to cooperate with locking plate 68 .
FIG. 5 illustrates the pivot pin 36 seated within the saddle assembly 52 with the locking pin 96 being positioned outwardly of the locking plate 82 to maintain the pivot pin 36 in the saddle assembly 52 . When the locking pin 36 is received within the saddle assembly 52 , the lower ends of the ring members 48 and 50 are received in the notches 112 and 114 of the mounting plate 108 . The close proximity of the ring members 48 and 50 to the side plates 66 and 68 limits the longitudinal movement of the pivot tube 32 and the side-dump body with respect to the saddle assembly 52 . The pivot pin 36 is supported upon the bearing block 116 with the lower end of the pivot pin 36 being disposed above the lower end 72 of the opening 70 in side plate 66 and above the lower end 106 of the opening 104 in the side plate 68 thereby preventing a metal-to-metal contact between the pivot pin and the side plates. The fact that the pivot pins are secured to the lower ends of the pivot tubes and the fact that the pivot tubes are secured to the forward end wall or the rearward end wall of a side-dump body transfers any forces imposed thereon to the front bulkhead rather than to the sides of the side-dump body.
Should the bearing block 116 become worn, the bearing block 116 is easily replaced or adjustably vertically moved upwardly by inserting washers or the like beneath the bearing block 116 above the mounting plate 108 .
To further describe the invention and assuming that the pivot tube 32 is disposed above the saddle assembly 52 as illustrated in FIG. 4 , as the pivot tube 32 is lowered, the ring members 48 and 50 may engage the portions 74 , 76 , 100 and 102 to move the pivot pin in a proper relationship with respect to the saddle assembly. As the pivot tube 32 is lowered with respect to the saddle assembly 52 , the ring members 46 and 50 guide the pivot tube downwardly into the recessed area 118 of the bearing block 116 . When the pivot pin 36 is seated in the recessed area 118 of the bearing block 116 , the locking plate 82 is pivotally moved upwardly from the position of FIG. 4 to the position of FIG. 5 so that the opening 86 of the locking plate 82 receives the end of the pivot pin 36 . The spring-lock assembly 92 is then actuated so that the pin 96 extends therefrom adjacent the outer side of the locking plate 82 to maintain the locking plate 82 in its locked position.
The side-dump body is pivotally movable from a transport position to a dumping position at either side of the wheeled frame by a hydraulic cylinder at the forward end of the side-dump body and a hydraulic cylinder at the rearward end of the side-dump body in conventional fashion.
Thus it can be seen that a novel pivot pin and saddle assembly has been provided for a side-dump trailer or truck which prevents metal-to-metal contact between the pivot pin and the saddle assembly and which limits the longitudinal movement of the side-dump body with respect to the saddle assembly. Thus it can be seen that the invention accomplishes at least all of its stated objectives.
Although the invention has been described in language that is specific to certain structures and methodological steps, it is to be understood that the invention defined in the appended claims is not necessarily limited to the specific structures and/or steps described. Rather, the specific aspects and steps are described as forms of implementing the claimed invention. Since many embodiments of the invention can be practiced without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended. | A pivot pin and saddle assembly is provided for a side-dump trailer or truck with the pivot pin and saddle assembly including structure which limits the relative movement between the side-dump body of the trailer or truck with respect to the frame of the trailer or truck. The saddle assembly of this invention includes a bearing block comprised of Nylon® or other composite material which supports the pivot pin to prevent metal-to-metal contact between the pivot pin and the associated saddle assembly. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a method for storage and recovery of thermal energy or, in particular, to a novel method for storage and recovery of thermal energy utilizing a medium substance for heat storage and transfer, which is not used hitherto in such a purpose, in which thermal energy can be stored as latent heat in the form of chemical energy and, when releasing of the heat is desired, the latent heat is readily and conveniently converted to sensible heat.
The invention also relates to a heat pump in which transfer of heat is effected by the above mentioned medium substance.
In recent years, there is a world-wide trend or demand for effective utilization of various thermal energies such as waste heat and solar energy as a heat source, which have been considered to be of low value owing to their diffused availability. In order to utilize these thermal energies with efficiency and convenience, it is necessary to develop a method that the thermal energy obtained from the heat source is concentrated and stored in a medium which is transported to the place where the thermal energy is utilized and the thermal energy is released as sensible heat when required.
There have been proposed various kinds of substances suitable for use as a heat-storage medium, among which one of the most promising classes utilizes the reversible exothermic and endothermic reactions in the combination reaction of reactants or decomposition reaction of a chemical compound where the thermal energy is converted into chemical energy and temporarily stored in the medium substance.
In particular, most of the prior art heat-storage method utilizes a solid compound as the medium which is decomposed endothermically with evolution of a gaseous product leaving a solid product which can be regenerated into the initial form with recovery of the thermal energy as released sensible heat.
These solid heat-storage media are defective since they are disintegrated into powder by the repeated cycles of evolution of a gas and absorption of the same gas so that the effective thermal conductivity rapidly decreases to an extent that the absorption and releasing of the thermal energy are extremely suppressed in the practical use of the medium substance. This problem is more serious when large scale use of the medium is intended. What is worse, a solid medium is inconveniently transported, for example, by use of a pump in comparison with liquid heat-storage medium substances and, when a combustible or explosive gaseous product such as hydrogen is involved in the reaction, there can be a danger of fire or explosion.
Accordingly, there has been eagerly desired to develop a heat-storage medium with high efficiency, in which large capacity for heat storage, good thermal conductivity and easiness in transportation as well as safety in handling are the key factors.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a novel heat-storage medium and a method for storage and recovery of thermal energy therewith.
Thus the method of the present invention for storage and recovery of thermal energy comprises the steps of
(a) supplying thermal energy to a liquid complex of sodium iodide and ammonia under a first equilibrium pressure of ammonia with simultaneous decrease of the pressure of ammonia to a second equilibrium pressure to liberate ammonia from the liquid complex whereby to effect absorption of the thermal energy into the liquid complex as latent heat, and
(b) subjecting the liquid complex with the thus decreased content of ammonia under the second equilibrium pressure to the first equilibrium pressure to regenerate the liquid complex with the content of ammonia before the absorption of the thermal energy whereby to convert the latent heat to sensible heat.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a pressure-temperature equilibrium diagram of sodium iodide-ammonia complexes.
FIG. 2 shows the molar ratio of ammonia to sodium iodide in the sodium iodide-ammonia complex as a function of the temperature of ammonia at varied partial pressures.
FIG. 3 is a schematic illustration of a heat pump as an apparatus for practicing the inventive method.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It is known that sodium iodide absorbs and reacts with gaseous ammonia at room temperature to form a complex typically expressed by the formula NaI.nNH 3 , where n is a positive number, and, as the partial pressure of ammonia is increased to the absorption of in excess of approximately 2.7 moles of ammonia per mole of sodium iodide, i.e. when n in the above formula is approximately equal to 2.7 or larger, the complex is a colorless, transparent liquid.
The complex of sodium iodide and ammonia is not always liquid but can be solid depending on the partial pressure of ammonia and the temperature. When placed under such conditions, the complex is at first a slurry composed of the liquid complex and the solid complex but the slurry is completely solidified with the lapse of time.
This situation is well illustrated in FIG. 1 showing the pressure-temperature equilibrium diagram of the sodium iodide-ammonia complexes. In the figure, the area shown by A is the region where the partial pressure of ammonia is low so that no liquid complex is formed and the area shown by C is the region where the stable phase is the solid complex so that, even if the complex is in a slurried state at first, the complex is wholly solidified. Both of these regions A and C are not suitable for the use of the complex as the heat-storage medium.
On the contrary, the area shown by B is the region where the liquid complex of sodium iodide and ammonia is the stable phase. That is, the liquid complex of sodium iodide and ammonia to be used in the present invention is desirably under the pressure and temperature conditions falling within this region. It is of course permissible that small amounts of solid complex are contained as slurried in the liquid complex insofar as no noticeable drawbacks are encountered in the storage and transportation of the liquid complex.
In particular, the liquid complex of sodium iodide and ammonia to be used as the heat-storage medium in the inventive method is desirably kept and handled under an ammonia partial pressure of 1 Kg/cm 2 or larger when the temperature is 32° C. or higher and 3.5 Kg/cm 2 or larger when the temperature is below 32° C.
Further, FIG. 2 illustrates the molar ratio of ammonia to sodium iodide in the complex as a function of the temperature at varied partial pressures of ammonia. In this figure, the area shown by B corresponds to the conditions under which the complex is in the liquid state and the area shown by C corresponds to the coexistence of the complexes both in the liquid and solid states.
As is understood from these FIG. 1 and FIG. 2, the changes in the temperature and ammonia partial pressure are always accompanied by the absorption or liberation of ammonia into or from the liquid complex. As has been established by the inventors, the absorption and liberation of ammonia into and from the liquid complex are exothermic and endothermic reactions, respectively, corresponding to several kilocalories of heat of reaction per mole of ammonia depending on the operational conditions of pressure and temperature. For example, about 7.2 kilocalories of heat is evolved per mole of ammonia absorption when the pressure is increased from 1 Kg/cm 2 to 5 Kg/cm 2 at 35° C.
Accordingly, when a liquid complex of sodium iodide and ammonia under equilibrium with a partial pressure of ammonia is brought under a lower partial pressure of ammonia, there takes place an endothermic reaction with liberation of gaseous ammonia so that the heat from the heat source is absorbed through the vessel walls into the liquid complex as latent heat.
On the other hand, when the liquid complex with decreased content of ammonia as produced in the above liberation step is brought under an increased partial pressure of ammonia, then the ammonia is absorbed into the liquid complex to enhance the ammonia content in the liquid complex which is accompanied by releasing of the latent heat as sensible heat.
The physical properties of the complex of sodium iodide and ammonia used in the inventive method depend largely on the ammonia/sodium iodide molar ratio, i.e. the value of n in the formula. For example, the density of the liquid complex varies in the range from 1.0 g/cm 3 to 1.6 g/cm 3 and the viscosity of the liquid complex is in the range from 0.2 to 2.0 centipoise, both at room temperature.
In practicing the method of the invention, the liquid complex of sodium iodide and ammonia contained in a pressurized vessel is heated with a heat source, e.g. waste or solar heat, to liberate ammonia with heat absorption and the thus produced liquid complex with decreased content of ammonia is stored or transported under a lower equilibrium partial pressure of ammonia corresponding to the decreased ammonia content in the liquid complex. When the thermal energy contained in the liquid complex as latent heat is to be recovered, the liquid complex is brought under an increased partial pressure of ammonia so that the liquid complex absorbs ammonia to regain the ammonia content before the liberation of ammonia with releasing of the thermal energy as sensible heat.
FIG. 3 is a schematic illustration of the principle in heat pump as an apparatus suitable for practicing the method of the invention.
In the figure, the liquid complex of sodium iodide and ammonia as the heat-storage medium is contained in the heat absorber 1, where the liquid complex is heated by the heat source 7 through the walls of the heat absorber 1 with the valve 12 closed whereby certain volumes of ammonia are liberated from the liquid complex to decrease the ammonia content in the liquid complex. The thus liberated gaseous ammonia is drawn by the pump 5 through the duct 9 with the valve 14 opened and introduced into the condenser 6 where it is chilled and liquefied and further sent to the vessel 3 for the liquid ammonia with the valve 10 opened and the valve 11 as closed.
On the other hand, the liquid complex with decreased ammonia content is drawn from the heat absorber 1 by means of the pump 4 through the valve 12 and the duct 8 and transferred into the heat regenerator 2.
When the thermal energy is to be recovered in the heat regenerator 2, the valve 11 is opened, the valves 10 and 13 being kept as closed, so that the partial pressure of ammonia in the heat regenerator 2 is increased whereby the liquid complex in the heat regenerator 2 absorbs the ammonia with releasing of the latent heat as sensible heat.
When an equilibrium is established in the heat regenerator 2 and absorption of ammonia by the liquid complex is no longer taking place, the valve 11 is closed and the liquid complex with increased ammonia content is sent back to the heat absorber 1 through the duct 8 by opening the valves 12 and 13 and operating the pump 4 reversingly.
In the above described apparatus, the liquid complex is transferred reciprocatively back and forth between the heat absorber 1 and the heat regenerator 2 through the duct 8 while ammonia is circulated in the direction from the heat absorber 1 to the liquid ammonia vessel 3 to the heat regenerator 2 as free ammonia and from the heat regenerator 2 to the heat absorber 1 as combined in the liquid complex. On the other hand, the thermal energy supplied by the heat source 7, such as the heat from an absorber plate of solar heat energy or waste heat in various kinds of processes such as in chemical plants and electric power plants, is transferred from the heat absorber 1 to the heat regenerator 2 through the duct 8 as borne on the liquid complex as latent heat.
In this case, the liquid complex of sodium iodide and ammonia as well as the ammonia liberated from the liquid complex are transferred by piping but it is of course optional that they are transported as contained in closed pressurized vessels according to need.
As is understood from the above description, the materials to be transferred in the inventive method are all in liquid or gaseous states so that the difficult problems inherent to the transportation of solid materials can be completely obviated by using simple means of piping and pumping. In addition, the storage density of the thermal energy in the liquid complex is considerably large to permit full industrialization of the process according to the invention.
What is more important in the present invention is that the releasing of the latent heat from the liquid complex can be effected at a temperature even higher than in the absorption of the thermal energy to the liquid complex. For example, the absorption of thermal energy by the liquid complex may be carried out at a relatively low temperature of, say, 35° C. to effect decomposition of the liquid complex to liberate ammonia while the liquid complex with the thus reduced ammonia content can be pressurized with ammonia to release the latent heat with increase of the temperature up to 60° to 70° C. or even higher where releasing of the latent heat is continued until an equilibrium is established under the increased partial pressure of ammonia. Therefore, the thermal energy can be transferred from a heat source of 35° C. or lower to the heat regenerator at 60° to 70° C. or higher, thus providing a practical heat pump means or a so-called chemical heat pump means.
In the following, examples are given to illustrate the method and the heat pump of the invention in further detail.
EXAMPLE 1
Into a pressurizable vessel was introduced sodium iodide and the vessel was evacuated by means of a vacuum pump. Then, ammonia gas was gradually introduced into the vessel while the temperature was kept constant at 32° C. When the pressure of ammonia reached about 0.7 Kg/cm 2 absolute (all of the values of pressure given hereinafter are in absolute pressure), sodium iodide and ammonia were combined to form a liquid complex under the pressure of ammonia.
By further increase of the pressure of ammonia, remarkable temperature elevation was recorded and it was necessary to cool the vessel from outside in order to keep the temperature at 32° C. The heat evolved isothermally in the course of pressure increase from 1 Kg/cm 2 to 6 Kg/cm 2 amounted to about 130 calories per gram of sodium iodide.
In the next place, the pressure of ammonia in the vessel was decreased isothermally at 32° C. and it was noted that remarkable heat absorption took place by the endothermic decomposition reaction of the liquid complex to liberate ammonia. The reversibility of the process was established by the exact measurement of the heat absorbed in the course of pressure decrease from 6 Kg/cm 2 to 1 Kg/cm 2 , which was identical with the heat evolved in the pressure increase from 1 Kg/cm 2 to 6 Kg/cm 2 .
EXAMPLE 2
The liquid complex obtained in Example 1, which was in equilibrium with ammonia of 6 Kg/cm 2 pressure at 32° C., was heated as contained in the vessel to 50° C. and the pressure of ammonia was decreased to 2 Kg/cm 2 . During these changes in the temperature and pressure, the heat absorbed by the liquid complex amounted to about 170 calories per g of sodium iodide.
The above process was reversed by cooling the liquid complex to 32° C. and increasing the pressure of ammonia to 6 Kg/cm 2 to find that almost the same quantity of heat was released as sensible heat as in the above heat absorption process. The storage density of heat between two equilibrium states was about 210 calories per ml of the liquid complex under the equilibrium ammonia pressure of 2 Kg/cm 2 at 32° C.
EXAMPLE 3
A liquid complex of sodium iodide and ammonia was prepared at 45° C. under an equilibrium ammonia pressure of 2.3 Kg/cm 2 and the partial pressure of ammonia over the liquid complex was increased to 5.7 Kg/cm 2 whereby heat was evolved so that it was necessary to cool the liquid complex from outside in order to avoid an excessive temperature elevation of the liquid complex. The overall heat evolved until an equilibrium was established at 45° C. under an ammonia partial pressure of 5.7 Kg/cm 2 amounted to about 61 kilocalories per kg of sodium iodide.
On the other hand, the power consumption in the compressor used for pressurizing ammonia from 2.3 Kg/cm 2 to 5.7 Kg/cm 2 was about 5.8 kilocalories giving a coefficient of performance of the heat pump means of about 10.5 at 45° C.
When the operating temperature of the above heat pump means in the releasing of the latent heat was increased to 55° C. instead of 45° C., the heat evolved amounted to about 35 kilocalories per kg of sodium iodide giving a coefficient of performance of about 6. | The invention provides a novel method for the storage and recovery of thel energy by utilizing a medium substance for the storage of heat. The medium substance is a liquid complex of sodium iodide and ammonia, which absorbs heat as latent heat when brought under a reduced partial pressure of ammonia to effect liberation of ammonia and releases the thermal energy as sensible heat when brought under an increased partial pressure of ammonia to absorb ammonia. Different from conventional solid medium substances for storage of heat, the liquid medium proposed is very convenient in handling so that a chemical heat pump with simple structure can be contrived by use of the inventive method. | 5 |
BACKGROUND AND FIELD OF INVENTION
[0001] The present invention relates to fiber optic Fabry-Perot interferometers and more particularly to a method and apparatus for quantitatively measuring the absolute length of a static gap in a Fabry-Perot interferometer. This application claims the benefit of application Ser. Nos. 60/562,492 and 60/562,682, both filed on Apr. 15, 2004.
[0002] Fabry-Perot sensors have broad utility for applications where the measurement of the absolute length of an interferometric gap in a Fabry-Perot sensor. These gaps may relate to pressure, temperature, strain or some other physical property of the material which bounds one side of the gap. For example, their simplicity of design allows these sensors to be embedded into large industrial applications including gas turbines, pressure vessels, pipelines, buildings, or other structures, in order to provide information about pressure, temperature, strain, vibration, or acceleration within the structure. Their size, durability and fast response time make these sensors advantageous.
[0003] In operation, Fabry-Perot interferometers are capable of spanning a range of gaps to create an interference pattern, regardless of whether via reflected light or transmitted light. Performing an optical cross-correlation of such an interference pattern, by reflecting or transmitting the interference pattern through a second interferometer, produces a distinctive signal that reaches a peak intensity of light when the length of the gap in the optical cross-correlator matches the length of the gap in the Fabry-Perot sensor. This distinctive peak intensity signal forms the basis for measurement of the absolute length of a gap in the Fabry-Perot sensor. Although previous systems known to the inventors use optical cross-correlators to make measurements of the length of gaps in Fabry-Perot sensors, the invention described herein is capable of making quantitative, absolute measurements with better sensitivity, greater dynamic range, greater frequency response, and lower cost than previously known systems.
SUMMARY OF INVENTION
[0004] The invention, at its most basic level, consists of one or more light sources, a first Fabry-Perot sensor spanning a gap which varies in response to changes in the environment (pressure, temperature, strain, etc.) and a second sensor having means for optically cross-correlating modulated light that is reflected by or transmitted through the first Fabry-Perot sensor. This second sensor includes means of controllably varying the length of the gap in the second sensor. A correlation burst signal detector is used, and means for verifying the gap distance of the second sensor are required. Lastly, means for comparing correlation burst signals from the first and second sensor in order to determine the absolute distance of the variable gap in the sensor are also included. Additional light sources may be provided, and the means for verifying the gap distance of the second sensor may comprise a set of known, fixed distance sensors which represent upper and lower limits for the sensitivity of the overall system.
[0005] The light sources may consist of a broadband light emitting diode (LED), edge light emitting diode (ELED), super luminescent diodes (SLEDs), wideband lasers such as a vertical cavity surface emitting laser (VCSEL), narrow band lasers such as a HeNe, or various tungsten lamps.
[0006] The means for optical cross-correlation of the modulated light reflected by or transmitted from the Fabry-Perot interferometric sensor preferably comes in the form of an optical cross-correlator placed in series with the Fabry-Perot sensor. As used throughout, the term optical cross-correlator should be understood to mean a system element having a variable gap where the gap is bounded on either side by partial reflectors. Preferably, the reflectivity of these boundary surfaces is between 20% and 50%. This optical cross-correlator is preferably configured as a Fabry-Perot interferometer. The amplitude or percentage of light reflected from or transmitted through the Fabry-Perot sensor and reflected from or transmitted through the optical cross-correlator is defined by the cross correlation product of the classic interferometric equation for each interferometer. For further discussion of such modulation, including the various equations that may be used to perform the calculations contemplated by this invention, refer to Principles of Optics, Chapter 7, Born and Wolf which is hereby incorporated by reference. This classic interferometric equation defines the intensity of light as a function of both the length of the gap in the interferometer and the spectral distribution of the light that is transmitted from the light source(s).
[0007] The length of the gap in the optical cross-correlator may be variable by oscillating or moving one or both of the reflectors in the Fabry-Perot optical cross-correlator via a lead-zirconate-titanate (PZT) or some other linear or rotary actuator. The means for controlling the position of the optical cross-correlators can be accomplished with any linear or rotary positioner such as stepper motors, PZTs, magnetostrictive actuators, lever arms or any combination thereof.
[0008] The resultant correlation may be detected by one or more detectors. The detectors may consist of silicon or InGaAs photodiodes. The detectors may view different light sources with different wavelength bands. The detectors convert the light signals into an electronic output, and an electronic processor converts the electronic signals into representative measures of the Fabry-Perot sensor gap which correspond to the pressure, temperature, strain, vibration, or acceleration of interest. The electronic signals from the detectors are also used to control the frequency and amplitude of the oscillations and/or the length of the gap in the optical cross-correlator.
[0009] Finally, the invention contemplates the processing of the electronic signals from a microprocessor where software is used to read the electronic signal, control the position of the optical cross-correlators, and generate an output signal indicative of the length of the gap in the Fabry-Perot sensor.
[0010] One embodiment of the present invention relies upon an optical cross-correlator configured as a Fabry-Perot interferometer with a variable length of gap to make absolute measurements of the length of a gap in a Fabry-Perot sensor at relatively high frequency and at with a higher dynamic range than can be accomplished via other means. In this embodiment, the variable gap optical cross-correlator does not oscillate but is moved via a PZT or similar device through a range of gaps until the length of its gap matches that of the Fabry-Perot sensor. Then the system tracks changes in the length of the gap in the Fabry-Perot sensor by dithering, (oscillating through a very small range of motion). By measuring or otherwise knowing the precise length of gap in the optical cross-correlator where the length of the Fabry-Perot gap is identical to the length of the gap in the optical cross-correlator, one also knows the precise length of the gap in the Fabry-Perot sensor.
[0011] In an alternate embodiment, the variable gap optical cross-correlator is configured as a Fabry-Perot interferometer using a PZT element that oscillates at a high rate to sweep through a range of gaps at high frequency. Twice in each oscillation or sweep cycle, the length of the gap in the optical cross-correlator precisely matches the length of the gap in the Fabry-Perot sensor and at these moments a peak in the correlation signal is produced. By precisely knowing or mesuring the time of the occurrence of each match and by knowing the amplitude and frequency characteristics of the oscillations of the optical cross-correlators, one also knows the precise length of the gap in the Fabry-Perot sensor.
[0012] The amplitude and frequency of the oscillations and the precise length of the gap in the optical cross correlator can be controlled and known by applying a known voltage to a PZT element. Further embodiments contemplate the use of one or two reference sensors spanning fixed, known gaps along with two or more light sources to increase the accuracy of the system.
[0013] In operation, the inventive system comprises a light source, a first Fabry-Perot sensor capable of spanning a range of gaps, an optical cross-correlator configured as a second Fabry-Perot interferometer spanning a gap of a known length and capable of changing the length of that gap in a controllable and known manner, detector means to convert the light signals into electronic signals, and the electronic means to control the length of the gap in the optical cross-correlators and to generate an output signal indicative of the parameter to be measured.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 a is a schematic of the invention using a transmissive optical cross-correlator.
[0015] FIG. 1 b shows an alternative embodiment for the optical cross-correlator which uses a reflective optical cross-correlator.
[0016] FIG. 2 a shows a typical output curve for a fixed sensor gap where the length of the optical cross-correlator gap varies when a narrowband light source such as an ELED is used according to the invention.
[0017] FIG. 2 b shows a typical output for a fixed sensor gap where the length of the optical cross-correlator gap varies when a wide bandwidth spectral source is used according to the invention.
[0018] FIG. 3 shows an alternative embodiment of the optical readout probe used to verify the position of the gap in the optical cross-correlator and improve the accuracy of the invention.
[0019] FIG. 4 shows alternative schematic for a reflective optical cross-correlator.
[0020] FIG. 5 shows an electronic schematic of a capacitance bridge that may be employed as a reference sensor in the embodiment depicted in FIG. 4 .
[0021] FIG. 6 a shows an alternate embodiment of the invention which includes the use of three separate light sources to determine the precise length of gap in the optical cross-correlator.
[0022] FIG. 6 b shows transmission versus wavelength for cut-off filter F 1 .
[0023] FIG. 6 c shows transmission versus wavelength for cut-on filter F 2 .
[0024] FIG. 6 d shows output signals from detectors D 1 ,D 2 ,D 3 that illustrate light intensity versus gap for in FIG. 6 a.
[0025] FIG. 6 e shows a typical output (light intensity versus gap for VCSEL starting from zero gap) for a fixed sensor gap where the length of the optical cross-correlator gap varies when a laser light source is used according to the invention.
[0026] FIG. 6 f shows another alternate embodiment of the invention.
[0027] FIG. 7 shows an embodiment for the invention which includes two reference interferometers to determine the positioning of the optical cross-correlator in transmission mode on the basis of time.
[0028] FIG. 8 shows a plot of the various signals generated and monitored by the embodiment depicted in FIG. 7 for two fixed reference sensors that have gaps with lengths of 6000 nm and 25,000 nm respectively, and a sensor with a gap of 15,000 nm over one cycle of oscillation.
[0029] FIGS. 9 a - 9 d depict alternative arrangements for the invention, also including signal calculation information.
[0030] FIG. 10 shows the absolute gap of 12,000 nm in the Fabry-Perot sensor when the peak amplitude of the time difference between the reference interferometer and the Fabry-Perot is 118 microseconds based on the linearization of the sinusoidal function.
[0031] FIG. 11 shows one possible block diagram of the elements of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0032] A first embodiment of the inventive system 10 is shown in FIG. 1 a. Light I o generated by source L 1 is modulated and reflected from the Fabry-Perot interferometer S 1 , which has an unknown variable gap length of G s , to a Fabry-Perot interferometer S 2 with a controllably variable gap G R that is mounted on a PZT element 14 . Voltage is applied to PZT element 14 to induce a stretching motion on the Fabry-Perot interferometer S 2 which causes a change in the length of the gap (separation of the parallel Fabry-Perot mirrors), thereby optically cross-correlating the light received by S 2 . The optically cross-correlated light is sensed by detector D. The controllably variable gap can be manipulated so that G R matches the length of the gap G s . S 1 may be a temperature, pressure, strain, vibration, acceleration, or other similar sensor. The voltage necessary to drive PZT 14 to the position where the length of the gap G R matches the length of the gap G s is directly proportional to the length of the gap G s so that the drive voltage can be directly related to the measure of the output. Notably, detector D converts the optical signal into an electronic signal and is used to determine when the match in the length of these gaps has occurred. As described in more detail below, a positional verification device (not pictured) is associated with the S 2 to confirm the precise positioning of S 2 so as to provide an absolute readout for the system.
[0033] For a Fabry-Perot sensor with a fixed length of gap, the intensity of the light will vary as a function of the length of the gap in the optical cross-correlator as shown in FIGS. 2 a and 2 b where the length of the gap in the Fabry-Perot sensor is 20 um and the length of the gap in the optical cross-correlator ranges from 15 um to 25 um. The plot in FIG. 2 a further assumes the light source is a light emitting diode (LED) with a center wavelength of 850 nm and spectral bandwidth of 50 nm. The plot in FIG. 2 b assumes the light source is a tungsten lamp with a center wavelength of 850 nm and an effective spectral bandwidth of 400 nm considering a silicon photodetector. In both FIGS. 2 a and 2 b, the interferometers are made using low finesse reflectors, i.e. approximately 30% reflectors.
[0034] A second embodiment of the inventive system 10 is shown in FIG. 1 b. Light reflected from the S 1 is sent to the detector D after being reflected from an optical cross-correlator configured as a Fabry-Perot interferometer S 2 . This optical cross-correlator is configured by placing an optical fiber with a 30% reflective coating perpendicular to a mirror mounted directly to the PZT 14 . Voltage is applied to PZT element 14 to induce a change in the length of the gap G R . Again, the voltage necessary to drive PZT 14 to the position where the length of the gap G R matches the length of the gap G s is directly proportional to the length of the gap G s so that the drive voltage can be directly related to the measure of the output. Notably, detector D converts the optical signal into an electronic signal and is used to determine when the match in the length of these gaps has occurred.
[0035] Notably, the signals generated in FIGS. 2 a and 2 b have the same characteristic shape although inverted when viewed in transmission vs. reflectance, i.e. configured as FIG. 1 a (transmission) vs. FIG. 1 b (reflectance).
[0036] The PZT actuator 14 may be configured as a stack or as a bimorph as illustrated in FIG. 4 . The bimorph 30 is a beam fixed at one end, consisting of two layers 30 a, 30 b of lead-zirconate-titanate material that are excited out of phase. This causes one layer to expand while the other contracts which results in deflection of the beam. The advantage of the bimorph configuration shown in FIG. 4 is that the desired displacement can be obtained at a lower drive voltage because of the lever arm effect of the beam which comprises bimorph 30 . This configuration is also particularly well suited to the use of secondary readout means (i.e., a means to verify the position of interferometer S 2 ), described below. Another configuration of the optical readout 24 which can be used as a means of verifying the position of the sensors S 2 is shown in FIG. 3 , with the reference numerals therein corresponding to FIG. 4 .
[0037] Overall system accuracy can be improved through variations to the elements shown in FIGS. 1 a and 1 b which provide the means for independent measurement of length of the gap G R . Such means include the use of one or more additional reference sensors to verify the position of the interferometer S 2 and can be configured as but not limited to strain gage, capacitive sensor, or a linear variable differential transformer (LVDT). All of these items are commercially available. A comparison of their characteristics are summarized in Table 1.
TABLE 1 Comparison of candidate readout methods for PZT length assuming at range of 15 μm Strain Gage LVDT Capacitance Resolution 1 nm 10 nm 0.1 nm Bandwidth Up to 5 kHz Up to 1 kHz Up to 10 kHz
[0038] While each of the items listed in Table 1 can be used in the present invention, it is important to note the limitations of each. The small bandwidth makes the LVDT and the strain gage less attractive than the optical sensor and capacitance sensor. Both the capacitance and the strain gage may have long-term stability problems due to creep of the adhesive needed to bond these sensors to the PZT. Nevertheless, these options, along with others known to those skilled in the art, are available in configuring an enhanced system according to the schematic of FIGS. 1 a or 1 b.
[0039] As seen in FIG. 4 , the optical measurement system 24 used as a positional verification device may also consist of two optical readout devices A, B, one on each side of the PZT which deliver light to the PZT and one on each side of the PZT which receive light reflected from the PZT. Each assembly A, B consists of a light delivery fiber and detector to measure the light intensity. The power delivered to the two detectors is a function of the length of the gap between the ends of the sensor fibers and the PZT. With a probe on either side of the PZT, the signal from one increases while the other decreases. The ratio of the two signals is independent of source intensity fluctuations and gives an indirect measure of the length of the gap in the optical cross-correlator. This optical reference sensor could be improved further by using fiber bundles in lieu of single fibers. Proximity sensors based this principle have been demonstrated for high speed, high-resolution measurement.
[0040] A capacitance sensor 50 which can be used as the positional verification device is depicted in FIG. 5 , although this particular arrangement can be relatively expensive. As shown in FIG. 5 , the particular arrangement of capacitors (C FIX , C gapA , C gapB ) is directed toward a positional verification sensor used with a PZT bender. The fixed capacitors C FIX act as references in a bridge circuit that measures capacitance differences. With reference to FIG. 4 , assume that the PZT bender 30 is a capacitor electrode placed between electrodes positioned in place of the optical readout device fibers A and B shown FIG. 4 . Then as the bender 30 moves closer to A, the capacitance of Capacitor A increases and capacitance of Capacitor B decreases. The capacitance change is detected as a change in voltage V out from the bridge circuit. A similar arrangement could be devised using a resistive bridge.
[0041] An alternative to the optical reference sensor would be to make a direct measurement of the length of the gap in the PZT interferometer (rather than the relative position of the PZT as in FIGS. 3-5 above), thereby eliminating the problems associated with calibration, long term drift, resolution, repeatability and accuracy of the PZT. This alternative employs a reference light source whose wavelength and intensity may slowly vary over time and thus are unknown at any point in time. Through this embodiment, the system self-calibrates the unknown reference light source periodically as explained below and the reference light is used to make an absolute measurement of the length of the gap in the PZT interferometer.
[0042] Such an alternate embodiment is shown in FIG. 6 a. A light source L 1 (preferably a Tungsten lamp) is connected to a 2×2 light splitter C 1 where the light is transmitted to the Fabry-Perot sensor S 1 through one of the output legs of C 1 . The other output leg is connected to a pair of light sources L 2 , L 3 (preferably a VCSEL at 1520 to 1540 nm wavelength and an ELED at 1310 nm wavelength) through a coupler C 4 . Reflected light from the sensor S 1 travels back through splitter C 1 to the interferometer S 2 (which includes PZT 14 for controllably varying the length of gap G R , all not shown in FIG. 6 a ), which acts as an optical cross-correlator for the modulated light from the sensor. Light transmitted through interferometer S 2 is modulated as the gap G R is changed by voltage applied to the PZT 14 . The modulation pattern in transmission is similar to the peak-to-valley modulation pattern in reflection from a Fabry-Perot sensor. The cross-correlated light from source L 1 then travels through a splitter C 2 and through a cut-off filter F 1 , which blocks (does not pass) the 1500 nm wavelength light from the VCSEL (see FIG. 6 b ), but passes all shorter wavelengths. The filtered light then travels through splitter C 3 to detectors D 1 and D 2 . The intensity of the light signal at detector D 1 (silicon) is converted into an electrical current. Notably the light from the ELED source L 3 is not filtered and is transmitted to detector D 1 . Since D 1 is a silicon detector it is insensitive to the ELED wavelength (1310 nm).
[0043] Light from sources L 2 , L 3 travels through splitter C 1 and the interferometer S 2 , which does not perform a cross-correlation because the light from sources L 2 , L 3 has not been modulated (i.e., it does not come into contact with interferometer S 1 ). However the interferometer S 2 modulates the light from sources L 2 , L 3 . After splitting at C 2 , the light from source L 2 passes through the cut-off filter F 1 , through a second interferometer R 1 with a known, stable fixed gap and then onto detector D 2 (InGaAs). R 1 acts as an optical cross-correlator for the ELED light modulated by the PZT interferometer, and detector D 2 converts the cross-correlated ELED light into an electrical current. Notably the long wavelength light from the tungsten lamp source L 1 is not filtered by F 1 and is transmitted to detector D 2 along with the ELED light. Since the intensity from the tungsten lamp is very low compared to the ELED, the tungsten light has a negligible effect on the signal at detector D 2 .
[0044] After splitting at C 2 , the light from the VCSEL source 51 travels through a cut-on filter F 2 , which passes the long wavelength VCSEL light but blocks the short wavelengths from the tungsten lamp and ELED (see FIG. 6 c ). The light is then detected by D 3 (InGaAs), which converts the VCSEL light into an electrical current.
[0045] FIGS. 6 d and 6 e show the signals generated at each detector as the interferometer S 2 is moved through a range of motion corresponding to the gap range ( FIG. 6 d ), and the full range of motion 0 to 30 um in FIG. 6 e . The output of detector D 1 is a correlation pattern that results from the broadband light from the tungsten source that is modulated and reflected by the sensor and cross-correlated by the PZT interferometer. In the example shown in FIG. 6 d, the sensor gap is 12 um. The output from detector D 2 is a different correlation pattern that results from the ELED light modulated by the interferometer S 2 and cross-correlated by the fixed reference interferometer at R 1 . In the example shown in FIG. 6 d, the fixed reference interferometer R 1 gap is 28 um. The output from detector D 3 is a signal that is modulated by the interferometer S 2 only and not cross-correlated. The modulation peaks (also called interference fringes or just “fringes”) from the output of detector D 3 are spaced λ/2 apart, where λ is the VCSEL wavelength. Each fringe may be identified by an integer order number, and the light intensity I is described by the relationship
I =1/[1 +F sin 2 (2π G R /λ)] (1) where G R is the length of the gap in the interferometer S 2 and F is a constant. When the interferometer S 2 is positioned to zero gap (home position) then as the PZT gap increases, the signal from detector D 3 changes as shown in FIG. 6 e. As the voltage continues to increase, software tracks the output from D 3 and counts the number of fringe peaks and the fractional part of the next fringe when the length of the gap in the interferometer S 2 is equal to the length of the gap in the reference interferometer R 1 , i.e. 28 um. The fractional part of the next fringe is a function of the light intensity which can be resolved to 1%.
[0047] The system operates in two modes, i.e. calibration mode and measurement mode. In calibration mode, the PZT 14 and interferometer S 2 are scanned through the range of motion 0 to 30 um. The signal from detector D 2 reaches a peak when the length of the gap G R in interferometer S 2 is equal to the length of the gap at reference interferometer R 1 , which has a fixed and known gap of 28 um in the example in FIG. 6 d . Detector D 3 , which measures light intensity from the VCSEL is monitored during calibration. Refer to Table 2. There is uncertainty in the wavelength of the VCSEL and this uncertainty ranges from 1520 to 1540 nm. When the length of the gap G R in the interferometer S 2 is scanned through the range of motion 0 to 30 um, the fringes are counted. Zero gap is verified when the VCSEL signal from detector D 3 does not change with applied voltage to the PZT. As shown in FIG. 6 e, 36.6 fringes are counted when the laser wavelength is 1530 nm (1.53 um). Using Table 2 and Equation (1), the fractional fringe count calibrates the VCSEL wavelength. As shown in Table 2 and verified in FIG. 6 d, there are 36.6 VCSEL fringes between the PZT starting position and the R 1 gap, which is known to be fixed at 28 um and is periodically monitored by the ELED source through the output from detector D 2 .
[0048] In measurement mode, the voltage to the PZT 14 is changed from its value that resulted in a gap of 28 um until the output signal from D 1 reaches its peak as shown in FIG. 6 d. As the applied voltage to the PZT is changed, software keeps track of the fringe count from detector D 3 . When the peak value in the correlation pattern is detected by D 1 , the fractional fringe count is recorded and subtracted from the fringe count obtained in calibration mode. Through Equation (1), the sensor gap is calculated in terms of the absolute wavelength of the VCSEL. Thereafter in measurement mode, the PZT voltage is dithered so that the correlation pattern signal from D 1 is tracked by software. Changes in the peak value are tracked by fractional changes in fringe shift at detector D 3 . Recalibration is performed periodically.
TABLE 2 Calibration of the VCSEL Wavelength VCSEL Known Gap Wavelength R1 (um) Fringes 1520 28 36.84 1521 28 36.82 1522 28 36.79 1523 28 36.77 1524 28 36.75 1525 28 36.72 1526 28 36.70 1527 28 36.67 1528 28 36.65 1529 28 36.63 1530 28 36.60 1531 28 36.58 1532 28 36.55 1533 28 36.53 1534 28 36.51 1535 28 36.48 1536 28 36.46 1537 28 36.43 1538 28 36.41 1539 28 36.39 1540 28 36.36
[0049] Another alternative to the optical reference sensor relies on making a direct measurement of the length of the gap in the PZT interferometer and thereby again eliminates the problems associated with calibration, long term drift, resolution, repeatability and accuracy of the PZT and the complexities of the embodiment described above. This alternative employs a very stable light source such as a HeNe laser whose wavelength is more stable than other sources. Through this embodiment, the need for system calibration occurs primarily at system startup.
[0050] This alternative is described in FIG. 6 f . A light source L 1 (preferably a Tungsten lamp) is connected to a 2×2 light splitter C 1 where the light is transmitted to the Fabry-Perot sensor S 1 through one of the output legs of C 1 . The other output leg is connected to a HeNe laser light sources with a wavelength 633 nm. Reflected light from the sensor travels back through splitter C 1 to the interferometer S 2 , which acts as an optical cross-correlator for the modulated light from the sensor S 1 . Light transmitted through the interferometer S 2 is modulated as the gap is changed by voltage applied to the PZT 14 . The modulation pattern in transmission is similar to the peak-to-valley modulation pattern in reflection from a Fabry-Perot sensor.) The cross-correlated light then travels through a splitter C 2 and through a cut-on filter F 1 , which blocks (does not pass) the 633 nm wavelength light from the HeNe laser but passes all longer wavelengths. The filtered light travels to detector D 1 where the intensity of the light signal is converted into an electrical current.
[0051] Light from the HeNe source travels through splitter C 1 and the interferometer S 2 , which does not perform a cross-correlation because the light from the HeNe has not been modulated. However the interferometer S 2 modulates the light from the HeNe. After splitting at C 2 , the light from the HeNe travels to detector D 2 (Si). Notably the long wavelength light from the tungsten lamp source L 1 is transmitted to detector D 2 along with the HeNe light. Since the intensity from the tungsten lamp is very low compared to the HeNe, the tungsten light has a negligible effect on the signal at detector D 2 .
[0052] FIGS. 6 d and 6 e show the signals generated at each detector as the interferometer S 2 is moved through a range of motion corresponding to the gap range ( FIG. 6 d ). The output of detector D 1 is a correlation pattern that results from the broadband light from the tungsten source that is modulated and reflected by the sensor and cross-correlated by the interferometer S 2 . In the example shown in FIG. 6 d, the sensor gap is 12 um. The output from detector D 2 is a signal that is modulated by the PZT interferometer only and not cross-correlated. The modulation peaks (also called interference fringes or just “fringes”) from the output of detector D 2 are spaced λ/2 apart, where λ is the HeNe wavelength. Each fringe may be identified by an integer order number, and the light intensity I is described by the relationship
I= 1/[1 +F sin 2 (2π G R /λ)] (1) where G R is the length of the gap in the interferometer S 2 . When the interferometer S 2 is positioned to zero gap (home position) then as the PZT gap increases, the signal from detector D 2 changes as shown in FIG. 6 e (Note the HeNe wavelength is different from the VCSEL but the concept is the same.) In general, the starting point for the light intensity is not zero as shown but can have any value between 0 and 1. As the voltage continues to increase, software tracks the output from D 2 and counts the number of fringe peaks and the fractional part of the next fringe when the length of the gap in the PZT interferometer is equal to the length of the gap in the sensor, i.e. 12 um. The fractional part of the next fringe is a function of the light intensity which can be resolved to 1%.
[0054] As before, the system operates in two modes, i.e. scan mode and measurement mode. In scan mode, the PZT is scanned through the range of motion 0 to 30 um. The signal from detector D 1 reaches a peak when the length of the gap at the interferometer S 2 is equal to the length of the gap in the Fabry-Perot sensor S 1 . Detector D 2 , which measures light intensity from the HeNe is monitored during scan and software keeps track of the fringe count continuously. Since there is negligible uncertainty in the wavelength of the HeNe, there is no need for a wavelength calibration as there is with a VCSEL or other unstable light source. Once the peak intensity in detector D 1 is found, the system changes into measurement mode.
[0055] In measurement mode, the sensor gap is calculated in terms of the absolute wavelength of the HeNe using Equation 1. Thereafter in measurement mode, the PZT voltage is dithered so that the correlation pattern signal from D 1 is tracked by software. Changes in the peak value are tracked by fractional changes in fringe shift at detector D 2 .
[0056] The frequency response is limited by the PZT scan rate and the absolute measurement accuracy is determined by the repeatability of the gap measurement using the reference sensor.
[0057] Yet another means for improving the resolution and accuracy involves the use of a time-based calculation on the absolute position of the Fabry-Perot sensor. This embodiment eliminates some of the hysteresis and creep in the lead-zirconate-titanate (PZT) modulator.
[0058] The elements of the time-based system are shown in FIG. 7 . Light source L preferably a tungsten light source travels through an oscillating interferometer that changes its length of gap at a constant frequency and amplitude. The oscillating interferometer S 2 includes a PZT or other high speed oscillator. The light from L is modulated by the interferometer S 2 and travels through splitter C 1 to the Fabry-Perot sensor on one leg and through a VOA (variable optical attenuator) to a second splitter C 2 where the light travels through reference interferometers R 1 and R 2 which have fixed and known gaps. These reference interferometers R 1 , R 2 and the Fabry-Perot sensor S 1 serve as optical cross-correlators for the modulated light from the oscillating interferometer S 2 . The purpose of the VOA is to reduce the reflected light signal that can interfere with reflected signal from the Fabry-Perot sensor at detector D 3 .
[0059] The cross-correlated signals from interferometers R 1 , R 2 , and the Fabry-Perot sensor S 1 are monitored continuously by detector D 1 , D 2 , and D 3 respectively (although the invention can be configured for fewer than three detectors as shown in FIGS. 9 a - 9 d and described otherwise below). Notably, the reference interferometers R 1 and R 2 and scanned gap G RT operate in transmission mode, whereas the Fabry-Perot sensor S operates in reflection mode.
[0060] As oscillating interferometer S 2 travels through its range of motion, the gap G R provides a range of gaps as a function of time. Each of the three detectors (D 1 , D 2 , D 3 ) sees a peak in the correlation burst pattern when the length of the gap G R matches the length of the gap in each respective interferometers (R 1 , R 2 , S). The peak detector signals from each interferometer S 1 , R 1 , R 2 are observed as a precise point in time that is a function of the amplitude and frequency of the oscillation gap G R in the oscillating interferometer S 2 . Refer to FIG. 8 . The signal from D 1 , D 2 , and D 3 trace out the correlation pattern that results from one cycle of oscillation of the G R gap. The peak intensity occurs at that moment in time during the oscillation when the gap G R equals the gap in reference interferometer R 1 , R 2 , and Fabry-Perot sensor S 1 .
[0061] The Fabry-Perot sensor gap G S is calculated based on the known precise gap and time of occurrence of the peak intensity of reference interferometers R 1 and R 2 and the sinusoidal functional dependence of the oscillating displacement of the range of gaps from G R .
[0062] These three signals as described are plotted in FIG. 8 , with P R1 representing the signal generated by the detector associated with R 1 , P ST representing sensor S 1 and P R2 representing R 2 . The microprocessor based timing circuit provides the signal plot P T in the bottom trace of FIG. 8 . The microprocessor measures the time differences t 1 between the R 1 peak and the Fabry-Perot sensor S 1 peak and time difference t 2 between R 1 peak and the R 2 peak. After linearization of the sinusoidal displacement of G RT , the sensor gap G ST can be computed from FIG. 10 and the following equation:
G S =( t 1 /t 2 )[ G R2 −G R1 )+ G R1
where G R1 is the gap of R 1 and G R2 is the gap of R 2 .
[0064] The equation for above assumes a linear change of the scanned gap with time. In fact, the change is sinusoidal and must be modified accordingly to deal with the nonlinearity. Specifically, the scanned gap is driven sinusoidally at frequency co and can be expressed as
G=A+B cox (ω t )
[0065] The correlation peaks of interest occur at the times when:
G R1 =A+B cos (ω t o )
G S =A+B cos (ω t 1 )
G R2 =A+B cos (ω t 2 )
where G R1 is the gap of the short reference sensor R 1 (as stated above, a known distance); G S is the gap of the sensor monitoring the unknown gap; G R2 is the gap of the long reference sensor R 2 (also a known value); and t represents the times of occurrence of the peaks in the correlation burst.
[0067] Using the equations and information above, it becomes possible to calculate the actual value of G S through accurate time measurement, as achieved by the aforementioned microprocessor, as follows:
G S =G R1 +( G R2 −G R1 )[(cos(ω t o )−cos(ω t o ))/(cos(ω t 2 )−cos(ω t o ))]
[0068] Notably, the equation above can be manipulated and used to achieve accurate time-based measurements according to any of the alternative embodiments described below.
[0069] To maximize the signal the lamp should be a quartz-halogen type that allows high filament temperature while maintaining long life. Exemplary filament temperatures in the range of 2700 K can burn for about 10,000 hours, while temperatures exceeding 3100 K drop that life span to around 100 hours. Notably, manufacturers define the lamp properties in terms of color-temperature, which is approximately 90 degrees higher than the actual filament temperature.
[0070] Clearly, there is an advantage to using the higher temperature lamp, but the added power comes at a cost of lifetime so there is a trade-off. One possible arrangement would be to use a lower temperature light source, and if there is a signal level problem, the higher temperature lamp can be substituted or integrated into system 10 as an alternative.
[0071] Additional consideration should be given to the radiance of the light source, which impacts the power delivered throughout the system. Further discussion of these principles can be found in the Photonics Handbook, the relevant portions of which are hereby incorporated by reference. As recognized by those skilled in the art, the radiance of the lamp filament can be determined with the temperature and the emissivity of the filament material (preferably tungsten). The radiance is also a function of wavelength, while the total integrated irradiance over the spectral range from 550 mn to 1050 nm is the quantity of interest for tungsten. Of course, these spectral limits are somewhat arbitrary, but are based on the basic fact that the detector response curve falls to about ½ its maximum value at these wavelengths.
[0072] The fraction of the input power delivered to the detectors is based on the reflectance from the sensors S 1 , S 2 , R 1 , R 2 . Ideally, this reflectance measured should be approximately 50% of the input light power.
[0073] Additional alternative arrangements of the optoelectronic components for system 100 are possible, although all of these are fundamentally rooted in the comparative calculation principle set forth in system 10 . For all of the variations discussed below, the previous designations utilized in FIG. 7 are applicable to all such alternatives unless specifically given a different meaning. By the same token, the denotations for reflectance and input power on FIG. 7 are for the same purposes as described in FIGS. 9 a - 9 d.
[0074] The first such alternative arrangement is presented 9 a. Light source L is provided to splitter C 1 . Notably, all of the sensors, as well as scanned gap G R operate in reflection mode. The reflectance from each gap is indicated by r i and beside the detector is indicated the magnitude of the power delivered through the system arrangement, where Io is the input power. Detector D is used to monitor all three sensors S 1 , R 1 , R 2 through appropriate routing by splitters C 2 and C 3 , and the power delivered to the detector consists of three terms, one from each reference and one from the sensor. In turn, these terms represent the product of two reflectances depending upon the routing of the light (e.g., r RT ×r R1 ) and are not simple products but rather the correlation product that yield individual burst patterns. Adjusting for these variations, further calculations are consistent with the principles described above (also depicted on FIG. 9 a ).
[0075] FIG. 9 b shows another alternate embodiment that employs one 2×4 splitter in place of the three splitters shown in FIGS. 7 and 9 a. Only one detector D is required.
[0076] FIG. 9 c shows yet another configuration requiring a single 2×2 splitter and a single detector D. Significantly, the first two terms in the expression for the power to the detector are simply the feed-through of half the power input to the splitter. These terms do not contain any correlation information and simply add noise.
[0077] FIG. 9 d shows yet another configuration requiring a single 2×2 splitter and a single detector D where the reference interferometers operate in transmission mode rather than reflection.
[0078] The signal levels provided for each configuration are summarized in Table 3. In some configurations, the signal level for the reference interferometers is different from that for the sensors. In these cases, Table 3 lists the worst case. It is assumed that the reflectance and transmittance of all sensors is the same, so the subscripts that are used for clarity in the Figures are omitted in Table 3. It is also assumed that there is no excess loss in the splitters.
TABLE 3 Comparison of optoelectronic configurations Figure reference Signal Level I/Io rr/16 .026 rr/64 .006 rr/64 .006 trtt/4 .029 tr/9 .034
[0079] To make valid comparisons based on the expressions in Table 3 requires quantification of the cross-correlation terms tt, tr, and rr. Based on 30% reflectance for the separated mirrors that define the gap for each sensor, the cross-correlation products are conservatively estimated to be: tt=0.37; tr=0.31; and rr=0.41. Using these values enables evaluation of the products in column 2 of Table 3 to obtain the fraction of power delivered to the detector, which is given in column 3. The preferred configuration of FIG. 7 is the best of the first five ( FIG. 7 - FIG. 9 d ).
[0080] It is appropriate to perform a signal-to-noise ratio analysis. Consider, for example a sensor signal update rate of 10 kHz. The scanned gap is sinusoidally driven by the oscillator at 5 kHz, providing the desired 10 kHz update rate. Assuming a total scanning range of 20 μm, the scanned gap is expressed as
g ( t )=10 μm(sin ω t )+ Q (5)
where Q is the gap in the absence of scanning and ω=2π(5000)rad/sec
[0082] The scanning rate, dg/dt, is a function of time. The maximum scan rate occurs at the time when sin ωt=0. At this point
10 μm(sin ωt)˜10 μm (ωt)
So, dg/dt= 10 μm ω=(10)2π(5000)=3.14×10 5 μm/sec or 314 nm/μsec (6)
[0083] A correlation model can be used to provide results in terms of intensity as a function of correlation element gap. The gap is converted to time using the scan rate Equation (6) above, and the correlation pattern can be viewed as a quasi-sinusoid with a frequency of 0.84 MHz. There are no high frequency features of interest. Accordingly, the photodiode amplifier is designed as a band pass amplifier with a range of 100 kHz to 1 MHz. This is the frequency response of the photodiode signal and not to be confused with the time resolution required to measure the sensor gap with a resolution of 0.1%, (10 nm assuming a full scale range of 10 μm). A 10 nm gap change converted to a time base using Equation (6) reveals a 32 nsec change in time. As a minimum, the time base needs a resolution of 32 nsec.
[0084] To quantify the effect of noise, consider 1 MHz sine wave with variable amplitude added to the signal. A 1 MHz noise frequency is considered because higher frequencies are filtered out and lower frequencies do not affect the peak. Noise with frequency content comparable to that of the correlation peak, however, does affect both the amplitude and position of the peak. Ideally, the signal processor should be capable of operating with SNR=50.
[0085] The amplifier noise increases with the capacitance of the photodiode. Thus a photodiode is needed with the smallest capacitance possible. A UDT Sensors PIN-020A has an active area with a diameter of 510 μm and a capacitance of 1.0 pf when reverse biased at 10 V.
[0086] Other noise sources that need to be considered for systems 10 , 11 or 12 include: shot noise due to DC signal current plus dark current; Johnson noise from the feedback resistor; noise due to amplifier input current noise; and noise due to amplifier input voltage noise. Conservative calculations show that the combined noise terms can be estimated and expressed as an RMS value of about i T =3.8×10 −10 A. Recall that the estimated light power level delivered to the detector was determined in paragraph 88 to be approximately 5.2×10 −8 Watts. The effective detector responsivity is on the order of 0.3 A/W, and the expected signal current is 1.6×10 −8 amps. Accordingly, the signal-to-noise ratio is 1.6×10 −8 /3.8×10 −10 =42. While this SNR falls slightly below the preferred value of at least 50, it is a worst-case estimate. The SNR can be improved by modifying the arrangement shown in FIG. 1 so that more light is transmitted through the system. In addition, the SNR can be improved through proper choice of light source. A tungsten filament lamp was assumed but other alternatives are a quartz halogen lamp or super luminescent light emitting diode. Notably, these examples are cited merely as illustrative solutions to improve the performance of the inventive system, and other solutions for improving the SNR and/or the performance of the system will be apparent to those skilled in the art and this disclosure is expressly intended to contemplate such improvements.
[0087] In the same spirit, the ideal performance ranges for system 10 as shown in FIG. 7 include gap G ST which may be anywhere from 5 to 18 μm in length and a visible white light tungsten filament lamp or quartz halogen lamp. Light is delivered to the scanned gap through a 2×2 splitter. Since both splitter outputs illuminate the scanned sensor driven by the oscillator, the light loss budget and SNR can be improved by a factor of 2 compared with the estimated power discussed above. The reflected light from the scanned sensor is modulated by the oscillator, split and transmitted through a 2×2 splitter to the sensor S and also through a 1×2 splitter to two reference sensors R 1 , R 2 and their detectors D 1 , D 2 . The modulated light that is reflected from the sensor S is transmitted back to a third detector D 3 . The two reference interferometers can be designed with gaps of 6 and 18 um, for example.
[0088] The oscillator for gap G R changes at a set rate, i.e. 1000 Hz and travels through a range of motion of approximately 20 μm. The ultimate range of motion is approximately 5 to 25 μm for the scanned gap, which consists of a moving mirror that maintains parallelism with the reflective end of an optical fiber. The range of motion and the rate of oscillation may be modified for specific applications. The trade off with increased bandwidth is increased noise and reduced dynamic measurement range of the Fabry-Perot sensor gap to be measured.
[0089] The detectors D 1 , D 2 , D 3 may be either silicon or InGaAs photodiodes. For short-range applications, i.e. up to 1000 meters, a quartz-halogen lamp provides the best performance. For long-range applications, i.e. 500 meters to 2500 meters the tungsten lamp provides somewhat better performance.
[0090] The inventive systems 10 , 11 , 12 can be easily multiplexed with several channels of optical data sharing a single oscillator and microprocessor, however, each channel requires its own set of reference interferometers and photodiodes.
[0091] Finally, the system electronics are depicted FIG. 11 . The power supply board converts 110 VAC to 12 VDC and 5 VDC and is used to power the microprocessor board. The photodiode board generates a voltage proportional to the amount of light that illuminates each photodiode. The output of the photodiode board is the input for the microprocessor board. The microprocessor board digitizes the signal from the photodiode board and determines the sensor gap. The microprocessor also provides a signal to the oscillator driver and provides a digital output, i.e. RS-232, to the control system. The final output of the system can be an analog signal, e.g. 0-5V or 4-20 mA. | A method and apparatus for quantitatively measuring the distance of an unknown variable gap is disclosed. Light is provided to two Fabry-Perot interferometers arranged in a series, one spanning the unknown gap and the other spanning a controllably variable gap. Means for verifying the positioning of the Fabry-Perot interferometer having the controllably variable gap work in conjunction with a signal processor, a correlation burst signal detector and means for conveying the light to the various system elements to perform a comparison of detector signals from the two interferometers and quantitatively establish the gap distance. The invention may also be varied to function on a time basis, include more than one source of light, possess filter means to distinguish between light sources and/or include one or more reference interferometers. | 6 |
TECHNICAL FIELD
[0001] The present disclosure relates to a fluid control valve and more particularly an apparatus and method for reducing fluid forces acting on a fluid control valve.
BACKGROUND
[0002] Fluid control valves are well known in the art to provide on/off control of fluid flow, through the use of electrical control signals. Such fluid control valves may find use in internal combustion engines, in fuel systems, and/or in systems that control motion of the engine valves, such as a compression release braking system, or a system in which typical camshaft-produced valve events are modified by way of fluid action. In some cases such fluid control valves may be inactive for a substantial period of time at a cold temperature. These fluid control valves may be prone to slow opening and closing until such time that the fluid viscosity changes due to temperature change as the engine warms up, or the local fluid viscosity changes due to shearing effects of fluid as the fluid control valve is repeatedly operated, or a combination of these and/or other changes.
[0003] Such problems are believed to be caused by fluid collecting in undesired regions where it can fully or partially restrict motion of the moving members of the fluid control valve, or by fluid that finds its way into the clearance spaces that exist between stationary and movable members of the fluid control valves.
[0004] U.S. Pat. No. 5,478,045 discloses draining damping fluid with respect to one cavity of an actuator chamber of a fluid control valve, but is silent regarding fluid in other locations of the device.
[0005] The present disclosure is directed to overcoming one or more of the deficiencies as set forth above.
SUMMARY OF THE INVENTION
[0006] In one aspect of the present disclosure, a fluid control valve has a body with at least one fluid passage, an axial bore, a movable member disposed in the bore, an actuator operatively connected to the movable member and adapted to move the movable member in the axial bore, and the body has at least one vent passage opening into the axial bore at an axial location relative to the axial bore between the fluid passage and the actuator, and the vent passage is adapted to vent leakage fluid.
[0007] In another aspect of the present disclosure, a method of reducing fluid forces acting on a movable member movable relative to a body, consisting of moving the movable member in the body with an actuator, and venting leakage fluid from a location between the actuator and a fluid passage.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 . is a schematic view of an engine utilizing fluid control valve modification of valve events,
[0009] FIG. 2 . is a diagrammatic cross-sectional view through one embodiment of a fluid control valve,
[0010] FIG. 3 and FIG. 3 b . are a diagrammatic cross-sectional views through another embodiment of a fluid control valve, and
[0011] FIG. 4 . is a diagrammatic cross-sectional view through yet another embodiment of a fluid control valve.
DETAILED DESCRIPTION
[0012] Referring to the drawings, FIG. 1 shows an internal combustion engine 10 , having an engine valve 50 movable between closed and open positions relative to a valve seat (all not shown) by a rocker arm 120 . The rocker arm 120 pivots about a center (not shown) in response to movement of a camshaft 40 . Additional components not shown may make up the engine, such as push rods, camshaft followers, lash adjustment mechanism, cylinder head, and the like.
[0013] A valve position modification system 15 has a fluid control valve 20 and a fluidically driven actuator 30 . The valve position modification system may control the opening and closing times of the engine valve 50 .
[0014] The valve position modification system 15 further has a sump 60 connected to a fluid supply 70 , which connects via a first conduit 80 to the fluid control valve 20 and via a second conduit 90 to a check valve 100 . Both the fluid control valve 20 and the check valve 100 connect via a third conduit 110 to the fluidically driven actuator 30 . The fluidically driven actuator 30 is movable to engage the rocker arm 120 . The camshaft 40 is also engages with the rocker arm 120 . The rocker arm 120 is engagable with the engine valve 50 or a valve bridge (not shown). A valve spring 130 may be positioned to bias the engine valve 50 into a closed position.
[0015] Referring now to FIG. 2 , the fluid control valve 20 has a body 140 with a first fluid passage 150 that intersects an axial bore 160 . A first annular portion 170 may be present in the body 140 or on a movable member 180 , in fluid communication with first fluid passage 150 . In the axial bore 160 is a movable member 180 , which has a valve element portion 190 capable of permitting and blocking fluid flow. The movable member has an axis (not shown) along which linear or axial movement is permitted. A clearance 200 of predetermined magnitude exists between the axial bore 160 and the movable member 180 . The valve element portion 190 may be configured to be either a 2-way or 3-way valve, as are well known in the art. Furthermore, valve element portion 190 may be a poppet-type valve or a spool-type valve, or a combination of these types, as are well known in the art. The embodiment of valve element portion 190 shown in FIG. 2 permits flow in a first position, and blocks flow in a second position. In the first position, a groove 210 disposed on the movable member 180 is operatively positioned to provide fluid communication between the first fluid passage 150 and a second fluid passage 220 . In the second position, the groove 210 disposed on movable member 180 is operatively positioned to block fluid communication between the first fluid passage 150 and the second fluid passage 220 .
[0016] The second fluid passage 220 intersects the axial bore 160 . A second annular portion 230 may be present in the body 140 or on the movable member 180 , in fluid communication with the second fluid passage 220 .
[0017] The fluid control valve includes a means 238 for reducing fluid forces in a fluid control valve. The means may include a vent passage 240 , which passes through the body 140 and opens into the axial bore 160 at an axial location relative to the axial bore 160 between the first fluid passage 150 and an actuator 250 . The vent passage 240 is adapted to vent leakage fluid and reduce fluid forces acting on the movable member 180 . The vent passage 240 may communicate with the axial bore 160 at a third annular portion 260 , which may be contained in the body 140 , or a fourth annular portion 270 contained in the movable member 180 , or both. The vent passage 240 may be a singular vent passage, or may be a plurality of vent passages.
[0018] An actuator cavity 280 of the fluid control valve 20 adjoins a body end face 290 . The actuator cavity 280 is partially formed by a spacer 300 which adjoins a portion of the body end face 290 , and the actuator 250 which adjoins the spacer 300 . Inside the actuator cavity 280 may be an armature 310 , which is connected to movable member 180 , or which may be formed as an integral portion of movable member 180 . The actuator 250 is operatively connected to the movable member 180 and is adapted to move the movable member 180 in the axial bore 160 to the second position. The actuator 250 may be of either an electromagnetic device or piezo-electric device, as both types are well known in the art. A cap 320 may adjoin the actuator 250 . The cap 320 may be integrally formed with the actuator. A fastener 330 may secure the armature 310 to the movable member 180 . A spring 340 may engage the cap 320 and the fastener 330 , to bias the fastener 330 , the armature 310 , and the movable member 180 to the first position. Other arrangements are possible in which the spring 340 engages the armature 310 or the movable member 180 , rather than engages the fastener 330 .
[0019] The actuator cavity 280 may be drained of fluid through a slot 350 or a passage 360 . The spacer 300 surrounds the armature 310 , and may have one or more slots 350 , in either a first face 370 of the spacer 300 nearer to the body end face 290 or a second face 380 nearer to the actuator 250 , or may have one or more passages 360 passing through the spacer 300 . The passage 360 may be formed by a variety of known methods such as drilling, forming, stamping, electrical discharge machining, laser drilling, or other methods and may optionally include an orifice 390 of smaller diameter or area than the passage 360 .
[0020] Now referring to FIG. 3 a , the means 238 for reducing fluid forces may also include an inclined drain passage 400 formed in the body 140 at the body end face 290 adjoining the actuator 250 . The inclined drain passage 400 may be arranged substantially radially relative to a centerline of axial bore 160 . As seen in FIG. 4 in another embodiment, the means 238 for reducing fluid forces may also include the parallel drain passage 410 arranged substantially parallel with respect to the body end face 290 . Each fluid control valve 20 may include a plurality of inclined drain passages 400 , a plurality of parallel drain passages 410 , or a combination of single or plural inclined drain passages 400 and single or plural parallel drain passages 410 .
[0021] Now referring to FIG. 3 b , the inclined drain passage 400 , and/or parallel drain passage 410 may be arranged to have passage walls 420 that are substantial parallel, or substantial divergent, or may be a combination of passages 400 , 410 having at least one drain passage 400 , 410 with passage walls 420 that are substantially parallel and at least one drain passage 400 , 410 having passage walls 420 substantially divergent. Substantially parallel walls 420 may be advantageous for high volume manufacturing, however, in some cases substantially divergent walls 420 may better drain the actuator cavity 280 than parallel walls 420 .
INDUSTRIAL APPLICABILITY
[0022] In operation and with reference to FIGS. 1 . and 2 ., fluid from the sump 60 is delivered by the fluid supply 70 thorough the conduit 80 and the fluid control valve 20 and through the conduit 90 and the check valve 100 to the conduit 110 , where fluid is delivered to the fluidically driven actuator 30 . The camshaft 40 rotates to move the rocker arm 120 and open the engine valve 50 in a well-known manner. The fluidically driven actuator 30 moves to follow the motion of the rocker arm 120 , and may or may not remain engaged with the rocker arm 120 . A first signal is delivered to the fluid control valve 20 , which moves the movable member 180 to the second position, thereby blocking fluid flow through the fluid control valve 20 . As the camshaft 40 continues to rotate, the rocker arm 120 and the valve 50 begins to return to the closed position, until the rocker arm 120 engages the fluidically driven actuator 20 , which then holds the engine valve 50 in a partially-open position, as fluid flow from the fluidically driven actuator 30 is blocked. A second signal is delivered to the fluid control valve 20 , which moves the movable member 180 to the first position, thereby permitting fluid flow through the fluid control valve 20 , and fluid flow from the fluidically driven actuator 30 . The fluidically driven actuator 30 moves to permit the rocker arm 120 to move so that engine valve 50 can close. The first signal and the second signal could be analog or digital signals and could be the presence of a signal or the absence of a signal.
[0023] In particular, when the second signal is delivered, the actuator 250 is de-energized, and spring 340 holds the movable member 180 in the first position to permit fluid to flow between the first fluid passage 150 and the second fluid passage 220 . At the first position, fluid flows from the fluidically driven actuator 30 and no modification of the valve events occurs. The valve spring 130 pushes fluid out of the fluidically driven actuator 30 , through the fluid control valve 20 , into the fluid supply 70 .
[0024] When the first signal is delivered, the actuator 250 is energized, and the force of spring 340 is overcome, and the movable member 180 responsively moves linearly or axially along its axis to the second position to block fluid flow between the first fluid passage 150 and the second fluid passage 220 . At the second position, the valve element portion 190 blocks flow of fluid from the fluidically driven actuator 30 and a modification of the valve closing timing occurs.
[0025] To improve the operation of the flow control valve 20 when fluid travels along the clearance 200 between the axial bore 160 and the movable member 180 , venting of fluid to the outside of the fluid control valve 20 occurs, through the vent passage 240 , before fluid reaches the actuator cavity 280 . Such venting reduces the amount of fluid present in the clearance 200 that can slow the opening or closing of the movable member 180 . Communication of fluid from the clearance 200 to the vent passage 240 may be enhanced by the presence of a first annular portion 170 on body 140 or a second annular portion 230 on movable member 180 , which collects fluid from the entire clearance 200 around the movable member 180 , rather than only at the intersection of the vent passage 240 and the axial bore 160 .
[0026] In the event that fluid does reach the actuator cavity 280 , the slot 350 or the passage 360 and the one or more drain passages 400 , 410 reduce the amount of fluid collected in the actuator cavity 280 that may slow the opening or closing of the movable member 180 . Operation of the fluid control valve 20 under hot conditions for a period of time is more likely to cause low viscosity fluid to reach the actuator cavity 280 , that drains out through the aforementioned slots 350 and/or passages 360 , rather than collecting, as collected fluid has a tendency to slow the opening or closing of the movable member 180 . Should collected fluid in actuator cavity 280 or fluid in the clearance 200 cool to a lower temperature during shutdown of the engine 10 for a period of time, the fluid becomes more viscous, requiring larger forces to move the movable member 180 when the operation of the engine 10 is resumed for a later period of time.
[0027] In operation, this disclosure provides a method of reducing the effect of fluid forces acting on a movable member 180 movable relative to a body 140 . The movable member 180 in the body 140 is periodically moved linearly or axially by an actuator 250 , and a continuous venting of leakage fluid occurs from a location in the body 140 between the actuator 250 and a fluid passage 150 . This venting reduces the effect of fluid forces that may be present. Operation is also enhanced when a change in operating temperature occurs, such as when the engine 10 and valve position modification system 15 has been operated repeatedly to move a movable member 180 when fluid is at a first temperature, then stopping operation of the engine 10 and valve position modification system 15 , which discontinues moving of movable member 180 , until a later time when fluid is at a second temperature is less than first temperature. By venting some fluid during warm operation, a lesser amount of fluid remains which can restrict motion of the movable member during cooler operation, when the detrimental effect of the fluid is increased due to an increase in fluid viscosity at lower temperatures. Furthermore, the efficiency of collection of fluid increases when venting leakage fluid includes an annular portion 260 , 270 as the fluid is collected from the entire circumference of the movable member 180 . Fluid reaching the actuator cavity 280 is drained near an end face through one or more drain passages 400 , 410 .
[0028] It should be understood that the above description is intended for illustrative purposes only, and is not intended to limit the scope of the present disclosure in any way. Those skilled in the art will appreciate that other aspects, and features of the present disclosure can be obtained from a study of the drawings, the disclosure, and the appended claims. | Particularly in an engine that has been inactive for a substantial period of time at a cold temperature, fluid forces acting on moving members, such as electronically-activated fluid control valves, may be significant until the engine warms up. A way to reduce the fluid forces and their detrimental effects is to reduce the volume of fluid which are creating the fluid forces, including venting all or some of this fluid to drain. Additionally, fluid that gathers can be drained away. In order to accomplish such venting, the present disclosure includes a fluid control valve having a body with at least one fluid passage connected to a bore, a movable member in the bore, an actuator connected to the movable member to move the movable member, and at least one vent passage opening into the bore between the fluid passage and the actuator. The disclosure may include additional drain passages to drain away gathered fluid from actuating components. | 5 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims benefit of priority of U.S. Provisional Patent Application No. 62/368,113, filed Jul. 28, 2016, entitled “TWO STAGE MELTING AND CASTING SYSTEM AND METHOD”, which is incorporated herein by reference in its entirety.
SUMMARY OF THE DISCLOSURE
[0002] A “metal alloy” as used herein is defined as an alloy based on a metal. One species is a multi-component alloy wherein the multi-component alloy realizes an entropy of mixing of at least 1.25. Species within the genus of “metal alloy” includes aluminum alloys, nickel alloys, titanium alloys, steels, cobalt alloys, and chromium alloys.
[0003] As used herein, “multi-component alloy product” and the like means a product with a metal matrix, where a plurality of elements, typically four or more different elements make up the matrix, and where the multi-component product comprises 5-35 at. % of the four or more elements. In one embodiment, at least five different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least five elements. In one embodiment, at least six different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least six elements. In one embodiment, at least seven different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least seven elements. In one embodiment, at least eight different elements make up the matrix, and the multi-component product comprises 5-35 at. % of the at least eight elements. As described below, additives may also be used relative to the matrix of the multi-component alloy product to achieve an alloy generated by the system.
[0004] This disclosure presents a system for two stage casting of any metal alloy product such as a multi-component alloy. The first stage involves melting multiple feedstock of elements or known alloys and generating a desired composition of matter by varying the speed of the feedstock advancement into a molten form in a high pressure inert gas or metal vapor environment such that all metals introduced into the first crucible are retained in a liquid state in the first crucible. The second stage involves casting the desired composition by pulling the liquid phase crucible contents from the first stage into a second cooling crucible through a passageway using a casting piston attached to the cooling crucible and permitting the composition to cool into a solid state as the piston slowly withdraws the cooling crucible.
[0005] Briefly, a metal alloy with a specific composition is selected to be casted. The elemental components for this metal alloy are prepared as feedstock for the two stage casting system and loaded via a high pressure vacuum chamber into a melting crucible that has a surface layer several inches thick of a metal salt. This metal salt typically comprises CaF 2 along with minor additives and is heated via resistive heating current supplied by an electrical circuit. The first melting crucible is electrically connected to an electrical current power supply. The primary element feedstock acts as an electrode in the electrical circuit. Electrical current through the primary electrode, through the slag to the surface of the first crucible causes the metal salt layer to heat up, generating a high temperature slag layer, which in turn causes the primary feedstock electrode and secondary feedstock elements immersed in the slag to melt and puddle in the first melting crucible.
[0006] Preferably the primary element feedstock electrode and secondary feedstocks are dispensed through a vacuum pressure chamber on top of the metal salt/slag layer on the melting crucible. This chamber is pressurized with inert gas or metal vapor and maintained at a temperature and pressure suitable to stop element evaporation during the melting process, since various metals melt at different pressures and temperatures. Once all of the feedstock elements have reached liquid phase in the crucible, the melted feedstock is stirred, preferably by inductive or electromagnetic stirring, to ensure consistent uniform distribution of each element or constituent of the melt. After being stirred to a homogenous state, the mixture is withdrawn through an extraction valve, passage or port into a second stage cooling crucible beneath the first or melting crucible using negative pressure from a casting piston. In the second stage crucible, preferably a cold wall crucible, the mixture is cooled and forms a quiescent metal head on the casting piston. The casting piston is then slowly withdrawn as the melt solidifies and the cooled and solidified metal alloy can then be removed for further treatment or modification.
[0007] A system for two stage casting of a metal alloy in accordance with the present disclosure preferably has in a first stage a first melting crucible, a pressurized inert gas or metal vapor chamber connected to the first crucible to adjust a volatilization rate of metals in the melting crucible such that all metals introduced into the first crucible are retained in a liquid state in the first crucible, and a feedstock control system to dispense multiple feedstock metals into the chamber and into the melting crucible. The feedstock metals are dispensed at a rate sufficient to achieve a target composition of a final metal alloy. At least one of the multiple metal feedstock metals is in the form of an electrode, part of an electrical power supply supplying electrical current to the electrode.
[0008] The second stage includes a second cooling crucible connected to the first melting crucible via a passageway. The system preferably includes a layer of metal salt/slag disposed on an upper surface of the melting crucible. A distal tip of the electrode is submerged below the upper surface of the metal salt/slag layer. Electrical current through the electrode passes through the upper surface layer of the metal salt/slag and resistively heats the slag layer to a temperature above the melting point of the electrode. Secondary feedstock elements are also positioned in the high pressure vacuum chamber so as to extend into the metal salt/slag layer. Some of the secondary feedstock elements may be high density materials. Other of the secondary feedstock elements may be hollow so as to carry low density materials into the slag layer and into the first melting crucible.
[0009] The slag layer preferably has an increasing temperature gradient from the upper surface of the layer to a bottom of the layer, and is preferably controlled such that the upper surface has a temperature below the melting point of the primary or secondary elements. The bottom surface of the slag layer preferably has a temperature greater than the melting temperature of the element having the highest melting temperature. Preferably the slag layer has a thickness sufficient to achieve a first temperature associated with its upper surface, and a second temperature associated with its lower surface, wherein the first temperature is lower than the melting point of the electrode and wherein the second temperature is higher than the melting point of the electrode.
[0010] A two stage method of producing a metal alloy in accordance with the present disclosure comprises placing a metal salt layer in a first crucible, wherein the first crucible is connected to a second crucible via a passageway, introducing a first electrode into the metal salt layer, passing an electrical current through the first electrode to produce a slag layer in the first crucible from the metal salt layer via resistance heating, pushing the electrode into the slag layer so that a tip of the electrode begins to melt into a molten composition below the slag layer in the first crucible, introducing secondary feedstock elements into the heated slag layer to melt the secondary feedstock elements into the molten composition in the first crucible and continuing to melt the electrode and the secondary feedstock elements into the composition until a desired volume of composition is reached. Once the desired volume of molten composition is achieved, the method comprises opening the passageway to the second crucible such that the molten composition flows into the second crucible; and cooling the composition in the second crucible to a solid state.
[0011] The method may further include progressively lowering a piston attached to a bottom of the second crucible as the molten composition solidifies bottom up in the second crucible. Preferably during the first stage the primary electrode is a metal having a highest melting point of any of the elements to be introduced into the first crucible. In one embodiment the electrode is a hollow tube. The electrode may be titanium or a titanium alloy. In an embodiment the resistive heating of the metal salt by the first electrode heats the slag layer to a temperature above a secondary element melting point. In one embodiment, as a bottom portion of the composition in the secondary crucible solidifies the secondary crucible is withdrawn via a piston such that the bottom portion is progressively lowered relative to a top of the secondary crucible, and this progressive lowering is preferably continued until a solid ingot of the composition can be withdrawn for removal from the secondary crucible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a schematic cross-sectional diagram of an exemplary embodiment of a two stage multi-component alloy casting system in accordance with the present disclosure.
[0013] FIG. 2 is a schematic cross-sectional diagram of the upper portion of the embodiment shown in FIG. 1 illustrating one embodiment of an electrical power supply circuit.
[0014] FIG. 3 is a schematic cross-sectional diagram of an upper portion of the embodiment shown in FIG. 1 illustrating an exemplary electromagnetic stirring arrangement.
[0015] FIG. 4 is a schematic cross-sectional diagram of the crucible passageway shown in FIG. 1 illustrating an exemplary passageway closure.
DETAILED DESCRIPTION
[0016] In the description that follows, like numerals are utilized to describe like components and subcomponents in the various views.
[0017] As noted above, this disclosure presents a system/apparatus for two stage casting of a metal alloy such as a multi-component alloy. The system includes a first melting crucible 6 and a second cooling crucible 8 connected to the first crucible 6 via a selectively closable passageway 7 . The upper surface of the first crucible 6 is layered with a metal salt that when resistively heated forms a relatively thick slag layer 20 on the upper surface of the first crucible 6 and the melt 11 formed thereon.
[0018] This slag layer 20 may be 4 to 6 or more inches thick. It must be thick enough to have a large temperature gradient from top to bottom such that the upper slag layer surface temperature is lower than the lowest melting point of the feedstock element. The bottom surface of the slag layer 20 preferably has a temperature higher than the melting point of any of the feedstock elements.
[0019] The feedstock elements 1 , 2 , 3 to produce the desired alloy composition shown as melt 11 include at least one feedstock element that acts as a first electrode 1 connected to a remote electrical power supply 21 via a feedstock controller 4 . Secondary solid elements 2 , 3 are also included, whose feed rate is also controlled by the feedstock controller 4 , that add secondary elements to achieve the desired end composition of melt 11 . These elements 1 , 2 , 3 may be solid, for high density materials. The distal ends of these solid elements will sit below at least the surface of the slag layer 20 . Hollow elements that act as a tube to feed high volatile/low density materials to below the surface of the slag layer 20 may also be utilized.
[0020] FIG. 1 shows basic diagram of a two stage metal alloy casting system 100 in accordance with one embodiment of the present disclosure. The system 100 allows feedstocks 1 , 2 and 3 to be fed from a feedstock controller 4 into a melting first crucible 6 . The exemplary feedstock elements 1 , 2 , and 3 are each comprised of elemental metals or pre-alloys which can be melted together to form a desired molten multi-component alloy 11. The feedstocks 1 , 2 , and 3 and crucible 6 are disposed within a pressurized gas chamber 5 that may be under a vacuum or pressurized with an inert gas (He, Ar, N) or metal vapor, in some embodiments, to lower the volatilization rate of the various metal feedstocks. Many metal elements utilized in alloying processes volatize or melt at different temperatures and pressures. Preferably the chamber 5 is maintained at a desired temperature and pressure to maintain all constituent elements in a liquid state during processing as described herein. Use of a pressure chamber 5 results in an as cast microstructure of the melt as well as the end product solidified alloy 9 that includes volatile ingredient elements such as Li, Mg, and Zn in mixture with Titanium that would otherwise have been vaporized if pressure chamber 5 were not utilized.
[0021] The feedstock motion and power controller 4 is electrically powered via a DC power supply 21 shown in FIG. 2 . DC power is supplied to the system 100 via the power supply 21 such that current is fed through a primary feedstock electrode element 1 . The feedstock controller 4 is given feed rate instructions based on the specific amounts of each feedstock 1 , 2 , or 3 needed to produce the desired multi-component alloy product. The primary feedstock element electrode 1 is fed through the vacuum chamber 5 into the melting first crucible 6 which has a surface layer typically several inches thick of slag 20 . This slag layer 20 typically comprises CaF 2 along with minor additives and is heated via the arc melting electrical circuit shown in FIG. 2 . The primary element feedstock 1 acts as an electrode in the melting electrical current circuit shown in FIG. 2 . The melting first crucible 6 is electrically connected to the power supply 21 , as a return, thus completing the electrical circuit. The slag 20 acts as a series resistive element in this electrical circuit of the power supply 21 . The current passing through the electrode 1 resistively heats the slag 20 and melts the tip of the primary electrode 1 into the first crucible 6 initially forming a melt 11 . Electrical current fed through the feedstock controller 4 via the primary electrode 1 , and through the slag 20 to the first crucible 6 via resistive heating causes the slag 20 to heat up, which in turn causes the primary feedstock electrode 1 and then the secondary feedstock elements 2 and 3 , also immersed in the heated slag 20 , to melt and puddle as a common melt 11 in the melting first crucible 6 .
[0022] The feedstock controller 4 regulates the feed rate of each of the feedstocks 1 , 2 and 3 into the crucible 6 in proportion to the desired composition melt 11 to be generated. Furthermore, the feedstock controller 4 adjusts the position of the primary electrode 1 tip in the slag 20 so as to promote melting at a controlled rate.
[0023] The composition melt 11 is preferably stirred in the first crucible 6 . Stirring of the melt 11 may be accomplished by induction or electromagnetic stirring, mechanical stirring, sonic or ultrasonic agitation, or other mechanism. One exemplary arrangement for electromagnetic stirring is illustrated in FIG. 3 . Multi-component alloy melts 11 may contain elements which have a significant difference in density. Since the properties of a multi-component alloy depend on the uniformity of the elemental composition throughout the material, it is necessary to stir the liquid phase metal components together to ensure uniformity before they solidify. The composition 11 may be stirred electromagnetically by providing AC power to at least one induction coil 13 using a magnetic stirring control system 12 .
[0024] FIG. 3 shows an electromagnetic stirring control 12 . The magnetic stirring control 12 allows the system 100 to dynamically modify the parameters which control the magnetic stirring of liquid phase metals 11 in the first crucible 6 . The magnetic stirring control 12 is a component capable of adjusting the power to a magnetic stirring mechanism, such as a series of coils 13 , in order to vary the magnetic field allowing magnetic stirring of materials with different densities. An AC power source 14 supplies the magnetic stirring controller 12 . The magnetic stirring controller 12 adjusts the power and phasing to the magnetic stirring induction coils 13 , in order to vary the magnetic field allowing magnetic stirring of materials with different densities.
[0025] Once the melt 11 is adequately stirred to form the desired consistency of the multi-component alloy product, the melt 11 is transported through an extraction valve, passageway, or port 7 into a second chamber including a cold wall cooling crucible 8 . The cold wall crucible 8 is cooled so that a quiescent metal alloy composition head 9 comprising a solid metal alloy composition may form in the cold wall crucible 8 on the casting piston 10 . The casting piston 10 may then be lowered or withdrawn and the solid metal head 9 removed from the top of the piston 10 for further use or treatment as may be desired.
[0026] The feedstocks 1 , 2 , 3 described herein include at least two separate sources of raw material for the multi-component alloy product, and may include any form of elemental metals (e.g. Li, Ti, Mn, Cr, Fe, Co, Ni, Cu, Ag, W, Mo, Nb, Al, Cd, Sn, Pb, Bi, Zn, Ge, Si, Sb, and Mg) or pre-alloys, which can be in cylindrical wire form, granulated pellets, or powdered, for example. Preferably the primary element electrode 1 is the highest melting temperature element or alloy, such as Titanium. This way, as current is fed through the electrode 1 into the slag 20 , it will be heated high enough to progressively melt the Titanium. The heated slag 20 will in turn heat and melt the secondary feedstocks 2 and 3 such that they melt through the slag 20 into the first crucible 6 to coalesce into the melt 11 .
[0027] Optionally, the first crucible 6 may be constructed of a consumable metal material itself such that a portion of the first crucible 6 melts into and forms part of the melt 11 in the first stage. Also, one of the feedstock elements may be a pre-alloy such as an Aluminum and/or Titanium alloy or one or more of the feedstock elements 1 , 2 , 3 may be a more complex multi-component alloy such as one that comprises at least three or four or more element metals pre-alloyed together in a prior two stage process as above described.
[0028] In the embodiments described herein, the feedstock elements and alloys may be in a cylindrical wire form, granulated pellets, or powdered, etc. The electrode 1 may be a solid rod or may be hollow, or a hollow tube filled with another component element or alloy to become a part of the melt 11 . Furthermore, the slag 20 may also contain one or more feedstock elements or additives within it that combine with the feedstock elements 1 , 2 , and 3 during formation of the melt 11 .
[0029] FIG. 4 shows one exemplary embodiment of the system 100 in which a cooled valve pin 30 is utilized to controllably open a conical entrance portion 29 of the passageway 7 out of the crucible 6 into the solidifying head 9 on top of the cold crucible 8 . The entrance 29 to the passageway 7 is closed during the melting and formation of the melt 11 as above described. At least the entrance 29 of the passageway 7 is closed by a hollow trapezoidal tip shaped valve disk pin 30 during those operations. The passageway 7 is shown in FIG. 4 exaggerated in size for explanation purposes. The passageway 7 may be essentially eliminated downstream of entrance 29 such that the entrance 29 is all that exists of passageway 7 into the second cooling crucible 8 . When it is desired to transfer the melt 11 into the crucible 8 , the valve pin 30 is slowly withdrawn while a cooling liquid 31 is circulated within the valve pin 30 . Raising the pin 30 opens a gap A which is carefully controlled such that the melt 11 passing by the tip of the pin 30 and through the passageway 7 via gap A does not change to a solid state prior to dropping onto the head 9 . This may be controlled by reducing or increasing the gap A and by regulating the temperature of the cooling fluid 31 within the pin 30 during the transfer operation. The first crucible 6 , if made of a conductive metal such as copper, may also be cooled or thermally regulated such that the melt 11 formed via resistive heating of the slag layer 20 remains liquid during the first stage formation of melt 11 described above and during the transfer process through passageway 7 .
[0030] While various embodiments of the new technology described herein have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. For example, the two stage process and apparatus may be utilized over and over again utilizing one or more intermediate solid multi-component alloys produced in a previous stage as a pre-alloy element 1 , 2 or 3 in a subsequent use of the system 100 . It is to be expressly understood that such modifications and adaptations are within the spirit and scope of the presently disclosed technology. | A system for two stage casting of a metal alloy is disclosed that dispenses multiple feedstock metals into an arc melting crucible via a pressurized inert gas or metal vapor chamber to lower the volatilization rate of metals in an arc melting crucible at a rate proportional to the composition of the final desired alloy. The melt from the melting crucible enters a second stage cold wall crucible through a passage, where the melt cools and solidifies. A casting piston is used to slowly and progressively withdraw the solidified alloy from the cold wall crucible as it cools. | 2 |
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to cable locks, and particularly to cable locks used in secure facilities where there is a risk of residents utilizing heavy, portable objects as weapons.
2. Description of the Prior Art
Secure institutions such as prisons, schools, and hospitals often have means for residents to store personal property, such as lockers, storage cabinets, or foot lockers. These storage facilities are typically secured by using a padlock of some sort, operable either by key or combination. The locks most commonly employed at present are constructed primarily from hardened steel, which increases the weight of the padlocks, and results in a rigid structure. One popular model weighs close to six ounces despite being less than three inches in length. This poses a security problem itself: the relatively heavy weight and rigid structure of the locks allows them to be effectively used as weapons by residents, either as a projectile or by placing the lock inside a sock to form a makeshift bludgeon.
A cable lock, with its flexible cable, greatly reduces the rigid structure of a traditional padlock and thus reduces the potential for injury if the lock is used as a projectile. Combination-operated cable locks are known in the prior art, being typically utilized to temporarily secure bicycles and other moveable objects to a stationary object. However, such locks typically have cables or chains several feet in length and of at least ¼″ in diameter to accommodate a variety of objects being secured, and to enable such objects to be secured to stationary objects of varying size and shape. The length and diameter of these cables renders them heavy and typically impractical or unusable for securing lockers and other containers in institutional settings such as prisons, schools, and hospitals.
Alternatively, lightweight cable locks having a rigid plastic body are known in the prior art, and are typically used by travelers to secure luggage. Such locks may have a significant length of retractable cable, which poses its own danger in an institutional setting as a weapon. Furthermore, the plastic bodies of these locks are not usually impact or tamper resistant, which diminishes their security.
U.S. Pat. No. 5,819,560 illustrates a padlock possessing a composite plastic body, which reduces weight. However, the padlock still possesses a rigid structure by virtue of its hardened steel and dense plastic structure, which increases the risk of injury if the lock is thrown. It also is key-operated, which present the added problem of keys that secured residents have to keep, with the risks of loss or theft.
BRIEF SUMMARY OF THE INVENTION
The present invention summarized is a locking device consisting of a flexible cable of small diameter and short length, attached at one end to a locking mechanism of a combination or permutation type capable of being engineered smaller and lighter than the combination locking mechanisms typically found in prior art cable bicycle locks. The other cable end is attached to a key designed to be received and secured into the locking mechanism. The key and locking mechanism are fabricated from a lightweight material, such as aluminum or titanium, and preferably in a relatively simple mechanical fashion to ensure light weight, while retaining strength, security, and reliability. The cable is made of a flexible material of high tensile strength that is cut-resistant, such as braided or twisted steel strands, as is well known in the art, and may be coated with a durable plastic sheath such as vinyl or PVC to further protect the cable. Additionally, the locking mechanism is designed to accept a master key, which enables the administrator of an institution that the locking device is ideally suited for to unlock any lock on the premises without needing to know each individual lock's unique combination.
In the preferred embodiment, the locking mechanism consists of a hollow cylinder surrounded by a series of numbered, notched dials. The key has arranged along its length a series of locking lugs corresponding to each of the numbered dials. To close and secure the lock the numbered dials are aligned to a preset combination, the key is inserted into the hollow cylinder, and is finally secured into the body of the lock when the numbered dials are aligned to any combination other than the preset.
It is an object of the invention to provide a reasonably strong and secure padlock for use primarily by patients, residents, or incarcerated inmates in an institutional setting which will allow residents to secure their property. It is a further object of the invention to provide a padlock that is small enough and light enough so that it is not practically useful as a weapon.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1A is a perspective view of a lock as constructed according to the present invention;
FIG. 1B is a sectional view of the lock as shown in FIG. 1A ;
FIG. 1C is an exploded view of the lock as shown in FIG. 1A ;
FIGS. 2A-E are component views of the notched numerical dials as shown in FIG. 1 that form part of the locking mechanism of the preferred embodiment;
FIGS. 3A-C are component views of the lock core as shown in FIG. 1 that forms part of the locking mechanism of the preferred embodiment;
FIGS. 4A-D are component views of the key as shown in FIG. 1 that forms part of the locking mechanism of the preferred embodiment;
FIGS. 5A-C are component views of the tabbed washers as shown in FIG. 1 that form part of the locking mechanism of the preferred embodiment;
FIGS. 6A-C are component and sectional views of the assembled lock core end housing as shown in FIG. 1 and lock core as shown in FIG. 3 that form part of the locking mechanism of the preferred embodiment;
FIGS. 7A and B are component views of the cammed locking washers disposed inside of the lock core end housing shown in FIG. 6 that form part of the locking mechanism of the preferred embodiment;
FIGS. 8A and B are component views of the swaged key fixably attached to the end of the cable as shown in FIG. 1 that forms a part of the locking mechanism of the preferred embodiment;
FIGS. 9A-D are component views of a lock core end housing half as shown in FIGS. 1 and 6 that form part of the locking mechanism of the preferred embodiment;
FIGS. 10A-C are component views of the numerical index ring as shown in FIG. 1 that forms a part of the locking mechanism of the preferred embodiment; and
FIGS. 11A-C are component views of the cammed key used to effect removal of the swaged key as shown in FIG. 8 from the lock core end housing as shown in FIG. 6 , useful with the locking mechanism of the preferred embodiment.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the figures, the preferred embodiment is showed in FIGS. 1A-C . The lock consists of a cable 6 , which is permanently attached at one end to a key 1 . The other end of the cable 6 is attached to a lock core housing 2 , which in turn holds a hollow core shaft 20 in place. A lock assembly 3 , formed from a plurality of numerical dials 30 interleaved with an equal number of tabbed washers 50 , is fitted onto the shaft 20 . The lock assembly 3 is held in place on the shaft 20 by affixing a retaining clip 4 onto the end of the shaft 20 distal from the core housing 2 . The cable 6 is attached to the key 1 by fastening means that are well known in the art. The cable 6 is attached to the core housing 2 by inserting a swage key 80 , which is permanently affixed to the end of the cable 6 , into the end of the core housing 2 where a securing mechanism housed therein locks the cable 6 into place. The cable 6 may be removed by inserting the master unlock key 7 into the end of the core housing 2 , thereby disengaging the securing mechanism and releasing the cable 6 . An alternative embodiment has the securing mechanism embedded into the end of key 1 , where the key is comprised of a separate key shaft secured into a key housing, and core housing 2 and shaft 20 comprising a single, unified, cast piece.
FIGS. 2A-D depict the numerical dials 30 which form a part of the lock assembly 3 . Each dial 30 is disc-shaped, possessing a first surface 37 , a second surface 38 , a third essentially circular surface 35 running perpendicular to the first surface 37 and the second surface 38 and defining the outermost circumference of the dial 30 , and a circular flange 36 normal to and extending from the second surface 38 , concentrically inset from the circular surface 35 . A center hole 31 is positioned concentrically in and runs perpendicular to the first surface 37 and the second surface 38 . A notch 32 radially extends from the center hole 31 and is sized to an identical width as channel 22 and a height sufficient to just accommodate locking lugs 12 a , 12 b , 12 c , and 12 d . The center hole 31 is sized so as to allow the dial 30 to slide onto the shaft 20 and spin freely in place, but with minimal play. The circular flange 36 should extend from the second surface 38 a distance at least equal to the length of one of the corresponding locking lugs 12 a , 12 b , 12 c , or 12 d , less the thickness of a tabbed washer 50 . Disposed and equally spaced upon circular surface 35 are a plurality of numbered concave depressions 34 equal to and corresponding with the number of stops on the numbered dial 30 . A unique symbol, number, or other identifying mark is affixed to each concave depression 34 to facilitate entry of the lock's preset combination. A series of small round depressions 33 , located on the first surface 37 , equal in number to the number of stops on the numbered dial 30 , and equally spaced around and radially positioned adjacent to the center hole 31 , engage a protrusion 54 on each interleaved tabbed washer 50 , thereby providing a positive stop for each depression 34 .
The lock core of the preferred embodiment is built upon a core shaft 20 , depicted in FIGS. 3A-C . The core shaft 20 is tubular in shape, possessing a center bore 21 and at least one radially disposed channel 22 that runs the length of the core shaft 20 . Core shaft 20 is of a length sufficient to accommodate the complete lock assembly 3 and ensure it is held fast with a minimal amount of play along the length of shaft 20 when the shaft 20 is secured into the core housing 2 and retaining clip 4 is affixed. The center bore 21 is sized and shaped to just accommodate key shaft 11 with a minimal of play, while the channel 22 is sized to accommodate the protruding locking lugs 12 a , 12 b , 12 c , and 12 d . Also radially positioned around the circumference of core shaft 20 are a plurality of notches 23 a , 23 b , and 23 c positioned so as to engage an equal number of protrusions 53 on each tabbed washer. The core shaft 20 is attached to the core housing 2 by fitting the two halves of the core housing 2 around notch 26 and flange 27 on shaft 20 . The lock assembly 3 of interleaved numerical dials 30 and tabbed washers 50 are secured in place on the core shaft 20 by use of retaining clip 4 , which is positioned in groove 24 . Ideally the core shaft 20 as depicted in FIGS. 3A-C is fabricated as a single piece of cast aluminum, to ensure simplicity, light weight, and low cost.
In FIGS. 4A-D the key 1 consists of a key shaft 11 of a diameter sized to fit within the center bore 21 of the core shaft 20 . Radially disposed along the length of the key shaft 11 are locking lugs 12 a , 12 b , 12 c , and 12 d , separated from each other by spaces 13 a , 13 b , 13 c , and 13 d . The lugs 12 a , 12 b , 12 c , and 12 d are radially positioned and each sized so as to engage channel 22 of the core shaft 20 and when fully inserted into the lock assembly 3 fit within the space between the numerical dials 30 created by each flange 36 . The spaces 13 a , 13 b , 13 c , and 13 d are each sized so as to accommodate the thickness of a numerical dial 30 as measured between the first surface 37 and the second surface 38 . Key 1 may be permanently attached to the end of cable 6 by crimping a barbed fitting onto the end of cable 6 and inserting the end into cavity 14 , where the barbed fitting can engage channel 15 ; however, any method which allows for the permanent and secure attachment of key 1 onto the end of cable 6 is appropriate and in keeping with the scope of the invention. Should a different attachment method be utilized, cavity 14 and channel 15 may be modified or omitted, as appropriate. Ideally the key 1 as depicted in FIGS. 4A-D is fabricated as a single piece of cast aluminum, to ensure simplicity, light weight, and low cost.
FIGS. 5A-C depict the tabbed washers 50 . Each washer 50 is roughly disc-shaped, possessing a first surface 51 in a second surface 52 . A center hole 55 is concentrically centered and runs perpendicular between the first surface 51 and the second surface 52 . A notch 56 radially extends from the center hole 55 and is sized to an identical width as channel 22 and a height sufficient to just accommodate locking lugs 12 a , 12 b , 12 c , and 12 d . The center hole 55 is sized so as to allow the washer 50 to slide onto the core shaft 20 with minimal play. A plurality of protrusions 53 are radially disposed around the circumference of the center hole 55 and placed so as to engage notches 23 a , 23 b , and 23 c on the core shaft 20 , thereby fixably placing notch 56 in line with the channel 22 and preventing the washer 50 from rotating around the core shaft 20 . A second protrusion 54 engages depressions 33 on numerical dial 30 so as to provide positive detents for each numbered depression 34 on numerical dial 30 . Tabbed washer 50 is ideally machined from steel for enhanced durability.
The cable 6 is secured to the lock core housing 2 through a securing mechanism contained in the end of the lock core housing as depicted in FIGS. 6 through 9 . Turning to the figures which show the preferred embodiment of the securing mechanism as assembled into the core housing 2 and its working components, swage key 80 , permanently affixed to one of the ends of cable 6 , is inserted into aperture 91 , where it makes contact with locking disc 70 . Increasing pressure on the swage key 80 results in the locking disc 70 rotating to accommodate the swage key flat 83 . Once the swage key flat 83 passes the locking disc 70 , circular spring 61 forces the locking disc 70 to rotate back around the swage key 80 through the swage key locking channel 82 , thereby securing the cable 6 to the core housing 2 . Turning to FIG. 8 , the swage key 80 is permanently affixed to the cable 6 by inserting an end of the cable 6 into the swage key end cavity 84 , then crimping the swage key barrel 81 onto the cable 6 .
Details of the locking disc 70 are depicted in FIG. 7 . The locking disc 70 is roughly disc-shaped, possessing a first surface 71 and a second surface 72 . A center hole 76 is concentrically centered and runs perpendicular between the first surface 71 and the second surface 72 . The circular spring 61 engages hole 73 to allow the spring 61 to rotate the disc 70 into a locked position. The disc 70 secures the swage key 80 in place by use of a flat 74 that corresponds to swage key flat 83 . As the swage key flat 83 passes the disc flat 74 , the circular spring 61 rotates the disc flat 74 out of alignment with swage key flat 83 , and into swage key locking channel 82 . A cam lug 75 extending radially from the outer circumference of the disc 70 engages the master unlock key 7 , which thereby forces the disc 70 to rotate against the tension of circular spring 61 , bringing flat 74 back into alignment with swage key flat 83 , and thereby allowing removal of the swage key 80 from the core housing 2 .
The core housing 2 is depicted in greater detail in FIG. 9 , and is assembled from two mirrored halves. The swage key 80 is inserted into aperture 91 , which is shaped so as to accommodate the cross-sectional profile of the swage key 80 as taken from the portion of the key possessing the flat 83 , thereby preventing the swage key 80 from rotating within the aperture 91 . Alternatively, recession 96 , located at the bottom of aperture 91 , may be shaped so as to receive the tip of swage key 80 so modified in shape as to prevent the swage key 80 from rotating within the aperture 91 . The locking disc 70 is placed into channel 95 , with the circular spring 61 located immediately beneath it, as viewed in FIGS. 9A and 9C . One end of the circular spring 61 engages notch 62 , to allow the spring 61 to be tensioned. An arc-shaped slot 94 is provided to insert the master unlock key 7 , allowing access to the locking disc 70 . End flange 27 and groove 26 on core shaft 20 fit into notch 93 , to fixably secure shaft 20 to end housing 2 . Once the shaft 20 and components of the mechanism to secure cable 6 are placed into one of the halves of end housing 2 , the two halves are mated and permanently secured together by use of two drift pins placed into holes 92 a and 92 b.
An index ring 100 , depicted in FIG. 10 , is slipped over the core shaft 20 to provide a fixed index mark 101 which serves as a reference for dialing the lock's unique combination into the numerical dials 30 . The index ring 100 is fixed in place and prevented from spinning around the core shaft 20 by the presence of a notch 102 , which is sized to just engage an index tab 25 with minimal play, located on the end of the core shaft 20 proximal to the core housing 2 .
The master unlock key 7 , depicted in FIG. 11 , is fabricated from a single curved piece of metal, and is sized so as to just fit inside slot 94 on core housing 2 . Into one end of the unlock key 7 a curve 111 is milled, and set partially into the inside curve of the key. This curve 111 engages cam lug 75 as described above, allowing for the quick opening of the lock.
To close the lock, the numerical dials 30 are turned to the lock's preset combination by lining up the appropriate numbered depressions 34 with index mark 101 , which causes notches 32 to line up with channel 22 . The key 1 is then inserted into the lock core shaft 20 , where locking lugs 12 a , 12 b , 12 c , and 12 d fit into the spaces created by flanges 36 . The numerical dials 30 are then turned to a combination other then the lock's preset combination, thereby securing the key 1 into the core shaft 20 as each notch 32 is rotated out of alignment with channel 22 . The lock may be opened by resetting the numerical dials 30 to the lock's preset combination, and then pulling the key 1 from the core shaft 20 .
The above embodiment is only used to illustrate one possible method of practicing the present invention, and is not intended to limit the scope thereof. A person having skill in the art will recognize changes that may be made thereto while still practicing the claimed invention. | A cable padlock having a thin flexible cable, with a key attached to one cable end and a locking mechanism for receiving and securing the key attached to the other cable end, preferably of a combination or permutation type. The key and locking mechanism are constructed of lightweight materials such as aluminum, providing for a lightweight, compact, and potentially inexpensive padlock. A mechanism for detaching the cable from the locking mechanism by application of a master key is provided to allow an administrator of a facility utilizing a number of the locks to remove each lock without needing to lookup each lock's unique combination. The lock is accordingly useful in prisons, institutions, and other secured facilities where there are concerns that a traditional heavier lock could be used as a makeshift weapon. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of Korean Patent Application No. 2003-58029, filed on Aug. 21, 2003, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a monitor apparatus, and more particularly, a monitor apparatus improved in a pivoting structure of a monitor main body relative to a base member.
2. Description of the Related Art
A monitor apparatus, in general, comprises a monitor main body, and a base member disposed on a flat surface like a table, to support the monitor main body.
Recently, a monitor main body is produced using an image display panel such as an LCD (Liquid Crystal Display) and a PDP (Plasma Display Panel) which make the monitor main body slim comparable to the size of a screen.
By using such a flat-typed image display panel, the monitor apparatus has an advantage of reducing its volume remarkably, and thus can be designed to be easily controlled in various angles of a clockwise and counterclockwise direction and a rotating direction for a user's convenience, and such a flexibility is recently in demand.
Especially, a pivoting function, rotating about the clockwise and counterclockwise direction of the monitor main body for the user's convenience, is increasing in demand in manufacturing the monitor apparatus.
However, if the monitor apparatus is pivoted as described above, a corner of the monitor main body contacts with the base member and the flat surface on which the base member is located causing problems of limiting or disabling the pivoting function of the monitor apparatus because a distance between the monitor main body and the base member or between the monitor main body and the flat surface where the base member is located is not sufficient. Such problems are obvious in a wide monitor apparatus which is increasing in demand recently.
Another problem is that when the monitor main body is pivoted without having its angle and height adjusted to match with a user's eye level, the user may feel uncomfortable watching the monitor.
Therefore, adjusting methods have been provided to control the angle and the height of the monitor main body.
However, two separate methods are provided in a conventional monitor apparatus, one for pivoting the monitor main body and the other for adjusting the angle and the height of the monitor main body, and both methods need to be operated separately. Thus, it is inconvenient and complicated to pivot the monitor main body and to adjust its angle and height simultaneously.
SUMMARY OF THE INVENTION
Accordingly, it is an aspect of the present invention to provide a monitor apparatus preventing a corner of a monitor main body from contacting with a base member or a flat surface on which the monitor is located, by controlling a distance between the monitor main body and the base member while the monitor main body is pivoting relative to the base member.
Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
The foregoing and/or other aspects of the present invention are achieved by providing a monitor apparatus comprising a monitor main body displaying an image; a base member supporting the monitor main body; a connecting member combined to the base member, and supporting the monitor main body to be pivoted; a first guide plate having a first side pivotably combined to the connecting member, and a second side to be slidably combined to the monitor main body; a sliding unit provided between the first guide plate and the monitor main body and supporting the first guide plate to be slidable on the monitor main body; and a link unit having a first side combined to a rear side of the monitor main body and a second side combined with the connecting member, wherein the monitor main body moves up and down with respect to the base member by sliding on the first guide plate when the first guide plate pivots with respect to the connecting member.
According to an aspect of the present invention, the first guide plate comprises a guide groove, wherein the second side of the link unit passes through the guide groove of the first guide plate and combines with the connecting member, and the guide groove of the first guide plate is formed to prevent the first guide plate from being interrupted by the link unit when the first guide plate is pivoting with respect to the connecting member.
According to an aspect of the present invention, the guide groove of the first guide plate limits an angle formed when the monitor main body is pivoting with respect to the base member, and the length of the guiding groove is predetermined depending on a range of the limited pivoting angle.
According to an aspect of the present invention, the sliding unit comprises a guide rail combined to one of the first guide plate and a rear side of the monitor main body; and a sliding member combined to one of the first guide plate and the rear side of the monitor main body to be slidably combined to the guide rail.
According to an aspect of the present invention, the monitor apparatus further comprises a second guide plate provided between a rear side of the monitor main body and one of the guide rail and the sliding member, which is combined to the rear side of the monitor main body, wherein the first side of the link unit is combined to the second guide plate.
According to an aspect of the present invention, the monitor apparatus further comprises a pivoting bracket provided between the connecting member and the first guide plate, wherein the first guide plate is pivotably combined with the pivoting bracket, and the second side of the link unit is combined with the pivoting bracket.
According to an aspect of the present invention, one of the pivoting bracket and the first guide plate comprises a pivoting shaft, and the other one of the pivoting bracket and the first guide plate comprises a pivoting shaft hole pivotably accommodating the pivoting shaft.
According to an aspect of the present invention, the pivoting shaft protrudes and passes through the pivoting shaft hole.
According to an aspect of the present invention, the pivoting shaft comprises a stopper on an end part thereof to prevent the pivoting shaft from being loosened from the pivoting shaft hole.
According to an aspect of the present invention, the stopper is bent such that the end part of the pivoting shaft which passes through the pivoting shaft hole contacts with an edge of the pivoting shaft hole, to generate rotation friction between the pivoting bracket and the first guide plate.
According to an aspect of the present invention, the monitor apparatus further comprises a washer disposed between the pivoting shaft and the pivoting shaft hole.
According to an aspect of the present invention, the pivoting bracket is tiltably combined with the connecting member.
BRIEF DESCRIPTION OF THE DRAWINGS
These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompany drawings of which:
FIG. 1 is a perspective backside view of a monitor apparatus according to an embodiment of the present invention;
FIG. 2 is a perspective backside view of a monitor main body in a state of pivoting;
FIG. 3 is an exploded perspective view of a pivoting structure of FIG. 1 ;
FIG. 4 is a front view of the pivoting structure of FIG. 1 ;
FIG. 5 is a front view of the pivoting structure of FIG. 2 ;
FIG. 6 is a side view of the pivoting structure of FIG. 1 ; and
FIGS. 7 and 8 are schematic views of an operation of a link unit used in the monitor apparatus according to the embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. The embodiments are described below to explain the present invention by referring to the figures.
An example of a monitor apparatus to be described hereafter will be an LCD (Liquid Crystal Display) and a PDP (Plasma Display Panel), wherein a flat image display panel is provided.
Also, as terminologies to be described in a detailed description of an embodiment of the present invention, a pivoting direction refers to the monitor main body rotating about a clockwise and counterclockwise direction, and a tilting direction refers to the monitor main body rotating about a forward and backward direction relative to a connecting member.
In FIG. 1 through FIG. 6 , the monitor apparatus according to the embodiment of the present invention comprises a monitor main body 10 ; a base member supporting the monitor main body; a connecting member 30 connecting the base member 20 and the monitor main body 10 ; a pivoting bracket 40 provided between the monitor main body 10 and the connecting member 30 , and supporting the monitor main body 10 to be pivoted; a first guide plate 50 provided between the pivoting bracket 40 and the monitor main body 10 , and pivotably connected with the pivoting bracket 40 ; a second guide plate 60 having a first side combined to a rear side of the monitor main body 10 and a second side combined to the first guide plate 50 ; a sliding unit 70 provided between the first guide plate 50 and the second guide plate 60 , and combining the second guide plate 60 to be able to slide on the first guide plate 50 ; and a link unit 80 having a first side combined to the second guide plate 60 and a second side passing through the first guide plate 50 and combined to the pivoting bracket 40 , and thus connecting the second guide plate 50 and the pivoting bracket 40 .
The monitor main body 10 generates an image using the flat-typed image display panel like the LCD and the PDP.
The base member 20 is located on a flat surface such as a table on which the monitor apparatus is located and supports the monitor main body 10 .
A bottom part of the connecting member 30 is combined to the base member 20 , and an upper part of the connecting member 30 is tiltably combined with the pivoting bracket 40 . A tilting hinge 31 is provided in the upper part of the connecting member 30 to be tiltably combined with the pivoting bracket 40 .
The first guide plate 50 comprises a guide groove 52 , and a first side which slides on the second guide plate 60 by the sliding unit 70 , and a second side with a pivoting shaft 51 protruded rearward.
The pivoting bracket 40 comprises a pivoting shaft hole 41 rotatably combined with the pivoting shaft 51 on a first side thereof, and a second side of the pivoting bracket 40 is combined with the connecting member 30 .
The pivoting shaft 51 protrudes from a center area of the first guide plate 50 and passes through the pivoting shaft hole 41 , preventing the pivoting shaft 51 from being loosened from the pivoting shaft hole 41 by having a stopper 56 at an end of the pivoting shaft 51 . The pivoting shaft 51 comprises at least one washer 42 combined thereto.
The stopper 56 is bent, wherein the end part of the pivoting shaft 51 which passes through the pivoting shaft hole 41 contacts with an edge of the pivoting shaft hole 41 , generating rotation friction between the pivoting bracket 40 and the first guide plate 50 . The rotation friction is overcome and the monitor main body 10 becomes rotatable by a predetermined force applied by a user.
The washer 42 is provided either between the first guide plate 50 and the pivoting bracket 40 , or between the first guide plate 50 and the stopper 56 , and provides elasticity to generate the predetermined rotation friction between the first guide plate 50 and the pivoting bracket 40 .
The sliding unit 70 comprises at least one guide rail 71 and a sliding member 72 slidably engaged to the guide rail 71 . The guide rail 71 is combined to one of the first guide plate 50 and the second guide plate 60 , and the sliding member 72 is combined to one of the first guide plate 50 and the second guide plate 60 . According to the embodiment of the present invention, a pair of guide rails 71 is combined to the second guide plate 60 , and a pair of sliding members 72 slidably engaged to the pair of guide rails 71 is combined to the first guide plate 50 .
The pair of guide rails 71 is combined with the pair of sliding members 72 accommodated therein, wherein the pair of sliding members reciprocatingly slide along the pair of guide rails 71 .
Unlike the embodiment described above, the pair of guide rails 71 may be combined to a rear side of the monitor main body 10 without being combined to the second guide plate 60 , and the link unit 80 may be directly combined to a rear side of the monitor main body 10 , and thus the second guide plate 60 may not be necessary. However, the second guide plate 60 should be included to increase efficiency of producing monitor apparatus according to the embodiment of the present invention in an assembling process.
The link unit 80 passes through the guide groove 52 of the first guide plate 50 and is combined to the pivoting bracket 40 at a position separate from a center of the pivoting shaft 51 accommodated in the pivoting bracket 41 .
Thus, the link unit 80 controls the second guide plate 60 to slide on relative to the first guide plate 50 , and thus the monitor main body 10 is moved upward relative from the base member 20 when the first guide plate 50 is pivoting relative to the pivoting bracket 40 .
The link unit 80 comprises a screw hole 81 respectively formed in end parts thereof, wherein a first hinge shaft 86 and a second hinge shaft 87 are respectively combined to each of the screw holes 81 , and spirals (not shown) formed in end parts of the first hinge shaft 86 and the second hinge shaft 87 , the link unit 80 is combined relative to the first guide plate 50 and the pivoting bracket 40 . Thus, the link unit 80 is rotatably combined to the second guide plate 60 and the pivoting bracket 40 .
A detailed description about an operation mechanism of the link unit 80 according to the embodiment of the present invention is as follows. In FIG. 7 and FIG. 8 , the link unit 80 is combined to an upper part of the pivoting bracket 40 in a point (b) located on an axis clockwise rotated about a center (a) of the pivoting shaft 51 at an angle of approximately 45 degrees with a vertical axis passing, and combined to the second guide plate 60 in a point (c) located on an axis passing the center (a) of the pivoting shaft 51 and separated farther than the point (b) where the link unit 80 is combined to the pivoting bracket 40 from the center (a) of the pivoting shaft 51 .
When the first guide plate is pivoting by rotating clockwise at an angle of 90 degrees relative to the pivoting bracket 40 , the second guide plate 60 slidably combined with the first guide plate 50 rotates along the first guide plate 50 . The link unit 80 is combined to the second guide plate 60 , therefore the link unit 80 also rotates clockwise about the point (b) where the link unit 80 and the pivoting bracket are combined to each other. Here, the link unit 80 rotates at an angle of 90 degrees, thus the point (c) is located in a lower part of the pivoting bracket 40 . Herein, the link unit 80 rotates as much as the first guide plate 50 is rotated.
According to the operation of the link unit 80 described above, when the first guide plate 50 is pivoting relative to the pivoting bracket 40 , the second guide plate 60 slides upward relative to the first guide plate 50 by the link unit 80 .
Based on this operation, an angle and a height of the monitor main body 10 are adjusted relative to the base member 20 by pivoting the first guide plate 50 clockwise and counter clockwise relative to the pivoting bracket 40 depending on combination locations of the link unit 80 and the pivoting bracket 40 , and of the link unit 80 and the second guide plate 60
The guide groove 52 , as shown in FIG. 4 and FIG. 5 , is not to be interrupted by the link unit 80 which penetrates the first guide plate 50 . Also, the guide groove 52 limits a pivoting angle of the monitor main body 10 relative to the base member 20 , and comprises a predetermined length depending on a range limited to desired angles of pivoting.
With such a configuration above, the operation of the monitor apparatus according to the embodiment of the present invention is as follows.
First, the monitor main body 10 rotates clockwise to pivot relative to the base member 20 , and the rotation causes the first guide plate 50 and the second guide plate 60 provided in a rear side of the monitor main body 10 to rotate relative to the pivoting bracket 40 . The link unit 80 , which passes through the first guide plate 50 and connects the second guide plate 60 with the pivoting bracket 40 , moves along the second guide plate 60 and thus, the point where the link unit 80 and the pivoting bracket 40 are combined rotates clockwise about a center axis of rotation. Here, the link unit 80 rotates as much as the first guide plate 50 rotates. However, the first guide plate 50 and the link unit 80 have different center axes of rotation, and thus the link unit 80 mechanically controls the second guide plate 60 to slide on the first guide plate 50 according to the operation of the link unit 80 described above, and the monitor main body 10 is raised relative to the base member 20 . Accordingly, the monitor main body 10 is raised at the same time it pivots relative to the base member 20 .
Herein, the monitor apparatus according to the embodiment of the present invention is designed to prevent a corner of a monitor main body from contacting with a base member or a flat surface on which the monitor apparatus is located when the monitor main body is pivoting relative to the base member by controlling a distance between the monitor main body and the base member. Also, the monitor main body maintains a proper height and angle corresponding to a user's eyelevel.
Although a few embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents. | A monitor apparatus includes a monitor main body displaying a picture; a base member supporting the monitor main body; a connecting member combined to the base member, and supporting the monitor main body to be pivoted; a first guide plate having a first side pivotably combined to the connecting member, and a second side to be slidably combined to the monitor main body; a sliding unit provided between the first guide plate and the monitor main body and supporting the first guide plate to be slidable on the monitor main body; and a link unit having a first side combined to a rear side of the monitor main body and a second side combined with the connecting member, the monitor main body moves up and down with respect to the base member by sliding on the first guide plate when the first guide plate pivots with respect to the connecting member. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is related to U.S. application entitled“APPLIANCE AND METHOD OF USING SAME HAVING A SEND CAPABILITY FOR STORED DATA” U.S. application Ser. No. 09/130,869, U.S. application entitled“APPLIANCE AND METHOD OF USING SAME HAVING A USER HELP CAPABILITY” U.S. application Ser. No. 09/130080, U.S. application entitled“APPLIANCE AND METHOD OF USING SAME HAVING A DELETE CAPABILITY FOR SAVED DATA” U.S. application Ser. No. 09/130082, U.S. application entitled“APPLIANCE AND METHOD OF USING SAME HAVING A CAPABILITY TO GRAPHICALLY ASSOCIATE AND DISASSOCIATE DATA WITH AND FROM ONE ANOTHER” U.S. application Ser. No. 09/130,789, U.S. application entitled“APPLLINCE AND METHOD FOR COMMUNICATING AND VIEWING MULTIPLE CAPTURED IMAGES” U.S. application Ser. No. 09/130081, U.S. application entitled“APPLIANCE AND METHOD FOR NAVIGATING AMONG MULTIPLE CAPTURED IMAGES AND FUNCTIONAL MENUS” U.S. application Ser. No. 09/130,584, U.S. application entitled “APPLIANCE AND METHOD FOR CAPTURING IMAGES HAVING A USER ERROR INTERFACE” U.S. application Ser. No. 09/130,572, U.S. application entitled “APPLIANCE AND METHOD FOR VIEWING CAPTURED IMAGES” U.S. application Ser. No. 09/131,258, and U.S. application entitled“APPLIANCE AND METHOD FOR MENU NAVIGATION” U.S. application Ser. No. 09/130,868, which are filed contemporaneously herewith and are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates generally to the field of capturing information (e.g., text, graphics, photos, etc.) for storage in a digital format and, more particularly, to a portable hand-held appliance for capturing images through digital scanning that has a graphical user interface for displaying the captured images for user manipulation and processing, and communicating those images to another device or appliance.
Intangible information is a vital business asset that can be exploited for competitive advantage if managed properly. In the past fifteen years, improvements in information processing have been achieved primarily from the widespread use of microcomputers in the workplace and their application in local and wide area networks. Through such applications as electronic mail (email) and networked access to document storage servers, the electronic communications market has exploded.
Nevertheless, business is still far from reaching a“paperless” workplace. For example, according to a 1993 report by BIS Strategic Decisions (hereinafter BIS), an information technology consulting firm, more than 90 billion documents were created in 1992 and more than 1 trillion copies of those documents were made. Moreover, BIS estimated that printing and copying expenses average between 6% and 13% of a typical company's revenue. These statistics illustrate the economic savings available for those businesses that are able to merge paper and technology in a unified information processing strategy.
One tool that has proven useful for translating between paper and electronic information is the digital scanner. Scanner-enabled document distribution endows paper-based documents with the speed and convenience of electronic communications. A desktop scanner or network scanner allows business professionals to scan paper-based documents, manage them-effectively and distribute them in a timely fashion. Users can share and distribute information easily by scanning directly to their email or personal computer (PC) fax applications. The growing popularity of fax modems and email is driving the acceptance of scanner-enabled document distribution in offices of all sizes. Fax/modem capabilities, which are available with virtually all modern PCs, enable users to send and receive faxes directly from a computer—at their desk or while traveling—and to check email remotely.
Nevertheless, while scanners are ideal for users who need to disseminate paper-based information to colleagues through PC facsimile and/or email, traditional flatbed scanners lack the convenience and flexibility that users have become accustomed to through such products as notebook computers and cellular phones. Hand-held scanners are an improvement in this regard; however, they are typically dependent on a host computer for displaying the scanned images and for providing power. U.S. Pat. No. 5,550,938 to Hayakawa et al. (hereinafter Hayakawa) discloses a portable image scanner designed to overcome these disadvantages. Specifically, Hayakawa discloses a hand-held cordless image scanner having a display/control screen, a memory for storing scanned images, a self contained power supply and an interface that allows the scanner to be received by a host computer as a memory card for transferring stored images from the scanner to the computer. While Hayakawa's scanner is effective in breaking the dependency on a host computer for image display and power, it still has several drawbacks. For example, Hayakawa's scanner offers no image processing features other than the capabilities of storing or discarding a newly scanned image and reviewing those images that have been stored previously. More advanced image processing would necessarily be done after transfer to a host computer. Moreover, Hayakawa does not offer a graphical user interface (GUI) containing icons and/or animations to assist users in operating their device. Finally, transfer of images is limited to those devices having ports for receiving an external memory card or the capability of reading the scanner memory through a memory card drive.
Accordingly, what is sought is a portable, hand-held image capturing device that allows users to process or manipulate captured images in the device and the ability to communicate the images directly to some other unit such as a computer, printer, or facsimile machine. In addition, the image capturing device should provide cordless operation and use a standard interface for transferring images to other devices. A GUI is preferred to assist users, particularly novices, in operating the device.
SUMMARY OF THE INVENTION
Certain novel features and advantages of the invention will be set forth in the description that follows and will become apparent to those skilled in the art upon examination of the following or may be learned with the practice of the invention.
To achieve the novel features and advantages, the present invention is generally directed to a portable hand-held image capture and communication appliance and method of using same by which images may be captured via capturing means and saved in an internal memory. The appliance includes a processor for manipulating and exhibiting the images on a built-in display screen. Program code stored in the internal memory and executed by the processor includes a capture page module for processing the image data acquired through the scanning means by filtering and discarding redundant image data to form a whole image.
According to an aspect of the invention, the capture page module includes a code segment for displaying a first animation. In the preferred embodiment, the first animation is designed as a metaphor to signify the progression of the image data processing taking place in the appliance. The metaphor used in the preferred embodiment is a bar graph in which the bar fills a space in proportion to the progress made in completing the image data processing.
According to another aspect of the invention, the capture page module includes a code segment for displaying a second animation in which the most recently captured image is shown displacing a previously captured image from the display. Advantageously, this animation communicates to the user the logical sequencing of the captured images as the new last image in the sequence displaces the previous last image in the sequence. Moreover, the display of the newly captured page or image allows the user to examine the page in detail to verify whether the correct scan path was followed and whether any desired content is missing from the image.
Should an error occur during the scanning process, the capture page module invokes an error utility module to display a textual dialog explaining the nature of the error.
The appliance according to the present invention has many advantages, a few of which are highlighted hereafter, as examples.
One advantage of the invention is that intelligent image processing features, normally reserved for a traditional computer, are provided in a portable, hand-held image capturing appliance.
Another advantage of the invention is that images or pages can be acquired using a simple and easy to learn scan technique.
Still another advantage of the invention is that animation is used during post capture processing to communicate to the user the results of the scan, including whether an errant scan path was followed and/or image content was missed during the scan.
Yet another advantage of the invention is that a GUI is provided, which allows new users to operate the appliance with minimal training or assistance.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Other features of the present invention will be more readily understood from the following detailed description of specific embodiments thereof when read in conjunction with the accompanying drawings, in which:
FIG. 1A is an elevation view of the hand-held image capture and communication appliance according to the present invention, which depicts a side of the unit containing the display screen, operation buttons, and navigation buttons;
FIG. 1B is an elevation view of the appliance of FIG. 1A depicting the opposing side to that illustrated in FIG. 1A, which contains the capture button for performing an image capture;
FIG. 1C is an elevation view of the appliance of FIGS. 1A and 1B depicting an end of the unit, which contains the power switch,
FIG. 1D is an elevation view of the appliance of FIGS. 1A, 1 B, and 1 C depicting the opposing end to that illustrated in FIG. 1C, which contains a brightness button for adjusting the visual clarity of the display screen;
FIG. 2 is a high-level block diagram of the internal hardware and software architecture of the appliance illustrated in FIGS. 1A-1D;
FIG. 3 is a high-level state diagram of the application software of FIG. 2;
FIGS. 4A and 4B illustrate the tools menus displayed on the display screen of FIG. 1A;
FIG. 5 illustrates the send menu displayed on the display screen of FIG. 1A;
FIG. 6 illustrates the delete menu displayed on the display screen of FIG. 1A;
FIG. 7 illustrates the help menu displayed on the display screen of FIG. 1A;
FIGS. 8A and 8B depict memory usage indicator icons on the display screen of FIG. 1A that provide a memory utilization report for the appliance;
FIG. 8C illustrates a thumbnail view of a captured image on the display screen of FIG. 1A;
FIG. 8D illustrates a zoom view of a captured image on the display screen of FIG. 1A;
FIGS. 9A and 9B are a flow chart describing the page or image capture process using the appliance of FIGS. 1A-1D and controlled by the capture page module of FIG. 2;
FIGS. 10A-10D depicts a proper scan path using the appliance of FIGS. 1A-1D; and
FIGS. 11A-11B depicts an improper scan path using the appliance of FIGS. 1A-1D;
FIGS. 12A-12B depicts another improper scan path using the appliance of FIGS. 1A-1D;
FIG. 13 illustrates a post-processing screen following an image or page scan displayed on the display screen of FIG. 1A;
FIG. 14 illustrates a scan error screen displayed on the display screen of FIG. 1A;
FIG. 15 illustrates a verification screen for a captured image or page displayed on the display screen of FIG. 1A; and
FIG. 16 illustrates a rectangularized version of a captured page displayed on the display screen of FIG. 1 A.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
While the invention is susceptible to various modifications and alternative forms, a specific embodiment thereof is shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that there is no intent to limit the invention to the particular form disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.
Architecture of the Image Capture and Communication Appliance
A portable, hand-held, image capture and communication appliance 22 embodying the principles of the present invention is shown in FIGS. 1A through 1D. Specifically, FIG. 1A depicts one side (i.e., front) of appliance 22 where a flat-panel display 24 along with user operation buttons 26 , 28 , 32 , 34 , 36 , 38 and user navigation buttons 42 , 44 , 46 , 48 are located. Display 24 is preferably of the flat-panel variety to accommodate the hand size dimensions of appliance 22 . Common types of flat-panel displays suitable for use in the present invention include electroluminescent displays, gas plasma discharge displays, and liquid crystal displays (LCDs). Display 24 is the means by which information, including captured images, text, icons, and animations, is communicated to the user. As used herein, the term“image” encompasses both text (binary) and color, graphic, or grayscale visuals. The user operation buttons comprise an image send or transmit button 26 , an image zoom button 28 , an image rotate button 32 , an image delete button 34 , a help utility button 36 and a tools menu button 38 . Send, zoom, rotate, and delete buttons 26 , 28 , 32 and 34 allow the user to electronically manipulate an image or page that has been captured into memory through photoelement array 52 . Note that an image captured in memory is interchangeably referred to herein as a“page” because the image is portrayed in appliance 22 as a physical page of text and/or imagery. Activation of tools button 38 presents the user with a menu that includes possible image operations (e.g., image attachment/grouping, image detachment/ungrouping), changing the mode of appliance 22 (i.e., toggling between text (binary) capture and color, graphic, or grayscale capture modes), calibrating appliance 22 , displaying a screen identifying important specifications such as a model number, hardware or software release number, memory equipage, etc., or other user utilities not deserving of a dedicated external button for activation. Help button 36 provides the user with access to general tutorials, process animations, how-to instructions on the operation of appliance 22 , and context sensitive instruction when help is requested while another operation or menu is active. The navigation buttons include an up button 42 , a down button 44 , a left button 46 , and a right button 48 and are controlled by the user to steer a course through menu items and to view images or pages that have been captured in memory.
FIG. 1B shows the side of appliance 22 opposite that illustrated in FIG. 1A (i.e., back). The back side of appliance 22 includes image capture button 54 , which is depressed by a user to capture an image through photoelement array 52 and is released once the image is captured. A power switch 56 is included at one end of appliance 22 as shown in FIG. 1C and a brightness control 58 for display 24 is located at the other end of appliance 22 as shown in FIG. 1 D. The positioning of the various buttons, power switch 56 , and brightness control 58 on appliance 22 as shown in FIGS. 1A through 1D is merely exemplary and can be modified as needed to satisfy the ergonomic requirements of the targeted user community.
Referring now to FIG. 2, the internal architecture of appliance 22 will be described hereafter. Appliance 22 includes a processor 62 , which communicates with a memory 64 via address/data bus 66 . Processor 62 can be any commercially available or custom microprocessor suitable for an embedded application. Memory 64 is representative of the overall hierarchy of memory devices containing the software and data used to implement the functionality of appliance 22 . Memory 64 can include, but is not limited to, the following types of devices: cache, ROM, PROM, EPROM, EEPROM, flash, SRAM, and DRAM. As shown in FIG. 2, memory 64 holds four major categories of software and data used in appliance 22 : the operating system 68 ; the application software 70 ; the I/O device drivers 72 ; and the image data 74 generated for each capture. Operating system 68 should be designed for real time embedded applications and, preferably, is relatively compact to make the most efficient use of memory 64 . One such example of a real time operating system meeting these criteria is the PSOSYSTEM operating system (pSOSystem® or pSOS®) sold by Integrated Systems, Inc., 3260 Jay Street, Santa Clara, Calif. 95054-3309, which is used in the preferred embodiment of the present invention. I/O device drivers 72 include software routines accessed through operating system 66 by application software 70 to communicate with devices such as display 24 , certain memory components 64 and I/O ports such as a serial port or infra red (IR) port for transferring data to another appliance, device or system. The digital representations of the images captured by appliance 22 is denoted by image data 74 . The format used for storing the images should be compatible with application software 70 . One common format used for encoding images is the CCITT standard, which is used in the preferred embodiment of the present invention; however, other public or proprietary standards can be used with equal success. For example, JPEG is a common standard used to encoded graphic or color images. Finally, application software 70 comprises the control programs that implement the various features of appliance 22 . Application software 70 and devices drivers 72 are typically written in a high-level programming language such as C or C++ for development convenience. Nevertheless, some drivers or application modules are sometimes written in assembly or machine language to optimize speed, memory usage or layout of the software in memory. In the preferred embodiment, the present invention uses C language to implement most application software 70 and device drivers 72 . Assembly language is used to implement time-critical code segments.
Application software 70 can be broken into several modules corresponding to the various features of appliance 22 , as shown in FIG. 2 . These software modules include an initialization module 76 , a capture page module 78 , a thumbnail view module 82 , a zoom view module 84 , a page rotation module 86 , an attach page module 88 , a detach page module 92 , a delete page module 94 , a send page module 96 , an error utility module 98 , a help utility module 102 and a menu/navigation interface module 104 . A brief overview of each of the aforementioned modules follows hereafter.
Initialization module 76 contains the boot software that is invoked when appliance 22 powers up. This module works closely with operating system 68 and device drivers 72 to perform any hardware initialization for processor 62 , memory devices 64 , display 24 , and software initialization for global resources, such as message queues and buffers, system tasks, and memory partitions. Capture page module 78 controls the acquisition of images through photoelement array 52 and their conversion into a suitable format for storage in memory 64 . The operation of capture page module 78 will be discussed in detail hereinafter. Thumbnail view module 82 provides the default visual for pages and icons shown on display 24 . For example, FIGS. 8A and 8B show a memory usage indicator icon for the cases where memory 64 is empty (i.e., no captured pages in memory) and where memory 64 holds 25 captured pages. In FIG. 8C, thumbnail view module 82 presents an entire captured page on display 24 . Zoom view module 84 allows the user to magnify a portion of a page as illustrated in FIG. 8 D. Page rotation module 86 allows the user to rotate a page either in thumbnail or zoom view in 90° increments. Attach page module 88 allows the user to logically join pages together to form a group of pages that can be manipulated as an individual unit. Conversely, detach page module 92 allows the user to separate a page or pages from a previously formed group. Delete page module 94 allows the user to purge a page or group of pages from memory 64 . Send page module 96 allows the user to transfer a page or group of pages to another appliance, device or system through the serial or IR communication ports of appliance 22 . Error utility module 98 provides notification to the user when the user attempts an invalid operation. Help utility module 102 provides the user, in real time, with general instructions through text and animation for operating appliance 22 and context sensitive instructions for performing a specific operation. Lastly, menu/navigation interface module 104 provides the user with graphical menus for performing various operations and processes the user's response thereto. Moreover, menu/navigation interface module 104 responds to navigation buttons 42 , 44 , 46 , and 48 that allow the user to steer a course through the graphical menus and view the stored pages.
A high level state diagram for application software 70 is shown in FIG. 3 . This state diagram is useful for gaining a broad understanding of the operation of application software 70 and its associated software modules. These states are representative of tasks or processes in application software 70 that act on messages from a message queue, which are generated as a result of user interaction with appliance 22 (i.e., activation of buttons). Appliance 22 and application software 70 begin and terminate from the off state 106 , which is controlled by the user through operation of power switch 56 . Off state 106 can clearly be entered from any other state in response to a user turning appliance 22 off through switch 56 . When a user turns switch 56 to the on position, the system will pass through a transient initialization state 108 during which time initialization module 76 is invoked to perform its functions. Once system initialization is complete, the system enters the thumbnail view state 112 , which is the default state for viewing any captured images. From thumbnail view state 112 , the system can transition to any one of several possible states depending on the action by the user. For example, the capture button can be pressed to enter capture state 114 to perform an image capture. After the image is captured, the button is released to return to thumbnail view state 112 . If the user wishes to change the orientation of the captured image, then activation of rotation button 32 will rotate the captured image 90° with each invocation. Moreover, now that an image is captured in memory 64 , a user can obtain a magnified view of a portion of the image or page by pressing zoom button 28 to enter zoom view state 116 . Similar to thumbnail view state 112 , the magnified image can also be rotated through application of rotation button 32 . The system will return to thumbnail view state 112 through operation of zoom button 28 .
From thumbnail view state 112 or zoom view state 116 , one of four menu states can be entered depending on the choice made by the user. First, activation of tools button 38 will transition the system into tools menu state 118 where a menu of possible page operations and/or features is exhibited on display 24 as illustrated in FIGS. 4A and 4B. Second, activation of send button 26 will transition the system into send menu state 122 where a menu of options for transferring a page or group of pages to another appliance, device or system is exhibited on display 24 as illustrated in FIG. 5 . Third, activation of delete button 34 will transition the system into delete menu state 124 where a menu of options for deleting a page or group of pages from memory 64 is exhibited on display 24 as illustrated in FIG. 6 . Lastly, activation of help button 36 will transition the system into help menu state 126 where a menu of help topics is exhibited on display 24 as illustrated in FIG. 7 . Once any of the aforementioned menu states is reached, the user can choose a desired menu option by using navigation buttons 42 and 44 and then validating the choice by pressing a confirmation button. In the preferred embodiment of the present invention, the confirmation button is simply the button by which the present menu on display is accessed. An icon indicating the appropriate confirmation button is displayed in the lower left hand side of the menus as illustrated in FIGS. 4 through 7. Menu states may be exited by simply invoking navigation button 46 to transition to a previous state.
An invalid response by the user (i.e., user presses an inactive button) will result in a transition to the default message handler state 128 where the user response is interpreted through the message that was generated internally. Frequently, the invalid response by the user will simply be ignored. Nevertheless, depending on the button that was invoked and the current state of application software 70 , a transition is sometimes made to the error dialog state 132 to notify the user of their error via a message or graphic (e.g., a blinking icon) on display 24 . Alternatively, error dialog state 132 can be entered directly if application software 70 detects an error in the execution of a valid operation. The most common example of this is when the user follows an improper capture path with appliance 22 during the image capture process.
The procedure of capturing an image or page with appliance 22 and the control exercised by capture page software module 78 will be described hereafter with frequent reference to (a) the flow charts of FIGS. 9A and 9B; (b) the animation scenes depicting proper and improper scan techniques of FIGS. 10A-10D, 11 A- 11 B, and 12 A- 12 B; the error screen of FIG. 14; and the image or page post-processing, verification, and rectangularization screens of FIGS. 13, 15 , and 16 .
Capturing a Page with the Appliance
A user initiates a page capture through activating image capture button 54 on the back of appliance 22 . Thus, as represented by decision diamond 134 in FIG. 9A, the process begins with capture page module 78 (see FIG. 2) processing a message indicating that capture button 54 has been activated. Depending on the current state of application software 70 , a page capture may not be a valid operation as indicated by decision diamond 136 . If page capture button 54 is not currently active or live, the user's attempt to capture a page is ignored. In the preferred embodiment, unless the system is in the process of actively sending a page to another device, which is encompassed in send menu state 122 of FIG. 3, or communicating an error to the user, which is represented by error dialog state 132 of FIG. 3, application software 70 will abort the current task and begin a page capture. Note that even if the system is currently displaying the send menu, as shown in FIG. 5, to start a send operation, a page capture initiation will override this state unless data is currently being transferred between appliance 22 and another device. Thus, if page capture button 54 is active, the process continues by following termination A where, as discussed in the foregoing, the current operation is aborted in step 138 .
Unless appliance 22 is currently being used to capture a new image, it is unnecessary to power photoelement array 52 (see FIG. 1 A). Accordingly, it is necessary in step 142 to redirect power from display 24 to photoelement array 52 at the beginning of the image capture process. Step 144 represents the capture process performed by the user, which will continue until capture button 54 is released, which is determined at decision diamond 146 or photoelement array 52 detects that appliance 22 has been lifted off the page or another capture error has occurred (e.g., scan speed was too fast, out of memory, too much rotation in the scan path, etc.), as represented by decision diamond 147 . Help utility module 102 provides an instructional animation that demonstrates both proper and improper techniques for executing an image scan. Scenes from this animation are provided in FIGS. 10A-10D, 11 A- 11 B, and 12 A- 12 B. Note that this animation does not run automatically as part of the image capture process. Instead, the animation is provided as part of the help feature accessed through help button 36 .
Turning first to FIGS. 10A-10D, the preferred scan path is illustrated in the collection of animation scenes shown therein. There are two requirements that must be followed to perform a successful scan: First, the user must maintain appliance 22 in engagement with the target image to be acquired. Second, the entire image must be traversed with photoelement array 52 . As shown in FIG. 10A, the user activates capture button 54 while appliance 22 is in engagement with the target. In FIG. 10B, the user is shown to make a first stroke or pass with appliance 22 thereby acquiring the left side of the image. Next, appliance 22 is slid to the right where a second stroke or pass is made to acquire the right side of the image. In the preferred embodiment, the two strokes should overlap by at least ½ inch to ensure that the entire image is captured and properly stitched together. Capture page module 78 detects the overlap and discards redundant image data when reconstructing a digital representation of the image. Once the entire image has been traversed, the user releases capture button 54 as shown in FIG. 10D to end the image capture procedure. While the scanning procedure just described is the preferred technique, alternative paths can be taken along the target image as long as the entire image is covered and appliance 22 remains in engagement with the target. Nevertheless, wandering paths that result in numerous sections of overlap or require extensive backtracking with appliance 22 to traverse the entire image will necessitate more extensive processing in filtering out redundant image data as capture page module 78 reconstructs the captured image.
FIGS. 11A-11B and 12 A- 12 B illustrate two common mistakes made by the user in scanning a new image. In FIG. 11A, the user is shown to leave the target image with appliance 22 thus acquiring unwanted image data. The error is highlighted in FIG. 1B with the X over the errant scan region. FIG. 12A illustrates a scan path that is very close to the preferred scan path shown in FIGS. 10A-10D. Notice, however, that in FIG. 12A the user failed to overlap the second stroke or pass made along the right side of the image with the initial stroke or pass made over the left side of the image. As a result, the center portion of the image is not acquired as indicated by the X in FIG. 12 B.
Returning to the flow chart of FIG. 9A, once the user releases capture button 52 , disengages appliance 22 from the target, or encounters any other capture error, the capture is terminated in step 148 and power is redirected to display 24 in step 152 . During this post capture period, capture page module 78 processes the acquired image by discarding redundant image data due to overlap during scanning and adds control data to save the new page in sequence with previously acquired pages. While this processing is taking place, however, the user can choose to discard the newly acquired image. As shown in FIG. 13, a post-processing animation is shown on display 24 that represents the processing carried out under the control of capture page module 78 during the post capture period. A horizontal bar graph is used to communicate the progress of the new page processing. Inasmuch as the task of processing the newly acquired image data requires a finite amount of processing time, the animated bar graph can be correlated to track this processing interval with a suitable degree of precision. Accordingly, once the bar substantially fills the block in which it is contained, post capture processing is complete. It will be appreciated that alternative progress icons can be used, such as an hour glass or a digital percentage readout, without departing from the spirit of the present invention. The bar graph block further notifies the user that post capture processing can be canceled and the newly acquired image discarded through invocation of navigation button 46 . This option is represented in the flow chart of FIG. 9A as decision diamond 154 . Thus, throughout the time that the post-processing animation is on display in step 156 , the user can choose to end the processing and discard the image by simply pressing navigation button 46 , which results in display 24 returning to the previous view (i.e., the content of display 24 prior to initiation of an image capture) in step 158 by following termination C in FIG. 9 B. To assist the user in making this decision, the bar graph is superimposed over a portion of a highlight or outline (i.e., no image content is displayed) of the scan path (see FIG. 13 ), providing an early indication that portions of the desired image could be missing and the captured page should be discarded.
If the captured image is not discarded, post capture processing will complete and the process will continue at termination D of FIG. 9 B. At decision diamond 162 , capture page module 78 determines whether an error occurred during the scan and, if so, transfers control to error utility module 98 where an error screen such as the example shown in FIG. 14 is displayed on display 24 in step 164 . Examples of errors identified in the preferred embodiment of the present invention include the following: a) appliance 22 cannot navigate across the target medium; b) the user lifted appliance 22 from the scan target while capture button 52 was depressed; c) the maximum scan speed was exceeded; d) the maximum capture size was exceeded; and e) memory 64 is full.
Capture page module 78 then displays a verification screen as shown in FIG. 15 in step 166 even if an error occurred because the verification may help a user understand the consequence of the error. Furthermore, the captured page may nevertheless be satisfactory for the user's purpose in spite of the error. The verification screen provides a fully processed view of the captured image that illustrates the path followed by the user in performing the image capture. The verification screen therefore allows the user to examine their scan results in detail for such errors as an incorrect capture path or missing content to determine whether the page should be kept or discarded. To reinforce the logical relationship between the captured images, a thumbnail view of the last page captured is briefly displayed on display 24 with the newly captured page shown to slide onto the display from the right thereby displacing the last page captured to the left. This animation conveys to the user that the verification screen of the newly captured image represents a new last page in the sequence of captured pages. The page shown in FIG. 15 is an example of a poor scan technique as portions of the image are clearly missing. As represented by decision diamond 168 , some operations attempted by the user while the verification screen is on display results in the page transforming through an animation into a rectangularized page as shown in FIG. 16 in step 172 . This includes such operations as a power cycle, an automatic shutdown, viewing another page, attaching to a previous page, capturing another page, or sending a page or group of pages to an external appliance or device. The verification screen will remain on display if other operations such as accessing a menu through any of buttons 26 , 34 , 36 , and 38 (see FIG. 1A) or a zoom or rotation operation is attempted through buttons 28 and 32 respectively. The rectangularization process places a border around the verification image to portray the image as it would be embodied in a printed page. Thus, for example, if the user decides after reviewing the verification screen that the newly captured image should be discarded, control will be passed to delete page module 92 upon activation of delete button 34 where the newly captured page can be deleted following the same process used to delete any captured page.
Application software 70 , which comprises an ordered listing of executable instructions for implementing logical functions, can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions. In the context of this document, a “computer-readable medium” can be any means that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The computer-readable medium can be, for example but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, device, or propagation medium. More specific examples (a nonexhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic) having one or more wires, a portable computer diskette (magnetic), a random access memory (RAM) (magnetic), a read-only memory (ROM) (magnetic), an erasable programmable read-only memory (EPROM or Flash memory) (magnetic), an optical fiber (optical), and a portable compact disc read-only memory (CDROM) (optical). Note that the computer-readable medium could even be paper or another suitable medium upon which the program is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in a computer memory.
The principles of the present invention have been disclosed herein as embodied in a portable, hand-held image capture and communication appliance that provides the flexibility of traditional hand-held scanners yet offers an array of intelligent features not heretofore known in the art. For example, images or pages can be acquired using the capture and communication appliance using a simple and easy to learn scan technique that can be executed using a single hand. Moreover, the appliance is capable of discarding redundant image data from overlapping paths taken during image capture thereby allowing the user to focus on traversing the entire target image. Once the image capturing process is complete, animation is used during post capture processing to communicate to the user the results of the capture, including whether an errant capture path was followed and/or image content was missed during the capture. If an error occurs, an error screen is displayed to explain the nature of the problem to the user, however, the image is still displayed in case the user has sufficient information captured.
In concluding the detailed description, it should be noted that it will be obvious to those skilled in the art that many variations and modifications can be made to the preferred embodiment without substantially departing from the principles of the present invention. All such variations and modifications are intended to be included herein within the scope of the present invention, as set forth in the following claims. | A hand-held image capture and communication appliance and method of using same are provided wherein images may be acquired via scanning means and saved in an internal memory. The scanning appliance includes a processor for manipulating and exhibiting the images on a built-in display screen. Program code stored in the internal memory and executed by the processor includes a capture page module for processing the image data acquired through the scanning means by filtering and discarding redundant image data to form a whole image. The capture page module includes a code segment for displaying a first animation that is designed as a metaphor to signify the progression of the image data processing taking place in the appliance. The metaphor used in the preferred embodiment is a bar graph overlaying a thumbnail of the capture path followed in acquiring the image. The capture page module includes a code segment for displaying a second animation in which the most recently captured image is shown as an outline displacing a previously captured image from the display. This animation communicates to the user the logical sequencing of the captured images as the new last image in the sequence displaces the previous last image in the sequence. Moreover, the display of the newly captured page or image allows the user to examine the page in detail to verify whether the correct scan path was followed and whether any desired content is missing from the image. Should an error occur during the scanning process, the capture page module invokes an error utility module to display a textual dialog explaining the nature of the error. | 7 |
This application is a continuation of U.S. application Ser. No. 09/165,026, filed Oct. 1, 1998, now U.S. Pat. No. 6,308,747.
FIELD OF THE INVENTION
The following invention relates generally to a method and apparatus for transferring fluid from a deformable ampule or vial into a syringe, injecting system (IS) or cannula without the need for a needle. More specifically, a male and female docking arrangement is disclosed coupled with structure for storing and transferring liquids so that the number of times needles are used in a medicating situation is kept to a minimum. The ampule has a structure which docks with the syringe, (IS) or cannula in a fluid tight sealing arrangement and the ampule is designed to collapse easily when extracting a substance such as liquid therefrom so as to preserve the fluid tight seal and therefor not allow air into the ampule, or syringe, or injecting system during the collapsing phase.
BACKGROUND OF THE INVENTION
Diseases such as nosocomial infections, hepatitis and AIDS, which are pathogens that can be transmitted with the body fluids of a person, are running rampant globally. As a result, medical environments such as hospitals spend considerable amounts of money, time and energy attending to the problems that arise when hypodermic needles are required.
Complex protocols are evolving which attempt to minimize the likelihood of a needle stick from the time that a needle has been removed from its sterile storage environment through loading, utilization and disposal. Examples of heightened care with respect to the use of hypodermic needles are chronicled in patent literature, in the development of anti-stick needle caps, devices which destroy the needle itself after use and other instrumentalities for receiving both the used needle and syringe for safe disposal. Thus, the prevailing systems are based on the premise of the very existence of the needle for the medicating process.
The instant invention to a large extent obviates the need for the needles themselves in the many common instances where syringe needles have heretofore been used. Typically, one scenario where the use of a hypodermic needle is now commonplace includes the steps immediately prior to injection in the patient. The process involves loading the syringe with a sterile, pharmaceutical-grade fluid by extracting medicating fluid from a vial by using the affixed needle of a syringe for access. When using an ampule, the tip is broken off and then the ampule is entered with a needle, often a filtered needle to filter out glass particles. Next, the patient who is to receive this medicating fluid is injected with a new needle.
Prior art drug containing vials are formed from an open mouthed bottle or jar wherein the walls of the container defining the vial are rigid and non-flexible. The opening of the jar includes a lip which supports a metal ferrule which supports an elastomeric diaphragm made from a rubber-type material having a resealable property such that once the diaphragm has been penetrated by a needle and then removed, the diaphragm reseals itself. Typically, a syringe body is first fitted with a hypodermic needle. It is common practice that prior to the needle being plunged into the vial through the rubber diaphragm, it is first loaded with ambient air. Because the prior art vials are rigid, the vial is first pressurized to assist in fluid withdrawal. While this technique makes it easier to withdraw fluid, it introduces non-sterile air into the vial. Technically, the needle is to then be replaced with a new needle prior to injecting a patient.
The syringe is, in general, an elongate cylindrical object having a plunger adapted to reciprocate within an interior hollow. By withdrawing the plunger from the interior of the cylindrical hollow, fluid is drawn from the vial and is loaded into the syringe. Once the syringe has been removed from the vial, great care must be exercised for a multiplicity of reasons. The medication contained within the syringe is now provided with the present ability to discharge the medication to any who come in contact with the needle, albeit inadvertently. In order to reduce the amount of time a “loaded” syringe is carried, the medicating healthcare professionals normally will use a cart which contains all pharmaceuticals which are to be distributed during rounds to the patients. This reduces the amount of time the healthcare professional is required to walk with an armed syringe whose needle has been exposed or whose exposed needle has been recapped. Recapping provides further risk of self sticking due to misaligning a needle cap with the syringe.
After dispensing the medicine to the patient, the healthcare professional typically has one of several choices, none of which is entirely satisfactory for safe disposal of the needle. In one scenario, the healthcare professional is required to carefully recap the needle hoping that in the multiple times this procedure is reperformed he or she does not misalign the cap with the needle and inadvertently suffer a needle stick.
Another device has been developed which appears like a pencil sharpener and allows the healthcare professional to place the leading end of the syringe into an opening where an electric current is applied to the needle which melts the needle.
A third strategy involves discarding the needle and the syringe in a container for subsequent destruction or internment as biomedical waste. This technique presents ongoing risk to people who subsequently handle this waste.
The Food and Drug Administration (FDA) has accordingly issued an alert urging hospitals to use needleless systems or recessed needle systems instead of hypodermic needles for accessing intravenous lines. Plastic cannulas now exist which can fit onto luer connections and penetrate sealable diaphragms on infusion catheters. Thus, the FDA is urging the use of hypodermic needles only to penetrate the skin.
The following prior art reflects the state of the art of which applicant is aware and is included herewith to discharge applicant's acknowledged duty to disclose relevant prior art. It is stipulated, however, that none of these references teach singly nor render obvious when considered in any conceivable combination the nexus of the instant invention as disclosed in greater detail hereinafter and as particularly claimed.
U.S. PATENT DOCUMENTS
U.S. PAT. NO.
ISSUE DATE
INVENTOR
829,178
Aug. 21, 1906
Stegmaier
2,486,321
Oct. 25, 1949
O'Sullivan
3,187,966
Jun. 8, 1965
Klygis
3,419,007
Dec. 31, 1968
Love
3,977,553
Aug. 31, 1976
Cornett, III et al.
4,046,145
Sep. 6, 1977
Choksi, et al.
4,130,117
Dec. 19, 1978
Van Eck
4,213,456
Jul. 22, 1980
Böttger
4,465,472
Aug. 14, 1984
Urbaniak
4,643,309
Feb. 17, 1987
Evers
4,944,736
Jul. 31, 1990
Holtz
5,035,689
Jul. 30, 1991
Schroeder
5,334,173
Aug. 2, 1994
Armstrong, Jr.
5,356,406
Oct. 18, 1994
Schraga
5,374,263
Dec. 20, 1994
Weiler
5,409,125
Apr. 25, 1995
Kimber, et al.
5,716,346
Feb. 10, 1998
Farris
FOREIGN PATENT DOCUMENTS
PATENT NO.
ISSUE DATE
INVENTOR
FR
2594-687-A
Aug. 28, 1987
Hosnedl
EP
0 324 257
Jul. 19, 1989
Smiths Industries
EP
0 350 772
Jan. 17, 1990
Hansen
Evers (see for example FIG. 3 or 6 ) only connects with a syringe because its “container (1) is provided with an outlet opening (2) having a surface in the form of an outwardly widening truncated cone” (see column 2, lines 27-29).
When the Evers device is installed on a syringe tip the vial ( 1 ) must first be axially advanced to the right of the Evers right-hand side drawing. This causes a radial force by distending the outwardly widening truncated cone ( 2 ). Once the axial force is no longer applied, there is still a tendency or a reaction of the plastic material forming the outwardly widening truncating cone ( 2 ) to return to its original unstressed configuration. Since the cone is acting on a surface which is canted with respect to the long axis of the vial, the surface has a force component parallel thereto which encourages the vial to slide off from the syringe. Evers featured a second embodiment (FIG. 6) wherein the opening “has been provided with peripherally arranged interior annular grooves across the outlet direction. Grooves of this kind apparently give improved sealing for the syringe tip ( 8 ) especially if the outlet opening is made of very thin and flexible plastic material.” (Column 3, lines 4-8.)
Kimber, et al. provides a neck portion ( 3 ) (FIGS. 2 and 5 ), but this is not the area of frangibility. Fracture occurs above the neck portion at outlet opening ( 7 ) and threads are located in the area between the opening ( 7 ) and the neck portion ( 3 ). These threads are intended to coact with the internal threads ( 15 ) carried on the peripheral wall ( 12 ) of a conventional luer coupling on the syringe. The threads are advanced until they bottom out against a bottom wall ( 13 ) on the luer coupling.
Holtz teaches the use of a cap interposed between the syringe and the vial. Holtz, column 3, lines 32, et seq. states “since the cap ( 5 ) makes the assembled bottle and adapter ( 1 ) completely sealed and caps ( 12 ) and ( 14 ) make the syringe completely sealed these two assemblies may be carried loose . . . with no fear of contamination . . . ”. Thus, the cap ( 5 ) and adapter ( 1 ) remain with the vial while the caps ( 12 ) and ( 14 ) remain with the syringe.
Stegmaier teaches the use of a cap tailored to never be reinstalled so as to prevent the bottle from being refilled. Thus, the portion that has indicia thereon includes a frangible section which precludes and “obviates the likelihood of refilling” (column 1, lines 10-11). Thus, once the cap has been removed from the bottle, it is never possible to be reattached. Thus, any indicia on the cap has limited value because it cannot be reassociated with the syringe that contains the contents heretofore in the vial.
Hansen teaches a vial constructed to more easily remove the tab, allowing access to the vial's interior.
SUMMARY OF THE INVENTION
This invention chronicles further efforts by the applicant enhancing U.S. Pat. No. 5,716,346.
By way of contrast, applicant's invention differs markedly from the foregoing. The vial 10 includes a tapering section 8 which converges to an opening 12 . When this convergent end (and its circular profile) runs over the cone shaped luer end of the syringe, it is distorted and distended. As it approaches an annular outer wall of the luer coupling it wedges between the annular wall and the cone of the syringe tip. The vial collapses during emptying, assuring no ambient air contamination.
The instant invention completely avoids the use of a needle when extracting fluid from a vial or ampule. In its essence, the instant invention takes advantage of a coupling that is the standard on a majority of syringes which had heretofore only been used in the past to support the hypodermic needle on the syringe. This coupling, called a luer fitting, has a male component and a female component. Typically, the syringe is configured with the “male” luer coupling which appears as a truncated cone that has an opening at its narrowest cross section. The luer coupling diverges toward an interior cylindrical hollow portion of the syringe. The instant invention replaces the “female” luer coupling and associated needle itself and instead replicates the female coupling on a specially formed ampule or vial so that docking between the ampule and a needleless syringe benefits from the pre-existing male coupling already found on common syringes. Walls of the ampule or vial are flexible to promote removal of the fluid therewithin.
The walls of the ampule are further tailored to promulgate collapse in a preordained manner. This collapse occurs by forming the ampule with a shape that provides a force gradient along the outer skin of the ampule when liquid is extracted beyond the fluid tight connection with the syringe.
With an opening of the ampule and the opening of the syringe in face-to-face docking registry and in fluidic communication, the ampule can be evacuated by any of a combination of manipulative steps. First, assume the syringe is in its initialized state, with its plunger nested well within the cylindrical hollow of the syringe body so that the plunger is in a compact, retracted state. The contents of the ampule can then be transferred with a negligible amount of air bleed at the ampule/syringe interconnection by deforming the side walls of the ampule and “milking” (i.e. applying hydrostatic force to) the liquid through the ampule walls and thus into the syringe. This causes the plunger of the syringe to translate along the cylindrical hollow. As the plunger advances along the cylindrical hollow, liquid enters the syringe.
Another strategy involves manipulation of the plunger to draw the fluid from the ampule by suction so that the filling of the syringe occurs by retracting the plunger to extract the liquid from the ampule while collapsing the ampule. The ampule is specially constructed to collapse. As before, the plunger starts well within the syringe and reciprocates outwardly of the cylindrical hollow.
A third strategy is a hybrid of the two previously discussed techniques which involves manipulation of both the ampule by (1) squeezing the ampule and suction by (2) moving the plunger out of the syringe cylindrical hollow. Thereafter, the ampule may be disconnected from the syringe for syringe deployment.
Once the ampule has been removed, a syringe has the intended fluid medication disposed therewithin. Unlike the prior art, no needle has yet been involved. Also, no air from the ambient environment has been mixed with the sterile fluid as was the case with prior art rigid wall vials. The seal between the syringe and ampule, coupled with ampule wall deformation excludes ambient air.
In one form of the invention, it is contemplated that the opening associated with the ampule is provided with a removeable cap having a luer-type coupling and an indicia bearing tab. The volume and medicinal contents of the ampule is stamped on the tab for identification purposes. With such an arrangement, it is possible to transfer the cap and tab from the ampule and connect the cap to the syringe to provide a tell tale of the contents of the fluid contained within the syringe. As an alternative, the ampule could remain docked to the syringe until subsequent use. The ampule would also note its contents on a surface thereof.
As a result of this system, the entire process for filling a syringe has been accomplished without the use of a needle. Personnel are able to operate more quickly with less fear of either inadvertent needle stick or inadvertent exposure to the medicine contained within the syringe.
It is to be noted that for many in-patients, the standard procedure in a hospital is to tap into a person's vein only once with an infusion catheter and to leave the catheter needle in place with tubing communicating therewith so that subsequent fluids such as intravenous drips and the like can be used. With such a system, a needle would never be needed with the syringe according to the present invention. “Y” connectors are well known in the art, one branch of which would have a complemental female luer coupling. Thus, for a patient's entire stay at a hospital, the only needle associated with that one patient, ideally, would be the one which initially had been placed in the patient's vein to support the infusion catheter. In this way, the opportunity for inadvertent needle sticks would be reduced to an absolute minimum.
The instant invention is further distinguished over the known prior art in that zones of programmable deformation are strategically provided which encourage collapse of the body of the ampule with less pressure than has been heretofore experienced. By providing this important feature, it is possible to provide wall thickness which can be somewhat thicker while still affording the same ability of the walls of the ampule to collapse on itself. The interplay of the present invention is between the sealing forces that exist between the docking of the syringe and the ampule. This sealing force should be as high as possible while providing the thickest wall possible on the ampule and still allow easy collapse of the ampule. By having a relatively thicker wall, the ampule is more robust and provides a further impediment to transpiration through the wall of the ampule. An ancillary benefit is that the criticality of the wall thickness during blow, fill, seal (BFS) manufacture has been lessened.
OBJECTS OF THE INVENTION
Accordingly, it is a primary object of the present invention to provide a method and apparatus for transferring sterile fluid from an ampule to a hypodermic syringe without the need of a hypodermic needle.
It is a further object of the present invention to provide a device and method as characterized above which reduces the amount of time which hospital staff must spend in transferring fluid from a sterile ampule to a hypodermic syringe while also eliminating the fear of an inadvertent needle stick thereby avoiding the possibility of both unwanted contamination and unwanted medication.
A further object of the present invention contemplates providing a device and method as characterized above which is extremely inexpensive to fabricate, safe to use and lends itself to mass production techniques.
A further object of the present invention is to provide a device which can reduce the number of times that needles are required in a hospital or other medical setting.
A further object of the present invention contemplates providing a device and method which minimizes the disposal problems of hypodermic syringes with needles.
A further object of the present invention contemplates providing a device and method for use in which a telltale is associated with first the ampule that stores the medicine, and then the syringe so that the fluid transferred from the ampule and into the syringe will be known at all times. In this way, the chain of custody of the fluid can be more readily monitored.
A further object of the present invention contemplates providing a system for loading syringes that obviates the need for the medicating health professional from having to trundle a miniature pharmacy on a cart from patient to patient. By pre-filling the syringes at a remote location added security and efficiency may be provided.
A further object of the present invention is to provide a programmed ampule wall structure that promulgates collapse before the seal that exists between the ampule and the syringe or other fluid receiving device admits air therein.
When viewed from a first vantage point it is an object to provide a needleless dosage transfer system for removing a sterile fluid from a sealed vial to a conventional syringe. The syringe has a plunger such that the plunger of the syringe translates from a first position telescoped within an interior cylindrical hollow of the syringe to a second position where the plunger has been displaced from the interior hollow and replaced by the fluid. The vial is defined by an end, collapsible sidewalls extending from the end thereby defining a blind bore and having an open end, a coupler at the open end of the vial, and a removable cap occluding the open end at the coupler. The vial coupler is provided with means to connect to a needleless opening of the syringe to be in fluid communication therewith, whereby fluid can be transferred to the syringe from the vial without an interconnecting needle.
Viewed from a second vantage point, it is an object to provide a method for transferring injectable fluids from a storage ampule or vial to a needleless syringe or other injecting device using a male luer fitting or other fitting. The syringe has a first coupling and an opening which communicates within an interior cylindrical hollow of the syringe so that fluid passes by the first coupling through the opening and into the hollow to load the syringe. The steps include providing a vial filled with fluid and with an outlet which has a second coupler defining the outlet. The vial is sealed by occluding the coupler outlet with a cap Subsequently, removing the cap and orienting the first and second couplers into complemental fluid tight docking arrangement (so that the opening of the vial registers with the opening of the syringe) allows transfer of the contents of the vial to the syringe without the need for a traditional needle extraction system.
Viewed from a third vantage point, it is an object to provide a method for forming an ampule to transfer medicine to be injected. The steps include forming an ampule with resilient walls so that the ampule can be collapsed, forming an opening on the ampule such that the opening is circumscribed by a coupler which is fashioned to receive a dose administering device, filling the ampule with the medicine and finally capping the ampule opening.
Viewed from a fourth vantage point, it is an object of the present invention to provide an ampule having a body with means to promulgate the body's collapse and a cap connected to the body and an opening at a scoreline between the body and the cap.
Viewed from a fifth vantage point, it is an object of the present invention to provide a method for transferring liquid from an ampule into a dosing device including the steps of: forming the ampule with the liquid by blow, fill and sealing; forming the ampule with a severable cap; and forming a body of the ampule with a zone of preprogrammed deformation to collapse upon liquid extraction.
These and other objects were made manifest when considering the following detailed specification when taken into conjunction with the appended drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the ampule according to the present invention prior to docking with a fluid receiving device such as a syringe.
FIG. 2 is a sectional view longitudinally of the ampule.
FIG. 3 is a perspective of the ampule.
FIG. 3A is a plan view of the cap and ampule near thereto.
FIG. 4 is a sectional view of the ampule docked with the fluid receiving device shown in section.
FIG. 4A is a sectional view detailing the locking of the ampule on the luer of the syringe.
FIG. 5 is a view similar to FIG. 4 showing the collapse of the ampule upon the extraction of the fluid therewithin into the syringe.
FIG. 6 is a sectional view of the cross-section of the ampule body according to one form of the invention.
FIG. 6A is a view of that which is shown in FIG. 6 when the ampule is collapsed.
FIG. 7 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a second variation of the invention.
FIG. 7A is a view of that which is shown in FIG. 7 when the ampule is collapsed.
FIG. 8 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a third variation of the invention.
FIG. 8A is a view of that which is shown in FIG. 8 when the ampule is collapsed.
FIG. 9 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a fourth variation of the invention.
FIG. 9A is a view of that which is shown in FIG. 9 when the ampule is collapsed.
FIG. 10 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a fifth variation of the invention.
FIG. 10A is a view of that which is shown in FIG. 10 when the ampule is collapsed.
FIG. 11 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a sixth variation of the invention.
FIG. 11A is a view of that which is shown in FIG. 11 when the ampule is collapsed.
FIG. 12 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a seventh variation of the invention.
FIG. 12A is a view of that which is shown in FIG. 12 when the ampule is collapsed.
FIG. 13 is a sectional view of the cross-section of the ampule body according to one form of the invention according to a eighth variation of the invention.
FIG. 13A is a view of that which is shown in FIG. 13 when the ampule is collapsed.
FIG. 14 is a perspective view of a series of ampules as they are produced and removed from a blow-fill seal machine.
FIG. 15 shows the syringe connected to the ampule cap, standing on end.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings now, wherein like reference numerals refer to like parts throughout the various drawing figures, reference numeral 10 is directed to the vial or ampule according to the present invention.
In its essence, the vial 10 is formed from two parts: a body portion 20 and a cap portion 40 . An area of transition noted as a scoreline 30 serves as an area of demarcation between the cap 40 and body 20 . The scoreline 30 allows the cap 40 to be dissociated from the body 20 so that the body 20 can dock with a syringe S as shown in FIGS. 1, 4 and 5 for filling the syringe S with a fluid F contained within the body 20 of the vial 10 .
More specifically, and referring to the drawings in detail, the vial 10 includes a body 20 having an end wall 2 , and an enclosing sidewall 4 . The peripheral side wall 4 has one proximal end coterminus with an outer periphery of the end wall 2 and extends away from the end wall 2 so that a blind bore 6 has been formed within which the fluid F is to be stored.
Typically, fluids such as a saline solution, water for dilution and injection, heparin or pharmaceutical drugs and other medicaments can be stored within the blind bore 6 . A distal end of the side wall 4 remote from the end wall 2 is provided with a tapering section 8 which converges away from the body 4 and towards a longitudinal axis CL of the vial 10 defining a converging portion of the vial 10 . This tapering section 8 converges to an opening 12 , or outlet and thereafter communicates with the cap 40 . The opening 12 defines a coupler of the vial 10 . The area of transition where the opening 12 is located is preferably coincident with the scoreline 30 to facilitate fracture of the vial 10 at the opening 12 . Thus, the cap 40 can be separated from the body 20 . After fracture (caused by shearing torsion—see M of FIG. 2 ), the plastic at the opening 12 tends to distort (forming a “chamfer” or “bevel”) (FIG. 4 A), forming a circular radially inwardly directed biting and/or sealing edge 21 . The edge 21 enhances the seal with a luer on the syringe, injection system, cannula, etc.
The cap 40 includes a flag type tab 42 on an exterior surface thereof upon which is printed the product contained within the vial 10 . The tab 42 is shown having a substantially rectangular, planar configuration to provide an exposed surface sufficient to place the name of the product on the tab. The tab 42 also serves as a purchase area to allow a person to grasp the cap 40 so that a twisting motion M of the cap 40 with respect to the body 20 will cause severing of the body 20 from the cap 40 at the scoreline 30 .
The cap 40 also includes an interior passageway 44 having a diverging contour 38 which substantially mirrors the slope of the tapered section 8 of the body 20 of the vial 10 about an axis of symmetry coincident with the scoreline 30 . This diverging passageway 44 extends a short distance within the cap 40 for purposes to be assigned.
As shown in FIG. 3, prior to docking with the empty syringe S (or IS or needleless cannula), the cap 40 will have been removed from the body 20 of the vial 10 . This allows the opening 12 of the body 20 to be exposed. The opening 12 has an inner peripheral dimension complemental to an exterior diameter of a male luer coupling L found on the syringe's or IS's or cannula's outlet. This coupling L defines an opening which forms a coupler of the syringe. Typically, this luer-type connection tapers and diverges as it approaches a cylindrical hollow H of the syringe S. Some luer connections include a cylindrical collar which overlies all but a tip of the male luer coupling. The collar usually has an interior thread or female bayonet coupling.
For a friction fit, and with respect to the syringe S shown in FIG. 1, the taper of the luer L traditionally couples to a needle. In the present invention, the syringe docks with the vial 10 as shown in FIGS. 4 and 5 such that the “male” conical taper of luer coupling L of the syringe S passes within the female opening 12 of the body 20 and becomes frictionally engaged in the tapering section 8 of the vial's body 20 . This connection may be enhanced by providing an exterior of tapering section 8 with a projection such as a male thread 13 (FIG. 1) or pip 15 (FIG. 3A) which enhances the force and sealing power the wall of opening 12 exerts on the luer L. A complemental “L”-shaped bayonet coupling 23 , shown in FIG. 3, and/or a ramp 25 (FIGS. 3 and 4A) could also enhance the seal with the syringe S by wedging with the collar/luer tip. Further, cutout(s) 17 near opening 12 and on peripheral flashing 19 (which surrounds the ampule 10 ) can exert holding force to the interior and leading edge of the syringe collar.
Note that the plunger P on the syringe S (FIG. 4) is in a contracted position such that the syringe's cylindrical hollow H, located on an interior portion of the syringe S has received the plunger P to its entire extent and the push rod of the plunger P is in a position immediately adjacent to the cylindrical barrel of the syringe S. In other words, the syringe S is empty.
With respect to FIG. 5, it should be noted that the side walls 4 of the vial 10 are formed from a material having the ability to elastically deform in the presence of force. In other words, the side walls 4 of the body of the vial 10 is designed to collapse. In this way, fluid F contained within the vial 10 can be transferred into the syringe S without leaking appreciable fluid or bleeding contaminating ambient air into the system. It is contemplated that one of three methods could be used to transfer the fluid F of the vial 10 into the syringe S.
One scenario, shown in FIG. 4, envisions the vial 10 being deformed by providing external force in the direction of the arrows D along the outer periphery of the side walls 4 . This causes the incompressible fluid F to be forced from the vial 10 and into the syringe S. The plunger P will now be forced by fluidic pressure, induced from the vial 10 , to move the plunger P from a first contracted position (FIG. 4) to a second expanded position (FIG. 5 ). The cylindrical hollow H of the syringe S receives the fluid F. In other words, the syringe S will now have been filled with the fluid F and the plunger P will have been extended to a second position for delivery to a patient.
A second preferred scenario involves docking the syringe S or needleless cannula with the vial 10 as described above. Rather than exerting force D on the vial 10 , instead the plunger P is pulled in the direction of the arrow A and causes negative pressure to exist in the cylindrical hollow H of the syringe S. Since the side walls 4 of the vial 10 are elastically deformable, the pressure induced by pulling the plunger P in the direction of the arrow A will cause the fluid F within the vial 10 to migrate into the cylindrical hollow H of the syringe S, filling the syringe S.
A third scenario involves a hybridization of the first two mentioned techniques. Namely, force D on the exterior side walls 4 of the vial 10 will be coupled in concert with pulling of the plunger P in the direction of the arrow A so that the incompressible fluid F will have migrated from the vial 10 to the syringe S.
FIG. 15 is directed to a final manipulation of one component of the apparatus according to the present invention. The cap 40 has indicia thereon correlative to the identity of the fluid F which has now been transferred from the vial 10 into the syringe S. FIG. 3 shows sodium chloride. The cap 40 has an interior passageway 44 and exterior contour 38 which mirrors the geometry of the ampule's conical section 8 and opening 12 , perhaps including thread 13 , dot(s) 15 , “L”-shaped bayonet coupling 23 or ramp(s) 25 . The cap 40 is placed in axial registry with and forced onto the luer of the syringe S or needleless cannula. Thus, the syringe S or cannula will be covered with cap 40 . As mentioned above, the scoreline 30 of the opening 12 defines an axis of symmetry between the tapering section 8 of the vial body 20 and the diverging contour 38 of the passageway 44 of the cap 40 . As shall now be evident, the cap 40 can be frictionally forced over the conical taper of a the syringe S thereby covering the male luer coupling L.
In this way, after the syringe S is loaded and ready for subsequent use, the contents of the fluid F within the syringe S will be known to the person dispensing the medication. Thus, different fluids can be pre-loaded into several syringes in a secure area. The healthcare professional can merely take a collection of the syringes or needleless cannulas to the site for ultimate medicating without having to use a drug preparation cart as is commonly in vogue today. The cap 40 can include a support foot 46 to support the syringe S or vial 10 on end. The foot 46 is located at an end of the cap 40 remote from passageway 44 and defines a planar surface transverse to the long axis 2 . This allows the on end orientation. The foot 46 is preferable faceted at extremities thereof so that the foot 46 prevents the syringe S or ampule 10 connected thereto from rolling when oriented as shown in FIGS. 1 and 5 . Note the ampule 10 is also marked with its contents (e.g., sodium chloride, FIG. 1) and can also be used as a cap for the syringe by leaving the ampule 20 on the syringe S as in FIGS. 4 and 5.
As had been mentioned briefly hereinabove, many people receiving home care and in hospitals as in-patients have infusion catheters operatively coupled at all times during their stay. Many of the infusion catheters include a male luer coupling complemental to the contour of both the vial 10 and the passageway 44 of the cap. When this is the case, the syringe S never needs to include a needle on the male luer coupling L. Instead, one can administer the medicine directly through the infusion catheter. In this way, the number of instances where trained medical personnel are exposed to administering fluids with hypodermic needles will be minimal. This reduces the amount of time and care required in the efficient performance of their tasks and minimizes both occasions for needle sticks and problems of needle disposal.
FIGS. 6 through 13 show variations in the cross-sectional contour that the ampule 10 can assume and will further suggest to the reader other geometrical shapes which are intended to be included as part of this invention. They can all be characterized as having a static structure which yields in the face of the pressure shown in FIG. 4 either along the direction of the arrow “A” and/or pressure along the arrows “D” so that they can collapse from their expanded positions (FIGS. 6 through 13) to their collapsed configuration (FIGS. 6 A through 13 A). For example, the FIG. 6 version (also depicted in FIGS. 1 and 3) in section shows a parallelepiped type structure, namely a parallelogram in section which collapses more readily into the FIG. 6A configuration with less force than for example a structure which would be triangular in section. Surprisingly, the included acute angles on the parallelepiped structure of FIG. 6 need not be as severe as shown in the drawings. In fact, for a given wall thickness the included angle can be approaching 90°, but as the material that forms the exterior skin gets thicker, the angle can decrease accordingly. Whereas FIG. 6 shows the flashing 19 that exists when forming the devices in a blow, fill, seal machine, as being medially disposed upon the two parallel sidewalls, FIG. 9 shows the flashing 19 as being located at diametrically opposed corners. While the flashing 19 may be located as shown in FIG. 9 on the major diameter, the flashing could similarly be located on the minor diameter as shown in dotted lines. Again referring to FIG. 6, although the flashing 19 is located medially along two parallel sidewalls, they can be moved up or down along the length thereof or on the walls which are shown as being horizontal in FIG. 6 . The key is to provide an area or a zone which promulgates deformation and to that end, all variations appear as polygonal in section with a least two acute included angles. FIGS. 7, 7 A, 10 , 10 A and 12 , 12 A show another “accordion fold” geometrical design which also lends itself to collapse. Also shown are various possible locations for the flashing 19 . As shown in section, each of these variations can be viewed as having (with respect to the body) an axis of mirror symmetry along a medial portion thereof where the symmetry on either side thereof is generally of the shape of two facing truncated triangles facing one another with the apexes removed. This provides two parallel sidewalls interconnected by “V”-shaped sidewalls having a central narrow area allowing collapse because of the “accordion-like” narrowing. Similarly, FIGS. 8 and 13 illustrate another variation wherein instead of having the one “V”-shaped sidewall directed inwardly towards the other, it is pointed outwardly to provide an arrow-shaped contour. As before, the flashing 19 can be oriented along different parts of the body 4 , FIG. 8 showing the flashing 19 as being centrally disposed and FIG. 13 showing the flashing as having one centrally disposed part and one adjacent a top wall 19 . In view of the other examples, other variations on the flashing location should now be evident. FIG. 11 is a further variation in which the second of two “V”-shaped sidewalls have been replaced with a perpendicular wall and the flashing is located as shown in FIG. 13, but could of course be located elsewhere as described above. The key in all of these variations is that the body is provided with a means to encourage and promulgate collapse of the body in the presence of a force which causes the fluid contained within the body of the ampule 10 to be removed. By providing a body with a tendency to collapse, and by providing the robust interconnection between the outlet of the ampule with its docking to the coupling on the syringe, greater flexibility in manufacturing is possible and the tolerances of the wall thickness and plastic choice become greater. It is desired, however, that the seal that exists between the syringe and the ampule have a force which is greater than the force required to collapse the ampule so that no air is admitted between the interconnected syringe and ampule during the filling process of the syringe.
FIG. 14 shows a series of ampules as they would appear oriented in side by side relationship and interconnected by a thin membrane at junctures between adjacent ampules and made using a blow, fill, seal machine. The FIG. 14 series is based on the example with respect to FIGS. 6, 1 and 3 .
FIG. 15 shows the syringe S standing on the cap 40 having a foot 46 .
Moreover, having thus described the invention, it should be apparent that numerous structural modifications and adaptations may be resorted to without departing from the scope and fair meaning of the instant invention as set forth hereinabove and as defined hereinbelow by the claims. | An ampule having flexible walls with a zone which is programmed to promulgate collapse. The ampule includes an opening that is adapted to dock with a fluid receiving device such as a syringe in air tight sealing engagement. The collapse of the ampule is engineered to occur before breaking the seal that exists between the opening of the ampule and the docking syringe luer tip to ensure sterile transfer of fluid without contamination, especially from ambient air. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. application Ser. No. 12/495,754 filed Jun. 30, 2009, which is a continuation-in-part of U.S. patent application Ser. No. 12/350,092 filed Jan. 7, 2009, which claims the benefit of U.S. Provisional Application No. 61/019,545 filed Jan. 7, 2008.
FIELD OF THE INVENTION
The embodiments of the present invention relate to lenses designed to decode three dimensional content displayed on television, movie, computer or similar screens or monitors.
BACKGROUND
Three dimensional movies for theatres have been around for decades. With technological advances, three dimensional content is being developed for television, computer monitors and home projectors. In the past, and even today, special glasses allow users to view three dimensional content. Flat paper eyeglasses using red and green film for lenses are the primary glasses being used today. However, flat paper eyeglasses are not very effective for facilitating the desired three dimension effect. In addition, the flat paper eyeglasses are not comfortable and are generally viewed as a novelty. Other flat lenses suffer from the same drawbacks.
One advancement has been the development of linear and circular polarization for decoding three dimensional content. Despite the advancement, the lens and eyeglass technology has not advanced significantly.
Thus, there is a need for lenses that take advantage of the linear and circular polarization technologies while more effectively creating the desired three dimensional effect. Advantageously, the lenses and eyeglasses should provide improved optics and contrast while providing user comfort and versatility. It is also beneficial if the lenses may be mounted into stylish frames.
SUMMARY
Accordingly, one embodiment of the present invention is a curved lens configured to decode three dimensional content comprising: a polarizing layer laminated with a polymeric material layer on one or both sides; a retarder layer laminated to a front of the polarizer layer directly or to the polymeric material to form a sheet, said retarder layer aligned to decode a desired circular polarization; and wherein a blank cut from the sheet is curved using a thermoforming process or high pressure process into a lens configured to decode three dimensional content.
Another embodiment is a lens configured to decode three dimensional content comprising: a polarizing layer laminated with a polymeric material layer on one or both sides; a retarder layer laminated to a front of the polarizer layer directly or to the polymeric material to form a sheet, said retarder layer aligned to decode a desired circular polarization; wherein a blank cut from the sheet is curved using a thermoforming process or high pressure process into an optical element configured to decode three dimensional content; and wherein said optical element is utilized in an injection molding process whereby one or more thickness layers are added to the optical element to form said lens.
Another embodiment of the present invention is a method of fabricating a curved lens configured to decode three dimensional content comprising: cutting lens blanks from sheets of material comprising: a polarizing layer laminated with a polymeric material layer on one or both sides; a retarder layer laminated to a front of the polarizer layer directly or the polymeric material, said retarder layer aligned to decode a desired circular polarization, and wherein said blanks are cut to maintain a specified alignment of a polarizing axis associated with said sheet; curving said blanks into lenses by: a. heating the blanks to a deformation temperature; and applying a vacuum suction and/or pressure; or b. applying high pressure.
In one embodiment, the retarder is a norbornene copolymer resin such as an Arton film (manufactured by JSR Corp.) or Zenor film (manufactured by Zeon corp.). Conventional adhesives (e.g., pressure sensitive adhesives) are used to bond the layers forming the lens. In one embodiment, a hard coating is applied to the front and back surfaces of the lens to allow for normal cleaning and extended life. In one embodiment, a lens thickness is between 750 and 1500 microns. In another embodiment, the lens thickness is between 250 and 1500 microns.
In an embodiment intended to decode 3D content displayed on computer screens or monitors, the blanks are cut from the sheet at a plus or minus 45 degree angle to correctly align the polarizing axis with the display of content on the television or computer screen.
Other variations, embodiments and features of the present invention will become evident from the following detailed description, drawings and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 illustrate an exemplary specification sheet for a first lens embodiment of the present invention;
FIGS. 3 and 4 illustrate an exemplary specification sheet for a second lens embodiment of the present invention;
FIG. 5 illustrates a flow chart detailing one embodiment of manufacturing the lenses according to the embodiments of the present invention;
FIG. 6 illustrates a flow chart detailing a second embodiment of manufacturing the lenses according to the embodiments of the present invention; and
FIGS. 7 a - 7 c illustrate various television and computer screen shots showing content parameters and polarizing axis alignment of corresponding 3D lenses.
DETAILED DESCRIPTION
For the purposes of promoting an understanding of the principles in accordance with the embodiments of the present invention, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Any alterations and further modifications of the inventive feature illustrated herein, and any additional applications of the principles of the invention as illustrated herein, which would normally occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the invention claimed.
Traditionally flat lenses and frames have been used in 3D glasses. One problem with the flat 3D glasses is that the lenses are distanced from the user's face and more particularly the user's eyes. Thus, light is able to enter the user's eyes from the top, bottom and side of the lenses reducing the visual acuity and contrast thereby reducing the effectiveness and comfort of the 3D experience. This is especially true at home or other locations outside of dark movie theatres. Moreover, the current one-size-fits-all approach to flat 3D eyeglasses reduces the quality of the 3D experience and in many cases results in an uncomfortable fit for most users. Accordingly, the embodiments of the present invention seek to overcome the disadvantages of the prior art flat 3D eyeglasses by creating 3D lenses and eyeglasses which are more akin to normal curved lenses and eyeglasses. Consequently, the lenses described herein are generally thicker than traditional flat 3D lenses and curved to prevent ambient light from interfering with the 3D experience and allow for better fitting glasses. Conventional flat 3D paper lenses are 0.3 to 0.4 mm thick while the embodiments of the present invention are substantially in a range of 0.75 mm to 1.5 mm. In an alternative embodiment, the lenses may be in range of 0.25 mm to 0.75 mm for use with an injection molding process as described below. The curvature further enables a better fit on the user's head. In addition, the thicker lenses enable them to be mounted into stylish frames to which people are more accustomed.
FIGS. 1-4 show specifications associated with lenses made utilizing the embodiments of the present invention. FIGS. 1 and 2 depict charts 100 and 105 listing lens specifications according to a first embodiment. The charts 100 and 105 depict dimensions, including width 110 and length 115 , polarization angle 120 , retardation angle 125 , transmittance percentage 130 , polarizing efficiency 135 , thickness 140 and retardation 145 . As shown in charts 100 and 105 , the width ranges from 495 mm to 505 mm; length from 700 mm to 710 mm; polarization angle from −1.0 degree to 1.0 degree; retardation angle from 44.0 degrees to 46.0 degrees (or 134 degrees to 136 degrees); transmittance percentage from 37.5% to 42.5% v; polarizing efficiency of 99% or greater; thickness of 1020 microns to 1080 microns (or 1.02 mm to 1.08 mm) and retardation of 110 to 150 nm. Larger ranges are possible for each of the aforementioned categories. Charts 101 and 106 shown in FIGS. 3 and 4 , respectively, depict similar lens specifications according to a second embodiment of the present invention.
Fabrication of the lenses is accomplished using lamination and thermoforming techniques. FIG. 5 shows a flow chart 200 detailing one method of fabricating lenses according to the embodiments of the present invention. At 205 , sheets are formed and, at 210 , lens blanks are cut from the sheets of material comprising: polyvinylalcohol polarizer film, polyethylene terephthalate or similar material laminated with triacetate on one or both surfaces (i.e., linear polarized film) and a retarder film laminated on a front surface thereof creating a circular polarized film. While triacetate is one material that can be used, others include polycarbonate, poly(methyl methacrylate), polystyrene, polyamide, cellulose acetate butyrate (CAB), cellulose acetate, cellulose diacetate (DAC) or cellulose triacetate (TAC), diacetate and similar stress-free (no birefringence) materials. The triacetate, diacetate or other materials may also be laminated onto the back (bottom) of the polarizer film to eliminate any unwanted retardation effects. A laminator machine forms the sheets of materials such that the axis of the polarizing film and retarder film are aligned properly to small tolerances. In one embodiment, the retarder is an Arton film (manufactured by JSR Corp.) or Zenor (manufactured by Zeon corp.). Other materials, such as polyurethanes, cellulose diacetate and polycarbonates, may also be used as the retardation film. Adhesives bind the materials together. The size of the blanks is dictated by the intended frame size. A typical size is 50 mm×70 mm. At 215 , the blanks are placed into a thermoforming machine which heats the blanks to a deformation temperature (e.g., 90° C. to 130° C.). At 220 , the heated blanks are curved using thermoforming techniques to an optically correct curved surface utilizing vacuum suction and/or pressure. To generate the desired base curve (e.g., 4, 6 and 8), a different combination of unique temperatures and times may be required. Once formed, at 225 , the curved blanks are cooled and removed from the machine. At 230 , the blanks, now lenses, can be finished with conventional lens dry cutting machines. At 235 , a hard coating is applied over the curved lenses. The hard coating allows normal cleaning and extended use while protecting the operational materials forming the lenses. The hard coat may also be applied prior to the thermoforming process by using a thermoformable hard coat material. At 240 , protective, removable sheets are applied to protect the lenses during subsequent operations including installation into frames, packaging and shipping. The protective sheets may also be applied to the sheets of the material prior to thermoforming process.
While thermoforming techniques are referenced in the flow chart 200 , extreme pressures may also be used to create the curved lenses. A machine known as the Wheel or similar machines generate extreme pressures and can be used to curve a blank into a lens. The process is known as press polishing whereby heat and pressure are applied to the blank via both sides of highly polished molds.
The triacetate and diacetate may comprises multiple layers themselves and have qualities, including transparency, low birefringence, lightweight and strength. Moreover, triacetate and diacetate are responsive to lamination and thermoforming processes and techniques as disclosed herein.
For the circular polarized lenses utilized in the embodiments of the present invention the polyvinylalcohol polarizer film is tinted and stretched in a linear direction to orient the polymer molecules. Polyiodine molecules are commonly used to allow polarizing efficiency and transmission to reach acceptable levels (e.g., >99% and >35%, respectively). Alternatively, dichroic dyes can be used to provide improved resistance to heat and humidity, but may have slightly lower polarizing efficiency and transmission. Both embodiments can produce the desired 3D decoding effect.
The curved lenses disclosed herein have numerous advantages over the flat 3D glasses of the prior art. The curved lenses provide a clearer and natural vision of 3D images with greater acuity and contrast. More particularly, the curved lenses reduce light entering the user's eyes from the side, top or bottom of the eyeglass frames thereby increasing the comfort and contrast associated with the viewed 3D images. The curved lenses can be fitted into commercial eyeglass frames to create a stylish pair of eyeglasses.
In another embodiment, as shown in the flow chart 300 of FIG. 6 , an optical element is made using the aforementioned process for use in an injection molded lens. Steps 305 - 330 coincide with steps 205 - 230 described above except that the resultant blanks are thinner than the lenses formed using the steps of flow chart 200 . At 335 , the blank becomes part of the final thicker lenses via an injection molding process. In other words, a thinner version of the lens described above is used as an optical element to make low cost injection molded polycarbonate (or polymethylmethacrylate and polymide) lenses. In this embodiment, the thermoformed optical elements are in a range of about 250-750 microns with a final injected 3D lens in a range of about 1000 to 2200 microns. Such lenses can be optically corrected with increased thickness and rigidity. In one embodiment, a back polymer layer of the lens is the same material as the injected material to provide good adhesion and reliability.
FIGS. 7 a - 7 c show various television and computer screens depicting content and polarizing axis orientation or alignment for corresponding 3D lenses. FIG. 7 a shows a television 400 displaying 3D content on a screen 401 configured with a vertical polarizing axis 402 and retarder axes 403 , 404 aligned at −45 and +45 degrees, respectively, relative to horizontal. Lenses 405 , 410 have a polarizing axis 415 aligned at 0 degrees (i.e., horizontal). A retardation axis 406 associated with the left lens 405 is at −45 degrees (i.e., rotated clockwise) relative to horizontal and a retardation axis 411 associated with the right lens 410 is at +45 degrees (i.e., rotated counter-clockwise) relative to horizontal. Accordingly, the left lens 405 and right lens 410 each allow only similarly polarized content emitted by the television screen to pass through thus creating the 3D effect. The configuration of lenses 405 , 410 is the same as the configuration of the movie lenses discussed above.
FIG. 7 b shows a first computer 450 displaying 3D content on a screen 451 with a polarizing axis 452 at +45 degrees from the horizontal and retarder axes 453 , 454 aligned at 0 degrees (horizontal) and 90 degrees (vertical), respectively, from the horizontal. Lenses 455 , 460 have a polarizing axis 465 aligned at −45 degrees from the horizontal. A retardation axis 456 associated with the left lens 455 is at 90 degrees and a retardation axis 461 associated with the right lens 460 is at 0 degrees relative to horizontal.
FIG. 7 c shows a second computer 480 displaying 3D content on a screen 481 with a polarizing axis 482 at −45 degrees from the horizontal and retarder axes 483 , 484 aligned at 0 degrees (horizontal) and 90 degrees (vertical), respectively, from the horizontal. Lenses 485 , 490 have a polarizing axis 495 aligned at +45 degrees from the horizontal. A retardation axis 486 associated with the left lens 485 is at 0 degrees and a retardation axis 491 associated with the right lens 490 is at 90 degrees relative to horizontal.
Although the invention has been described in detail with reference to several embodiments, additional variations and modifications exist within the scope and spirit of the invention as described and defined in the following claims. | Curved lenses configured to decode three dimensional content and method of fabricating the same. The lenses decode three-dimensional content displayed on televisions or computer monitors. Sheets from which the lenses are cut have either (i) a polarizing axis of 0 degrees relative to horizontal and one sheet has a retarder axis at −45 degrees relative to horizontal and the other sheet has a retarder axis of +45 degrees relative to horizontal; (ii) a polarizing axis of −45 degrees relative to horizontal and one sheet has a retarder axis at 0 degrees relative to horizontal and the other sheet has a retarder axis of 90 degrees relative to horizontal; or (iii) a polarizing axis of +45 degrees relative to horizontal and one sheet has a retarder axis at 0 degrees relative to horizontal and the other sheet has a retarder axis of 90 degrees relative to horizontal. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to PCT Application No. PCT/EP2014/061436, having a filing date of Jun. 3, 2014, based on DE 10 2013 105 687.3, having a filing date of Jun. 3, 2013, the entire contents of which are hereby incorporated by reference.
FIELD OF TECHNOLOGY
[0002] The following relates to an apparatus and a method for transporting containers.
BACKGROUND
[0003] Such apparatuses and methods have been known for a long time from the prior art and serve, for example, to transport containers, during production, from a first treatment station, such as a blow moulding machine for example, to a further treatment station, such as a filling machine for example. Usually it involves starwheels or the like, on which a plurality of holding elements for holding the containers are arranged and which thus transport these containers along a predefined transport path. Also known, in addition, are chain conveyors which have on a chain said holding elements for holding the containers. These transport devices have the disadvantage that the spacing between the individual holding elements is fixed and cannot be varied. In addition, these apparatuses also do not permit a variable transport speed of individual holding elements.
[0004] Also known are transport devices in which the principle of a linear motor is used for moving the transport elements. Such apparatuses usually have a plurality of electromagnets arranged in a stationary manner, as well as transport elements which are movable relative thereto and which may also have magnetic means, such as permanent magnets for example. With such apparatuses, however, the problem arises that the transport elements are purely passive elements which cannot carry out any processing operations on the containers. However, it would often be desirable to carry out certain treatment operations also during transport of the individual containers, such as, for example, sterilizing operations, application operations, inspection operations or even just an opening and closing of the holding elements in order to allow a handover to further transport devices. However, this has hitherto proven to be difficult since the movement or drive for the movement also takes place by means of magnetic forces and a suitable energy transmission for such drives arranged on the transport elements is difficult to implement.
SUMMARY
[0005] An aspect relates to a transport device for transporting containers which is based on magnetic forces and which also offers a possibility of arranging electrically operated working elements on these transport elements.
[0006] An apparatus according to embodiments of the invention for transporting containers has a circumferential or even non-circumferential transport path and at least one transport element which is arranged such as to be movable relative to this transport path. This transport element can be driven at least partially by means of a magnetic force. Furthermore, the transport path has a plurality of magnetic elements and at least one magnetizable element is also arranged on the transport element. Furthermore, a movement of the transport element relative to the transport path can be achieved by actuating the magnetic elements (of the transport path and/or of the transport element). In one preferred embodiment, the transport path may be a circumferential transport path.
[0007] According to embodiments of the invention, an electrically operated working element (hereinafter also referred to as an electrically operated drive device), which can be supplied inductive with electrical energy, is arranged on the transport element. It is therefore proposed that one transport element and in particular a plurality of transport elements is provided, which can be moved relative to the transport path by magnetic forces, wherein said drive device or the working element, which can also be supplied preferably inductive with power, is provided on at least one of these transport elements.
[0008] For example, this working element or this drive device may be an actuator which actuates for example the holding element in order thus to effect a holding or release of the container. For example, the holding elements may be configured both as active and as passive holding elements, that is to say a release or holding of the container may also take place actively, for example by means of magnetic forces. An electric drive device will be understood to mean a drive device selected from a group of working elements or drive devices that includes electric motors, in particular rotation or linear motors, magnetic elements and the like. Preferably, the energy for generating the movement of the transport element relative to the transport path is transmitted in a contactless manner. The energy for the drive device is also advantageously transmitted in a contactless manner.
[0009] It is advantageous that at least one transport element is designed in such a way that it can compensate, as it travels relative to the transport path, for a difference in speed of transport between a container treatment device upstream of the transport apparatus and a treatment device downstream of the transport apparatus.
[0010] In a further advantageous embodiment, the apparatus has a plurality of transport elements which are movable relative to the transport path, and the movements thereof relative to the transport path are controllable independently of one another. In this way, for example, different spacings can be set in a highly individual manner.
[0011] In a further advantageous embodiment, the transport path has at least one buffer section into which at least one of the at least one transport element can run in order to vary the density of the transport elements on the transport path.
[0012] In a further advantageous embodiment, the transport path is configured as a magnetic suspension track of a magnetic suspension railway. However, it would also be conceivable that the individual transport elements slide along the transport path via rollers.
[0013] In a further advantageous embodiment, the at least one transport element is mounted on the transport path in an entirely magnetic or partially magnetic and partially mechanical manner.
[0014] In a further advantageous embodiment, the transport path may have any geometric shape. For instance, the transport path may have a substantially rectilinear profile in the region in which the transport elements each carry containers, but may optionally also have curved profiles.
[0015] In a further advantageous embodiment, the apparatus has a rotating device which rotates the containers through a predefined angle of rotation relative to their longitudinal axis. In this case, the drive device may be a rotation drive which brings about said rotation. In a further advantageous embodiment, at least one treatment device which serves for treating the containers transported by the transport elements is arranged along the transport path. It is possible that several such treatment devices are arranged for example in series or parallel to one another. For instance, it would be possible that a plurality of identical treatment elements, that is to say treatment elements which each carry out the same treatment step, are arranged parallel or next to one another. However, it would also be possible that a plurality of treatment elements which carry out different treatment steps are arranged on the transport path.
[0016] In a further advantageous embodiment, the transport elements are mounted on the transport path by means of roller elements and in particular rollers.
[0017] In a further advantageous embodiment, the transport elements each have magnetic elements which serve for achieving the movement, wherein these magnetic elements are preferably permanent magnets. Advantageously, further magnetic elements are provided which serve for supplying energy to the drive device. Advantageously, the magnetic elements arranged on the transport element, which serve for moving the transport element as a whole, and the magnetic elements (arranged on the transport element) which serve for supplying the drive device are offset relative to one another and in particular are offset relative to one another in a transport direction of the transport elements. Preferably, those magnetic elements of the transport element which serve for supplying the drive device are arranged upstream of said permanent magnets (which serve for generating the movement) in a movement direction of the transport element.
[0018] In a further advantageous embodiment, the transport elements have energy storage means for supplying the drive devices with electrical energy. It is possible that these energy storage means are also charged by the inductive measures described above. In addition, voltage smoothing means may also be provided, which smooth a supplied voltage for outputting to the drive device. Rectifying devices for rectifying the inductively supplied voltage may also be provided.
[0019] In a further advantageous embodiment, at least one (electric) coil element is provided on the transport device, which coil element serves for providing the electrical energy to the drive device. By means of this coil, currents can be generated or induced by the magnets arranged on the transport path, which currents are in turn supplied to the drive device. This will be explained in more detail with reference to the figures. This coil element may be wound around a core. Preferably, the ends of this core point towards the transport path or the electromagnets thereof This coil element is preferably electrically conductively connected to the drive device.
[0020] In a further advantageous embodiment, at least some of the magnetic elements of the transport path are electromagnets. By suitable actuation of these electromagnets, on the one hand a movement of the transport elements relative to the transport path can be achieved, but on the other hand it is also possible to supply the drive device inductive with electrical energy by means of suitable actuation.
[0021] In a further advantageous embodiment, therefore, said magnetic elements of the transport path also serve for the electrical supply to the drive device. Advantageously, at least one magnetic element is suitable, by virtue of appropriate actuation, both for achieving the movement of the transport element in its entirety and also for supplying the drive device. However, it would also be possible, for example, that two parallel paths of magnets are arranged on the transport path, wherein one of these paths serves for generating the movement and the other serves for supplying the drive device.
[0022] In a further advantageous embodiment, the apparatus has a control device which supplies the magnetic elements with a movement-generating voltage, by which a movement of the transport elements is brought about, and/or which supplies the magnetic elements with an activator voltage which supplies the drive device with electrical energy. Advantageously, both voltages are alternating voltages. In this case, it is possible to control on the one hand a speed of the transport element relative to the transport path, but also an activation or actuation of the drive device.
[0023] In a further advantageous embodiment, the activator voltage has a higher frequency than the movement-generating voltage. In the case of the movement-generating voltage, for example, it is possible that the individual magnets are magnetized in a predefined order and thus the transport element is drawn forwards by the magnetic force. The voltages used to operate the at least one working element on the transport element are of higher frequency in comparison thereto, in order in this way not to interfere with the movement of the transport element.
[0024] In a further advantageous embodiment, the transport path has a plurality of coil elements for supplying the magnetic elements. It is possible in each case that two electromagnet ends arranged next to one another are supplied by one coil, so that, depending on the direction of current within the coil, one of the two regions becomes the magnetic plus pole and the other becomes the magnetic minus pole.
[0025] Embodiments of the present invention are also directed to a method for transporting containers, wherein the containers are moved by a plurality of transport elements along a transport path which is preferably but not necessarily circumferential, and wherein the transport path has a plurality of magnetic elements and the movement of the transport elements along the transport path is generated by a magnetic force. At least one magnetizable element is also arranged on the transport elements, which magnetizable element serves for the movement of the transport element along the transport path.
[0026] According to embodiments of the invention, a drive device which can be operated by electrical energy is arranged on at least one transport element, and this drive device is also supplied inductive with electrical energy.
[0027] The containers are preferably plastic containers and in particular plastic bottles or plastic preforms. Advantageously, the containers are transported from a first treatment device, which treats the containers in a first predefined manner, to a second treatment device, which treats the containers in a second predefined manner.
[0028] Advantageously, the magnetic elements of the transport path are supplied with a movement-generating voltage, by which the movement of the transport elements is brought about, and with an activator voltage which supplies the drive device with electrical energy. Preferably, the supplying with the respective voltages takes place simultaneously at least at times. However, it would also be possible that the supply to the drive devices takes place not continuously but rather, for example, only at certain path sections. For example, it would be possible that energy storage means, such as batteries or capacitors, are provided on each of the transport elements and these energy storage means are charged, for example, in those regions in which no container is located on the transport elements.
[0029] In a further advantageous method, a first magnetic field, which brings about the movement of the transport elements, is transmitted in a first predefined region in relation to the transport element and a second magnetic field, which supplies the drive device with electrical energy, is transmitted in a second region in relation to the transport element. The two regions are advantageously offset relative to one another. Advantageously, said second region is located upstream of the first region in a transport direction of the transport element relative to the transport path.
[0030] However, it would also be possible that the two magnetic fields are transmitted in the same regions, and in particular by the same magnetic elements. For instance, on the one hand the movement of the respective transport element could be achieved by the magnetic elements, but at the same time the voltage applied to these magnetic elements could be modulated with a further voltage which serves for supplying the electric drive device.
[0031] Advantageously, the transport elements are moved relative to the transport path by means of roller bodies.
[0032] In a further advantageous method, the transport elements are moved in one plane and particularly preferably in a horizontal plane.
[0033] In a further advantageous embodiment, the transport elements are moved at least in some sections along a transport path of finite curvature. Advantageously, the transport elements are also moved along a transport path with different directions of curvature, that is to say with radii of curvature having different signs.
[0034] Advantageously, the movement of at least one transport element is controlled independently of the movement of at least a second transport element. This means that, for example, a relative speed of one certain transport element in relation to the relative speed of a second transport element can change during the transporting of the transport elements relative to the transport path.
[0035] Advantageously, a spacing between two successive transport elements changes at least temporarily during transport along the transport path.
BRIEF DESCRIPTION
[0036] Some of the embodiments will be described in detail, with reference to the following figures, wherein like designations denote like members, wherein:
[0037] FIG. 1 shows an arrangement for treating containers, having an apparatus; and
[0038] FIG. 2 shows a detail view of an apparatus.
DETAILED DESCRIPTION
[0039] FIG. 1 shows a system for treating containers. This arrangement has a first treatment machine 10 , which treats the containers in a predefined manner. The arrangement additionally has a second treatment machine 20 , which is arranged downstream of the first treatment machine in a transport direction of the containers and which treats the containers in a second predefined manner. For example, the first apparatus may be an oven which heats the plastic preforms, and the second treatment apparatus may be a transforming device which transforms the (heated) plastic preforms into plastic containers. However, other arrangements and/or combinations of machines would also be conceivable, for example a transforming device and a filling device arranged downstream thereof, a filling device and a capping device arranged downstream thereof, and the like.
[0040] Located between these two apparatuses 10 , 20 is an apparatus 1 according to embodiments of the invention for transporting plastic containers. This apparatus 1 has a transport path 2 which is arranged in a stationary manner and relative to which a plurality of transport elements 4 move. However, only three of these transport elements are shown in detail here. The individual transport elements can thus move along the transport path 2 , which is a closed transport path here. This transport path has a carrier, relative to which the individual transport elements can move.
[0041] However, embodiments of the invention permit independent control of the movements of the individual transport elements. For example, the spacings between two adjacent transport elements can be increased and reduced largely at will. The transport elements can also be moved more quickly or more slowly independently of one another.
[0042] The procedure according to embodiments of the invention also offers the advantage that the transport path can also be adapted to the configurations of the downstream apparatuses, in this case in particular to a circular transport path which results in the region of the first treatment apparatus 10 and the second treatment apparatus 20 . The individual transport elements have here a carrier 46 and a holding element 48 arranged thereon for holding the plastic containers (not shown). During operation, it would be possible, for example, that the plastic preforms are accepted by the first apparatus 10 for treating plastic containers and then are brought relatively quickly into the region of the second apparatus, where they are again transported at a speed adapted to the second treatment apparatus 20 .
[0043] FIG. 2 shows a detailed view of an apparatus 1 according to embodiments of the invention. The transport path 2 is again shown. Here, this transport path 2 has a plurality of magnetic elements 22 , 24 . These are each connected in series and each have a magnetic core, around which a coil 26 , 28 is wound. By appropriate actuation of this coil, the magnetic elements 22 , 24 can be actuated at will.
[0044] A transport element 4 , which is denoted 4 in its entirety, can move relative to this (stationary) transport path 2 in a movable manner. For this purpose, rollers 42 are provided here, by means of which the transport element can roll relative to the transport path 2 .
[0045] However, it would also be possible that the transport element 4 is designed in the manner of a magnetic suspension railway. By suitable actuation of the successive magnetic elements 22 , 24 , the transport element 4 can be moved, for example, in the direction from left to right in the figure (arrow P 1 ). For this purpose, magnetizable elements, and here in particular permanent magnets 44 , 46 , are also arranged on the transport element 4 . These magnetizable elements are preferably provided with alternating polarities. In the situation shown in FIG. 2 , the transport element is still being pulled to the right by the suitable magnetization of the magnetic elements 22 , 24 .
[0046] A drive device 6 is additionally arranged on the transport element 4 . Said drive device is shown only schematically here, and it may be, in particular, any type of electric drive, in particular electric motors, electromagnets and the like.
[0047] Preferably, this drive device can carry out a working operation with the container to be transported.
[0048] In addition, the transport element 2 has a further coil arrangement 64 and also an iron core 62 . By means of this arrangement, current and/or voltage can be supplied to the drive device 6 via an alternating magnetic field. Preferably, the drive device 6 can thus be supplied with voltage in a contactless manner. For this purpose, there is applied to the coil 28 of the magnetic element 24 a (high-frequency) alternating voltage which generates a corresponding alternating magnetic field. Via this alternating magnetic field, the drive device 6 can be supplied with current.
[0049] Reference 50 denotes a control device which actuates the individual magnetic elements. It is pointed out here that the individual magnetic elements 22 and 24 can serve, depending on their position, both for the movement of the transport element 4 and for supplying current to the drive device 6 . Therefore if, for example, the transport element 4 has moved further by one position starting from the situation shown in FIG. 2 , the magnetic element 24 brings about the movement or onward pulling of the transport element and the further magnetic element 34 , neighbouring the magnetic element 24 to the right, supplies the drive device 6 with voltage. This means that, during operation, the application of the alternating electric field to the magnetic elements 22 , 24 for supplying the drive device also migrates, namely preferably at the same speed at which the transport element 4 also moves relative to the transport path 2 .
[0050] Preferably, therefore, the distance between a magnetic element which is presently responsible for supplying energy to the drive element 6 and a magnetic element which is presently responsible for the movement of the transport element 4 is constant.
[0051] In other words, the control device is configured in such a way that the respective forwarding of the alternating field or alternating current for the magnetic elements proceeds at the same speed as the magnetizing wave, which magnetizing wave is in turn responsible for moving the transport element 4 .
[0052] As mentioned, however, at a given point in time, the same magnetic element can also be used both for generating the transport element in its entirety and for the electrical supply to the drive device 6 .
[0053] However, it would also be possible that magnetic elements are provided exclusively for the movement of the transport element 4 , and magnetic elements arranged for example in parallel therewith are responsible exclusively for supplying current to the drive device 6 . In this case, it would likewise be conceivable that the energization or actuation of these two magnetic elements proceeds in each case at the same speed, in particular at the speed of the transport elements relative to the transport path 2 .
[0054] Preferably, therefore, the coil device 64 can form with the coil devices of the transport path a pairing which is constructed on the same principle as a transformer. Besides the actual magnetic field which serves for the movement of the transport element, the abovementioned second magnetic field can move with the two poles. This second magnetic field changes direction with a higher frequency, and thus generates an alternating magnetic field relative to the coil device 64 .
[0055] Preferably, this second magnetic field can be switched on and off at will, which is also due to the design of the arrangement as a linear motor. As mentioned above, this induced voltage can be used to switch, for example, an electromagnet or electrocylinder and thus, in any position and for any length of time, can carry out an action such as, for example, a clamping, rotation or displacement.
[0056] Preferably, this switching process or this supply to the drive device represents in the control device a second movement device which is arranged at a fixed distance from the first drive that is responsible for the movement of the transport element. In this case, control software may be provided for changing with a higher frequency the magnetic field for supplying the drive device.
[0057] In addition, it would also be possible that the apparatus has trigger devices which switch on or off a supply to the drive device at predefined positions of the transport element relative to the transport path. For example, there could be arranged on the transport element and/or on the transport path a light barrier device which detects a position of the transport element 4 . Preferably, the drive device can be controlled depending on a position, thus detected, of the transport element 4 relative to the transport path.
[0058] However, it would also be conceivable that a position of the transport element relative to the transport path is determined by the transport path and/or on the basis of currents induced here.
[0059] For example, a gripping device arranged on the transport element 4 for gripping the containers could be actuated in such a way that it grips a container at a predefined position of the container and/or releases the grip on the container at another predefined position of the transport element relative to the transport path.
[0060] In this case, it would be possible that commands, for example control commands for the drive device, are also transmitted to the drive device (for instance through suitable modulation of the signal) along with the supply energy for the electrical supply of the drive device.
[0061] Furthermore, it would also be possible that several drive devices are arranged on at least one transport element ( 4 ). In this case, it would be possible that these drive elements are controlled and/or supplied with energy independently of one another. This energy may in each case be transmitted in the manner mentioned above, that is to say inductively.
[0062] Furthermore, it would also be possible that a processor device or a control device for controlling the drive device is arranged on the transport element. Furthermore, it is also possible that the apparatus has a detection device for detecting a position of a drive element of the drive device.
[0063] The applicant reserves the right to claim as essential to the invention all the features disclosed in the application documents in so far as they are novel individually or in combination with respect to the prior art.
[0064] Although the present invention has been disclosed in the form of preferred embodiments and variations thereon, it will be understood that numerous additional modifications and variations could be made thereto without departing from the scope of the invention.
[0065] For the sake of clarity, it is to be understood that the use of “a” or “an” throughout this application does not exclude a plurality, and “comprising” does not exclude other steps or elements. The mention of a “unit” or a “module” does not preclude the use of more than one unit or module.
LIST OF REFERENCE SIGNS
[0000]
1 apparatus according to the invention
2 transport path
4 transport elements
6 drive device
10 first treatment machine
20 second treatment machine
22 , 24 , 34 plurality of magnetic elements
26 , 28 coil
42 carrier
44 , 46 permanent magnets
48 holding element
50 control device
62 iron core
64 coil arrangement | An apparatus for transporting containers, having a circumferential transport path and at least one transport element which is arranged such as to be movable relative to this circumferential transport path, wherein this transport element can be driven at least partially by means of a magnetic force, wherein the transport path has a plurality of magnetic elements and at least one magnetizable element is also arranged on the transport element, and wherein a movement of the transport element relative to the transport path can be achieved by actuating the magnetic elements of the transport path is provided. According to the invention, an electrically operated working element, which can be supplied inductive with electrical energy, is arranged on the transport element. | 1 |
This is a divisional application of Ser. No. 07/813,013, filed Dec. 24, 1991, now U.S. Pat. No. 5,240,185.
BACKGROUND OF THE INVENTION
This invention relates to an improved paint powder supply device for use in electrostatic power painting apparatus as extending from a paint powder tank to a painting gun and adapted to effect a uniform discharge of paint powder through the painting gun and thus to create a painted surface having a uniform paint film thickness.
A conventional paint powder supply device has various problems. First, the paint powder tank has the following problems. Heretofore, a fluidized type paint powder tank has been used as the tank of the electrostatic paint powder apparatus.
In such a paint powder tank, a porous resin plate is provided at the bottom of the tank. Compressed air is supplied into the tank through the porous resin plate to stir and dehumidify the paint powder in the tank. The density of the paint powder in the tank changes with its amount in the tank.
For example, as the amount of paint powder in the tank decreases, i.e. as the level of the paint powder in the tank becomes lower, the density of the paint powder decreases correspondingly.
Thus, if the paint powder in the fluidized type powder tank is drawn out by a discharge device such as an injector, the discharge rate changes according to the paint powder level in the tank as shown by line a in FIG. 1.
Thus, it was impossible when using such a conventional fluid type paint powder tank to discharge the paint powder at a uniform rate.
Secondly, there have been the following problems in drawing out the paint powder from the paint powder tank. A conventional device for drawing the paint powder out of the paint powder tank comprises a discharge pipe provided at the lower part of the paint powder tank and a pinch valve attached to the discharge pipe and adapted to close the flow line when air is supplied thereto. The paint powder in the paint powder tank can be discharged by opening and closing the pinch valve.
In this type of device, if the discharge of paint powder is stopped for a long time by the pinch valve, the paint powder left in the part of the discharge pipe upstream of the pinch valve may become moist so that the discharge pipe can become clogged with the paint powder at that part. This makes it difficult for the paint powder to drop smoothly when the pinch valve is opened and thus to supply the paint powder smoothly.
Thirdly, a paint supply device for supplying the paint powder in the paint powder tank to the painting gun had the following problems.
In a conventional paint supply device, an injector is directly attached to the side or top of the paint tank containing the paint powder. The injector is coupled to the painting gun through a hose. The paint powder in the paint tank is drawn out by the injector together with air. The air is used to send the paint powder to the painting gun.
The discharge rate through the painting gun is determined by the air pressure and amount of air in the injector. In order to create a painted surface having a uniform film thickness, the discharge rate through the painting gun has to be uniform.
But even if the air pressure and amount of air in the injector are unchanged, when the amount of paint powder in the paint tank decreases, the air content in the paint powder increases and the pressure changes according to the thickness of the paint powder, so that the amount of paint powder sucked by the injector decreases. This in turn causes a decrease in the rate at which the paint powder is discharged through the painting gun. Thus, it was difficult to form a paint film having a uniform thickness. This may result in transparent paint films or defective painted goods.
If paint powder sticks to the inner surface of the hose extending from the injector to the painting gun or if the hose is closed with foreign matter, a pressure loss will occur in the hose. This reduces the amount of paint sucked into the injector, thus changing the discharge rate of the paint powder.
Thus, in a conventional paint supply device having an injector attached to the paint tank so as to directly aspirate the paint powder from the paint tank, it was difficult to discharge the paint powder through the painting gun at a uniform rate.
SUMMARY OF THE INVENTION
The present invention has been developed in order to overcome the above-described drawbacks of the prior art electrostatic powder painting apparatus.
It is therefore a first object of the present invention to provide a fluidized type powder paint tank which can discharge paint powder at a uniform rate without being affected by the level of the paint powder in the tank.
A second object of the present invention is to provide a paint powder discharge device which prevents the discharge pipe from getting clogged with paint powder and thus can assure a smooth discharge of the paint powder from the tank.
A third object of the present invention is to provide a paint powder supply device which assures a uniform discharge rate of powder paint through the painting gun.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and objects of the present invention will become apparent from the following description made with reference to the accompanying drawings, in which:
FIG. 1 is a graph of the relation between the level of the paint in the tank and the discharge rate in the conventional apparatus and in the apparatus according to the present invention;
FIGS. 2-6 are schematic diagrams of preferred embodiments of the paint powder tank according to the present invention, FIGS. 2, 4 and 6 being side views of the various embodiments and FIG. 3 being a plan view of the embodiment shown in FIG. 2;
FIG. 7 is a sectional view of the outlet portion of an embodiment of the paint powder tank according to the present invention;
FIG. 8 is a side view of the outlet portion shown in FIG. 7;
FIG. 9 is a front view, partially broken-away, of the paint powder supply device according to this invention;
FIG. 10 is a sectional view of a portion of the device shown in FIG. 9; and
FIG. 11 is an enlarged view of a portion of the device shown in FIG. 10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
To achieve the first objection of the present invention, the fluid type paint powder tank is improved. Its embodiments are described with reference to FIGS. 2-6.
The fluidized type paint powder tank 1 according to this invention has a fluidizing chamber 2 for moving paint powder A as a fluid and a storage chamber 3 for holding the paint powder A, drawn from the fluidizing chamber 2, in a stationary state.
A discharge device 4 is attached to the storage chamber 3 to discharge the paint powder A therefrom. The paint powder tank of the embodiment shown in FIGS. 2 and 3 is provided with a partitioning wall 5 on the righthand side thereof, defining the fluidizing chamber 2 to the left of the wall 5 and the storage chamber 3 to its right.
In the fluidizing chamber 2 at the lower part thereof, a porous plate 6 is provided slightly spaced apart from the bottom thereof. Compressed air 7 is fed under the porous plate 6. An air vent 8 is provided at the top of the fluidizing chamber 2.
The fluidizing chamber 2 and the storage chamber 3 communicate with each other at the lower part of the fluidizing chamber 2. An air purge nozzle 9 is provided in the fluidizing chamber 2 at the lower part thereof to discharge the paint powder A in the fluidizing chamber 2 into the storage chamber 3 by intermittently feeding air toward the storage chamber 3. As shown in FIG. 3, this nozzle 9 may take the form of three nozzle members connected so as to receive air in common. Instead of the air purge nozzle 9, a scraper which moves on and along the porous plate 6 toward the storage chamber 3 may be used to discharge the paint powder A in the fluidizing chamber 2 into the storage chamber 3.
The bottom of the storage chamber 3 is at a level lower than the bottom of the porous plate 6 and the bottom of that portion of the tank 1 beneath the fluidizing chamber 2.
An injector as the discharge device 4 is mounted at the lower part of the storage chamber 3. A painting gun 11 is connected to the injector 4 through a powder supply hose 10. The embodiment shown in FIG. 4 has the same structure as the embodiment shown in FIGS. 2 and 3 except with regard to the discharge device 4.
The discharge device 4 in this embodiment has the following structure. Namely, a screw 13 rotated by a motor 12 is mounted at the bottom of the storage chamber 3. A discharge port 14 is formed in the side of the storage chamber 3 at the front end of the screw 13. Beside the discharge port 14, there is provided a cylindrical flow straightener 15 having a drop hole in the bottom thereof. Beside the flow straightener 15, a spring housing 16 is provided. A lid plate 18 is secured to the end of the screw 13 and is pressed against the discharge port 14 by a spring 17 housed in the spring housing 16.
By rotating the screw 13 with the motor 12, the powder A at the bottom of the storage chamber 3 is pushed out toward the discharge port 14. The spring 17 is compressed and the lid plate 18 is opened by this pushing force, so that the power is blown out through a gap between the lid plate 18 and the discharge port 14. The powder thus blown out impinges and moves along the inner peripheral surface of the flow straightener 15 and is discharged in uniform amounts into a hopper 19 provided thereunder. An injector 20 is mounted to the bottom of the hopper 19. The powder is fed from the injector 20 into the painting gun 11 through a powder supply hose 10.
In the embodiment shown in FIG. 5, a porous plate 6 is provided above the bottom of the tank 1 so as to cover the entire bottom surface of the tank 1. A partitioning wall 5 is provided to divide the space over the porous plate into the fluidizing chamber 2 and the storage chamber 3. A shield plate 21 is provided on the portion of the porous plate 6 located in the storage chamber 3 to prevent air from being supplied through the porous plate into the storage chamber 3. Otherwise, the embodiment shown in FIG. 5 has the same structure as the embodiment shown in FIG. 1.
The tank 1 of the embodiment shown in FIG. 6 has the same structure as that of the embodiment shown in FIG. 5. The discharge device 4 has the same structure as that of the embodiment shown in FIG. 4. In the embodiment shown in FIG. 6, the motor 12 for the screw 13 is mounted on the tip of the screw.
The paint powder tank according to this invention can discharge the paint in constant amounts irrespective of the paint level in the tank, as shown by line (b) in FIG. 1. Thus, the thickness of paint can be kept constant.
In order to achieve the second object of the present invention, improved means for drawing out the paint powder is provided. The embodiment of the drawing out means is described with reference to FIGS. 7 and 8.
In a paint powder tank 31, a porous plate 32 is mounted at the bottom thereof. Compressed air is supplied under the porous plate 32 to move the paint powder in the tank.
An outlet port 33 is formed in the side wall of the tank 31 at its lower part. An outlet pipe 34 is connected to the outlet port 33.
A pinch valve 35 is connected to the bottom end of the outlet pipe 34. It comprises a collapsible tube 36 made of rubber or the like and a casing 37 covering the tube 36. An air supply pipe 38 is connected to the casing 37. By supplying air through the air supply pipe 38 into a gap between the inner wall of the casing 37 and the outer wall of the tube 36, the tube collapses, thus closing the flow path. When the supply of air is stopped, the tube 36 expands, thereby opening the flow path.
The air supply pipe 38 has a branch pipe 39 connected to the outlet pipe 34 above the pinch valve 35. In the branch pipe 39 is provided a check valve 40 to prohibit fluid flow from the outlet pipe 39 toward the air supply pipe 38.
When the pinch valve 35 is closed by supplying air into the air supply pipe 38 of the pinch valve 35, the air is also supplied through the branch pipe 39 into the outlet pipe 34 thereby bypassing the pinch valve 35. Thus, while the pinch valve 35 is closed, the paint powder in the outlet pipe 34 is continuously moved by the air supplied. This prevents the clogging of the outlet pipe 34.
When the pinch valve 35 is opened by stopping the supply of air into the air supply pipe 38, the supply of air into the outlet pipe 34 through the branch pipe 39 is also stopped. Thus, the paint powder in the paint powder tank 1 is drawn out downwards through the outlet pipe 34 and the pinch valve 35.
The paint powder drawn out through the pinch valve 35 is supplied into the painting gun through a hopper 41.
According to this invention, even if the drawing out of the powder paint is stopped for a long time by shutting the pinch valve 35, the outlet pipe 34 will never clog. Thus, when the pinch valve 35 is opened to resume the drawing out of the paint powder, it will be drawn out smoothly.
Even though no air is supplied through the porous plate 32 provided at the bottom of the paint powder tank 31, air is supplied into the paint powder tank 31 through the outlet pipe 34. Thus, the paint powder in the paint powder tank will be stirred by this air flow even while the device is not in operation.
In order to achieve the third object of the present invention, an improved powder paint supply device is provided for supplying paint powder from the paint powder tank into the painting gun. Its embodiment is described with reference to FIGS. 9-11.
A paint powder tank 51 is of a fluidized type. In this type of paint powder tank, in order to improve the dispersibility of the paint powder, air is uniformly blown into the powder layer, through a porous plate 52 provided at the bottom of the tank, to fluidize the paint powder.
To the lower part of the paint tank 51 is connected a discharge pipe 54 provided with a pinch valve 53. By opening the pinch valve 53, the paint powder in the paint powder tank 51 can free fall so as to be discharged downward.
The discharge pipe 54 is connected to the top of a hopper 55, which is provided with a level switch 56 for detecting the level of the paint powder stored in the hopper. The hopper 55 is provided with a lid 57 on top thereof. The lid 57 is provided with an air vent to expel excess air present in the paint powder fed into the hopper 55. Thus, the amount of the paint in the hopper 55 per unit volume will be uniform.
Under the hopper 55 is provided a screw feeder 58 for feeding powder. The screw feeder 58 has a screw 59 having its tip protruding into a discharge port 60 formed in the side of the hopper 55 near its bottom. The rear end of the screw 59 protrudes out of the hopper 55 and is coupled to a motor 62 through a joint 61. Adjacent the discharge port 60 there is provided a cylindrical flow straightener 63. Adjacent the flow straightener 63 there is provided a spring housing chamber 65.
To the tip of the screw 59 is coupled a support shaft 66 extending through the flow straightener 63 and the spring housing 65. A lid plate 67 is slidably fitted on the support shaft 66 at its portion located in the flow straightener 63 to close the end face of the discharge port 60. Further, a pipe 68 is fitted on the support shaft 66 at its portion behind the lid plate 67. The pipe 68 has its tip end protruding into the spring housing 65 and its rear end secured to the back of the lid plate 67. A spring 69 is fitted on the support shaft 66 at its portion located in the spring housing 65. The lid plate 67 is pressed by the spring 69 through the pipe 68 against the discharge port 60.
A support plate 70 for supporting the end of the spring 69 is mounted on the tip of the support shaft 66 so as to be movable relative to the support shaft. In order to adjust the force of the spring 69, the support plate 70 is moved by turning a threaded cap 85 provided at the end of the spring housing 65.
An air inlet pipe 71 is connected to the spring housing 65. Its interior is kept at positive pressure, thus preventing paint powder from flowing into the spring housing 65.
An agitating rotary wheel 72 is mounted in the hopper 55 at its lower part. Its periphery is provided with protrusions 73 at predetermined intervals so that they can bit into the pitch gaps defined by the screw 59. Thus, the agitating rotary wheel 72 is adapted to rotate as the screw 59 turns.
A damper plate 74 is provided in a drop port 64 of the flow straightener 63. By changing the angle of the damper plate 74, the size of the drop portion 64 can be changed. Thus, even when supplying a small amount of paint powder, the paint powder is prevented from being scattered. The screw feeder 58 is detachably mounted to the hopper 55. Further, the screw 59 of the screw feeder 58 and a casing 75 are replaceable.
As the screw 59 is rotated by the motor 62, the paint powder forming the lower layer in the hopper 55 is pushed out toward the discharge port 60. By this pushing force, the spring 69 is compressed and the lid plate 67 is opened, so that the paint powder pushed out through a gap between the lid plate 67 and the discharge port 60 will blow out. The paint powder blown out past the lid plate 67 and the discharge port 60 then hits the inner surface of the flow straightener 63 and is discharged at a constant rate through the drop port 64 while moving along the inner peripheral surface of the flow straightener 63.
A chute 76 (FIG. 9) is provided under the drop port 64 of the flow straightener 63. To an outlet 77 of the chute 76 is coupled an inlet port 79 of an injector 78. A hose 81 is coupled to a discharge port 80 of the injector 78. A painting gun 82 is coupled to the tip of the hose 81. A sensor 83 provided in the chute 76 is adapted to detect a predetermined amount of paint powder. The amount of air to be fed into the injector 78 will be sufficient if the paint powder supplied in regular amounts to the inlet port 79 of the injector 78 from the screw feeder 58 can be discharged through the hose 81 and the painting gun 82. An electropneumatic regulator may be provided in the air circuit to regulate, under electrical control, the amount of air supplied to a minimum value corresponding to the discharge amount.
A sieve may be provided in the drop port 64 of the screw feeder 58 to improve the dispersibility of the paint powder. In FIG. 9, numeral 84 designates a height-adjustable base.
In the operation of this paint supply device, the pinch valve 53 is opened and closed at predetermined intervals so that the paint powder in the paint tank 51 will accumulate in the hopper 55 in predetermined amounts. The amount is detected by the level switch 56. Any abnormality in the supply of powder can be detected by electrically monitoring the opening and closing of the pinch valve 53 and the time taken until the powder reaches the level switch 56.
Namely, if clogging should occur somewhere in the powder supply line, since the paint powder in the hopper 55 is not consumed, the time taken until the paint powder reaches the level switch 56 after opening the pinch valve 53 will become shorter than a monitoring cycle time. If the powder supply line from the paint tank 51 to the hopper 55 should fail, the time taken until the paint powder reaches the level switch 56 will become longer than the monitoring cycle time. If the time is out of the range of the monitoring cycle time, the line is stopped on the assumption that it has failed.
Any excess air in the paint powder supplied into the hopper 55 is spontaneously expelled while being accumulated. The paint powder in the hopper 55 is fed out at a constant rate through the discharge port 60 by the screw feeder 58. By this push-out force, the spring 69 is compressed and the lid plate 67 is opened, so that the paint powder pushed out through a gap between the lid plate 67 and the discharge port 60 will blow out. The paint powder blown out past the lid plate 67 and the discharge port 60 then hits the inner surface of the flow straightener 63 and is supplied at a constant rate into the inlet port 79 of the injector 78 through the drop port 64 and the chute 76.
The paint powder supplied into the injector 78 is then supplied by air through the hose 81 and is discharged through the painting gun 82.
If the hose 81 is clogged with paint powder, the paint powder will flow over the inlet port 79 of the injector 78 and remain at the outlet 77 of the chute 76. The accumulation of the paint powder at the outlet of the chute 76 is detected by the sensor 83. This makes it possible to stop the painting line when an abnormality is detected. Thus, the production of defective articles can be minimized.
As described above, according to this invention, since paint powder can be supplied at a uniform rate into the injector, the amount of paint discharged through the painting gun can be kept uniform even if there is a slight pressure loss in the hose of the painting gun.
Since the amount of paint powder to be supplied into the injector can be changed by changing the revolving speed of the screw of the screw feeder, the discharge rate through the painting gun can be set to any desired value. | A fluidized type paint powder tank has a fluidizing chamber for fluidizing paint powder and a storage chamber into which the paint powder in the fluidizing chamber is fed to keep it still. There is also provided a paint supply device for an electrostatic powder painting apparatus that includes a paint tank for containing paint powder and a painting gun coupled to the paint tank through an injector and a hose. The device includes a discharge member for discharging the paint powder from the paint tank and a hopper for receiving the paint powder discharged by the discharge member. A screw feeder is provided under the hopper. With this arrangement, the paint powder supplied at a uniform rate by the screw feeder is fed into the injector. | 1 |
This is a continuation of application Ser. No. 003,203 filed Jan. 14, 1987, now abandoned.
TECHNICAL FIELD
This invention is related to amorphous thin film magneto optic recording media. More particularly, it pertains to the protection of the amorphous thin film alloy active layer in such media from deterioration by chemical contaminants or corrosion.
BACKGROUND
Magneto-optic recording media are also known by several other names: thermomagnetic media, erasable optical media, beam addressable files, and photo-magnetic memories. All of these terms apply to a storage medium or memory element which responds to radiant energy permitting the use of such energy sources as laser beams for both recording and interrogation. Such media modify the character of an incident polarized light beam so that the modification can be detected by an electronic device such as a photodiode.
This modification is usually a manifestation of either the Faraday effect or the Kerr effect on polarized light. The Faraday effect is the rotation of the polarization plane of polarized light which passes through certain magnetized media. The Kerr effect is the rotation of the plane of polarization of a light beam when it is reflected at the surface of certain magnetized media.
When a magnetizable amorphous film is deposited on a reflector, the magneto optic rotation is increased because the Faraday effect is added to the Kerr effect. The former effect rotates the plane of polarization of the light as it passes back and forth though the magneto-optic layer while the Kerr effect rotates it at the surface of the layer.
A change in orientation of polarization of the light is caused by the magneto-optical properties of the material in the bit or site on which the polarized light is incident. Thus, the Kerr effect, Faraday effect or a combination of these two, is used to effect the change in the plane of light polarization. The plane of polarization of the transmitted or reflected light beam is rotated through the characteristic rotation angle Θ. For upward bit magnetization, it rotates Θ degrees and for downward magnetization -Θ degrees. The recorded data, usually in digital form represented by logic values of 1 or 0 depending on the direction of bit magnetization may be detected by reading the change in the intensity of light passing through or reflected from the individual bits, the intensity being responsive to the quantity of light which is rotated and the rotation angle.
The main parameters that characterize a magneto optic (MO) material are the angle of rotation, the coercive force (H c ), the Curie temperature and the compensation point temperature. The medium is generally comprised of a single element or multicomponent system where at least one of the components is an amorphous metal composition. Binary and ternary compositions are particularly suitable for these amorphous metal alloys. Suitable examples would be rare earth-transition metal (RE-TM) compositions, such as Gadolinium-cobalt (Gd-Co), Gadolinium-iron (Gd-Fe), Terbium-iron (Tb-Fe), Dysprosium-iron (Dy-Fe), Gd-Tb-Fe, Tb-Dy-Fe, Tb-Fe-Co, Terbium-iron-chromium (Tb-Fe-Cr), Gd-Fe-Bi (Bismuth), Gd-Fe-Sn (Tin), Gd-Fe-Co, Gd-Co-Bi, and Gd-Dy-Fe.
The susceptibility of Re-Tm alloys to corrosion is well known. When used as a thin film in MO disks, the alloy is usually protected from contact with the ambient atmosphere by surrounding it with dielectric layers, partially as an effort to prevent corrosion by water which may be aided by other materials (e.g., chlorides). The RE-TM alloy and surrounding dielectric layers are often deposited on a transparent substrate, e.g. transparent polymer such as polycarbonate or polymethylmethacrylate. Such protection prevents observable corrosion for short periods (several months) of time under ambient conditions. However, extensive lifetimes (5-10 years) without corrosion are required of optical disks.
Because the active MO layer is usually quite thin, once significant corrosion has occurred the corrosion sites can become apparent as transparent or bright spots on the recording medium where the active RE-TM alloy may have been disrupted or converted to transparent oxide, exposing the underlying reflector. The result of this corrosion is a loss of stored information. Over time, the corrosion sites grow and increase the amount of lost information.
Previous literature references to corrosion of MO media indicate that additions of titanium, platinum and other elements are effective in inhibiting corrosion in samples of bare MO media exposed to aqueous salt solutions (Imamura, N., et al., "Magneto-Optical Recording on Amorphous Films", IEEE Transactions on Magnetics, September 1985, p. 1607 and Kobayashi, et al., IEEE Translation Journal on Magnetics in Japan, August, 1985). However, the present inventors have found that complete multilayer disk constructions do not exhibit the same corrosion performance as bare MO films.
DISCLOSURE OF INVENTION
The problem of corrosion has been approached by modifying the RE-TM alloy composition through the addition of certain elements. The invention is summarized as a magneto optical recording medium comprising a substrate; a magnetizable rare-earth transition metal alloy layer which is protected from contact with ambient atmosphere by a layer or layers on all sides, one of which layers may be the substrate; and a reflective surface; wherein the magnetizable alloy comprises a combination of an iron-terbium alloy together with an added metal selected from the group consisting of yttrium, tantalum, and combinations thereof.
Both tantalum and yttrium have been shown to be effective in retarding corrosion, and both additions are made by adding the yttrium or tantalum to the source material (i.e., sputter target or targets) from which the components of the magnetizable RE-TM alloy layer originate. The addition of yttrium or tantalum has been shown to significantly reduce the occurence of local corrosion during testing of MO disks at accelerated aging conditions of 70° or 80° C. and 90% relative humidity. These accelerated aging tests are used to predict long term disk stability under normal operating and storage conditions.
During environmental testing at high humidity and high temperature, water penetrates the plastic substrate, resulting in local corrosion at locations where the protective dielectric layers may have tiny pinholes, cracks, or pores. These faults can result from minute deformities in the stamper or mold used to form the substrate. Experiments have shown that the appearance of localized corrosion (pits or pinholes in the active MO layer) is strongly influenced by the presence of chlorine- or sulfur-containing compounds in the substrate or environment.
The addition of yttrium or tantalum in concentrations sufficient to reduce corrosion has only a small influence, if any at all, on the properties of the magnetizable alloy layer other than corrosion resistance. Therefore, the information storage capability of MO media made using the films of improved corrosion resistance is only slightly affected.
Many film substrates can be used. They may be formed of any material which is dimensionally stable, minimizing radial displacement variations during recording and playback. Semiconductors,insulators, or metals can be used. Suitable substrates include glass, spinel, quartz, sapphire, aluminum oxide, metals such as aluminum and copper, and polymers such as polymethyl-methacrylate (PMMA), polycarbonate, and polyester. The substrate is typically in the form of a disc.
The reflective surface may be a smooth, highly polished surface of the substrate itself (e.g., aluminum), or it may be the surface of a separate reflecting layer deposited by techniques known in the art such as vacuum vapor deposition. It is located within the recording medium construction so as to reflect light back through the magnetizable alloy layer. The reflective surface or layer usually has a reflectivity greater than about 50% (preferably 70%) at the recording wavelength. Deposited reflecting layers usually are about 50 to 500 nanometers thick. Useful as reflective surfaces or layers are copper, aluminum or gold.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is an optical photomicrograph of an MO disk of the present invention containing 2.5% tantalum, which disk had been exposed to conditions of 80° C. and 90% relative humidity for 434 hours, taken at 520×magnification. Corrosion sites are visible as light spots in FIG. 1.
FIG. 2 is an optical photomicrograph (taken at 520×magnification) of another MO disk, identical to the disk in FIG. 1 and made in the same molding equipment, except that the magnetizable RE-TM alloy contained no tantalum. The photomicrograph was taken at the same area on the disk as was used for FIG. 1, so that it would be exposed to the same minor defects and scratches which may have been transferred from the molding equipment, and the environmental condition to which the disk was exposed were the same (i.e., 80° C. and 90% relative humidity for 434 hours). The corrosion sites are plainly visible as light spots in FIG. 2. The number and size of corrosion sites in FIG. 2 are much larger than in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
The magnetizable RE-TM alloy layers in the media of this invention are generally between 5 and 200 nm (nanometers) thick. The concentration ranges of the components are usually as follows:
Iron =--balance
Terbium =--10-30 atom percent (preferably 15-30%)
Cobalt =--0-30 atom percent
Tantalum =--0.1-10 atom percent (preferably less than 5%)
Yttrium =--0.1-10 atom percent (preferably no more than 5%)
The RE-TM alloy is also generally characterized as amorphous, that is a noncrystalline solid which does not possess spatially periodic atomic arrangements. Amorphous materials have no long range atomic order. When analyzed by electron beam diffraction, amorphous alloys produce a broad diffraction line followed perhaps by a number of weak, broad lines. Such diffraction patterns with broad lines or halos are not easily assigned to a crystalline structure, although some localized atomic ordering on a very small scale may be present.
The RE-TM alloy layer may also be characterized as having a multiplicity of magnetic domains, preferably all of which are less than 500 angstroms in largest dimension. A domain refers to the smallest stable magnetizable region in the alloy; although, in common usage, a domain is a uniformly magnetized region of any size. Domain size, as used herein, means the greatest dimension of the domain measured in the plane of the RE-TM alloy layer.
A triode sputtering process is suitable for depositing the RE-TM films of this invention. The triode sputtering apparatus comprises a vacuum chamber containing a sputtering cathode target where the metal alloy is placed. The alloy sputters to provide an accumulation on the substrate which is placed on the substrate holder. The cathode target is water cooled, and the substrate can be made to rotate through an external drive means. A shutter is usually provided between the target and the sample to allow sputter cleaning of the target prior to deposition. The sputtering chamber itself is made of stainless steel.
In operation, the sputtering chamber is typically pumped down to some initial background pressure (e.g., 4.0×10 -7 Torr) after which the sputter gas (argon) is introduced. Typically, the target is cleaned by presputtering for about 60 seconds at a bias voltage of about 300 volts. The substrate is exposed to the flux of atoms from the target after the predetermined sputtering conditions have been reached.
The yttrium and tantalum additions were made by placing pieces of the desired addition on top of an Fe-Tb-Co target in a sputtering apparatus. The concentration of both yttrium and tantalum added to the sputtered RE-TM films was varied by varying the area of added pieces on top of the Fe-Tb-Co target. It is also possible to produce the desired alloy film by sputter deposition using a target which is an alloy of all the desired elements.
The rare earth-transition metal film is one component of a complete magneto-optic medium. Other elements are a rigid substrate and various transparent dielectric films and reflective metallic films. If the light beam addresses the magnetizable film from the substrate side (substrate incident medium), a substrate of a transparent plastic (polycarbonate, polymethylmethacrylate, etc.) or glass can be used. If the light beam addresses the rare earth-transition metal from the side opposite the substrate (air incident medium) the substrate may be an opaque and/or reflective material such as aluminum, copper, or other metals and semiconductors. In both cases (substrate and air incident) the substrate provides a rigid base for material deposition and may contain physical features (such as grooves) for laser beam tracking.
Thin transparent dielectric layers (typically 10-200 nanometers (nm) thick) may be positioned on either or both sides of the RE-TM film. The dielectric layers can be deposited by vacuum deposition techniques such as sputtering or evaporation. These films serve the dual role of enhancing the optical signal from the RE-TM film and protecting the RE-TM film from corrosive and oxidative environments such a water, water vapor, air, and corrosion enhancing chemicals such as chlorine and sulfur. Suitable materials for the transparent dielectric are: silicon dioxide, silicon monoxide, aluminum oxide, and aluminum nitride. Use of other materials is also possible. The criteria for selecting them are that they should have transparency, an index of refraction greater than about 1.2 and good chemical stability (i.e. not degraded over time or by chemicals likely to be encountered).
If the MO medium is air incident and a non-reflective substrate is used and for substrate incident media, a film of reflective material (e.g. metals such as aluminum, copper, gold, or silver) may be used to reflect light which has been transmitted through the RE-TM film back through the RE-TM film. By this means, the MO signal is enhanced.
It is desirable to protect MO media with a thick transparent protective covering or defocusing layer. This protective layer helps in preventing damage to the medium through handling and leaves fingerprints and dust particles on the surface out of focus relative to the lens apparatus which reads the light beam reflected from the RE-TM layer. The defocusing layer is usually at least 1.2 mm thick. In the substrate incident construction, the substrate acts as the protective covering.
Despite the use of protective films and substrates to keep corrosive chemicals such as water, water vapor, chlorine, and sulfur from coming in contact with the RE-TM film, corrosion of the rare earth-transition metal film is observed. This corrosion takes place at sites where the protective measures break down due to water penetration through the protective films and substrates. This penetration may occur due to a diffusive process or through defects, cracks, or pinholes. By use of tantalum and/or yttrium additions to the rare earth-transition metal film, the severity of corrosion can be greatly suppressed.
The invention will be further clarified by considering the following examples which are intended to be purely exemplary.
EXAMPLE I
Six deposition runs were made using identical conditions with the exception that in two of the runs no yttrium was added to the FeTbCo film and in four runs an identical amount of yttrium was added to the FeTbCo films. For each run two injection molded, grooved polycarbonate substrates and two glass slides were loaded into a vacuum chamber which was evacuated to about 5×10 -7 torr. The sample rotating platen or planetary was used to rotate the disks about the chamber center and their axes during deposition. First a 525 Angstrom (Å) thick SiOx film was deposited at 4.5 Å/sec using a resistance heated evaporation boat filled with silicon monoxide powder. Then a 330 Å thick film of FeTbCo or FeTbCoY was deposited at about 3 Å/second by magnetically enhanced triode sputtering in argon gas. The source material (target) for the sputtering cathode was 51 mm×152 mm and consisted of bars of iron, cobalt, and terbium whose relative size had been selected to give films of good magneto-optic properties. The yttrium addition was made by placing two disks of yttrium 6.4 mm in diameter on top of the iron in the triode target. Based on previous ICP (Inductively Coupled Plasma) experiments, the approximate atomic composition of the FeTbCo films was Fe-65%, Co=13%, Tb-22%. For the FeTbCoY films the approximate atomic composition was Fe-61%, Co=13%, Tb=22%, Y=4%. During sputter deposition the argon flow rate was 30 sccm (standard cubic centimeters per minute) and the chamber pressure was 1.3×10 -3 torr. Other parameters were: Target voltage=200 volts, target current =1.25 Amps, emitter current=33 Amps, plasma voltage=68 volts, plasma current=5.9 Amps. Following deposition of the metal alloy films, a 400 Å thick film of SiOx was deposited at about 2.9 Å/second using the resistance heated evaporation boat. Finally, a 1400 Å thick film of aluminum +2 atomic percent chromium was deposited at about 8 Å/second using a DC planar magnetron sputtering source. Argon flow was 34sccm, pressure was about 1×10 -3 torr, target current was 10 Amps, and target voltage was 520 volts.
Disks from these six runs were tested using an optical recorder to determine carrier to noise ratio (CNR). The CNR for the yttrium-doped and yttrium-free disks were both good. The average CNR obtained using a 6 mw laser write power was 51 dB for the yttrium-free disks and 52 dB for the yttrium-containing disks.
One disk from each run was exposed to 70° C., 90% relative humidity corrosion testing which was interrupted at 397 hours and 536 hours to make optical microscopy studies of corrosion defect formation and growth. The number of defect sites in an arbitary area on the disks was determined. The average number of defect sites per disk in the arbitary area after 397 hours was 150 for the disks containing no yttrium and 23 for the disks containing yttrium. After 536 hours, the disks without yttrium had an average of 213 defects and the disks with yttrium had 74 defect. These results show that yttrium greatly reduced the formation of corrosion defects.
EXAMPLE II
The beneficial effects of yttrium addition are further shown through the results of a deposition run in which two MO disks were made of atomic composition 23% Tb, 14 Co, and 3.6% Y, the remainder being Fe. Three base line deposition runs were also carried out without yttrium addition for the purpose of comparison. Their atomic compositions were as follows: run 460: 21.8% Tb, 12.9% Co, remainder Fe; run 462: 21.4% Tb, 13% Co, remainder Fe; and run 467 22.8% Tb, 13.5% Co, remainder Fe. These four-layer media were made under conditions identical to Example I. All the disks were exposed to an environment of 70° C. and 90% relative humidity and periodically removed and checked by optical microscopy and by using an optical laser recorder to determine the ratio of the number of bit errors to bits of recorded data (i.e. Bit Error Rate or BER). Over the total test time of more than 400 hours, the BER of the inventive yttrium doped media increased only from about 3×10 -5 to about 1×10 -4 . On the other hand, while the disks of runs No. 462 and 467 had about the same initial BER as the inventive media disks, the BER for run 467 increased to 4×10 -4 in about 200 hours and the BER for run 462 increased to 4×10 -4 in about 380 hours. The disk of run 460 had an initial BER of about 2×10 -4 which increased to 4×10 -4 in about 120 hours. This dramatic reduction in the rate of increase in BER with time under severe conditions can be attributed to protection from local corrosion, and this reduced local corrosion in the yttrium doped disks was confirmed by optical microscopy.
EXAMPLE III
Seven injection molded grooved polycarbonate disks 130mm in diameter and 3 glass slides were mounted in a vacuum deposition system which was evacuated to <2×10 -7 torr. The vacuum deposition system was equipped with a planetary which allowed the disks to be rotated both about their axes and an axis at the vacuum chamber center in order to ensure uniform film depositions. First an SiOx film 500 Å in thickness was deposited at a rate of about 4 Å/sec using a resistance heated evaporation boat filled with silicon monoxide powder. A 300 Å thick film consisting of an alloy of Fe, Co, Tb and Ta was deposited by triode sputtering at about 1.7 Å/sec using a magnetically enhanced sputter source. The sputter target was 51 mm×381 mm and comprised 68% Fe, 8% Co, and 24% Tb (atomic percent) onto which a piece of tantalum 25 mm×13 mm had been placed. During deposition the argon sputtering gas flow was 220sccm and the chamber pressure was 1.3×10 -3 torr. The following were the source operating conditions: Target voltage=500 volts, target current=2.2 Amps, plasma voltage=80 volts, plasma current=5 amps, emitter current=34 amps. After depositing the FeTbCoTa alloy, the system was re-evacuated to 8×10 -7 torr and a 300 Å thick film of SiOx was deposited using the resistance heated evaporation boat filled with silicon monoxide powder. Finally, a 1500 Å thick film of aluminum +2 atomic percent chromium was deposited at about 3.6 Å per second using a DC planar magnetron sputter source. The argon flow rate was 40 sccm and the chamber pressure was 8×10 -4 torr. The magnetron sputtering target voltage and current were 700 volts and 2.2 amps.
The composition of the FeTbCoTa film which had been deposited on the glass slides during the experiment was determined using ICP analysis. The result in atomic percent was:
Fe:=68.1%
Tb:=22.0%
Co:=7.9%
Ta:=2.0%
Two methods were used in determining the influence of various tantalum concentrations on the corrosion resistance of Fe-Tb-Co alloys.
EXAMPLE IV
In the first method, films 1000 angstroms thick were deposited on polymethylmethacrylate substrates which had been coated with a 500Å thick layer of SiOx. Their electrochemical polarization curves were determined in a nitrogen saturated 0.1 N NaCl water solution in accordance with the ASTM Standard Practice for Standard Reference Method for Making Potentiostatic and Potentiodynamic Anodic Polarization Measurements (ASTM G 5-82) using a scan rate of 2mV/sec. This is a standard method used to measure the corrosion resistance of materials. The apparatus used for controlling and changing the voltage potential was an EG & G Princeton Applied Research Potentiostat/Galvanostat Model 273, and the reference electrode used was a saturated calomel reference electrode.
The alloys tested by this method were the same except that two of the three alloys had 2.5 and 5 atom % tantalum, respectively, while the third, control, contained no tantalum. The tantalum addition significantly moved the corrosion potential (the voltage for which corrosion current is zero) in a positive direction. The corrosion potential for the control was about -710 mV, while the corrosion potential for the 2.5% Ta alloy was about -640 mV relative to a saturated calomel electrode. This more positive voltage represents a reduced driving force for the corrosion reaction. In addition, the curves of voltage potential versus current showed that the tantalum doped alloys experienced significantly reduced corrosion currents as voltage was increased. For example, at a voltage of about -450 mV corrosion current for the inventive alloys was reduced over that for the undoped control by a factor of more than 100.
EXAMPLE V
The second test for determining the influence of tantalum concentrations on corrosion resistance was to make full construction MO media which incorporated Fe-Tb-Co-Ta films as made in Example III. These media were exposed to 80° C. and 90% relative humidity for 434 hours, and the extent of corrosion was determined by optical microscopy. The full construction media consisted of: an injection molded polycarbonate substrate, a 500 angstrom thick layer of SiO x , a 300 angstrom thick layer of Fe-Tb-Co-Ta alloy, 400 angstrom thick SiO x layer and 1500 angstrom thick layer of A1-2% Cr reflective layer, a quadrilayer medium of the substrate incident structure. Corrosion sites were found to occur at defects and scratches transferred to the MO disks during molding. Therefore, it was possible to locate the same defects in disks of various tantalum levels and to locate the same defects from the molding process on different disks made on the same molding equipment. Comparison of these identical areas showed that the number and size of corrosion sites was significantly reduced by the presence of tantalum.
This is apparent by comparing FIGS. 1 and 2 which represent the same corresponding area on an inventive disk and a control disk having no tantalum in the RE-TM alloy, respectively. The inventive disk of FIG. 1 shows far fewer corrosion sites, and those which are apparent are smaller than those in FIG. 2.
The beneficial effects of tantalum would be meaningless if an MO medium with good magneto optic properties could not be produced. Therefore, MO disks of various tantalum concentrations were tested to determine the carrier-to-noise ratio (CNR) and threshold write laser power (laser power at which significant CNR is obtained). The results showed that increasing tantalum concentration reduced threshold write power somewhat and also reduced CNR a little. However, in all of the samples, the CNR was acceptable. CNR for the control disk without tantalum was about 53 decibels (dB), while the CNR for the 2.5% tantalum doped sample was about 52 dB and for a 3.8% Ta doped sample about 50 dB.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made in this invention without departing from its true spirit or scope which is indicated by the following claims. | Magneto-optic recording media have been made more resistant to corrosion by incorporating small amounts of tantalum and/or yttrium into the rare earth-transition metal active layer of the recording media. This improvement should help make magneto-optic media more reliable in the long term storage and retrieval of information. | 8 |
This application is a continuation of U.S. application Ser. No. 07/751,824 filed Aug. 30, 1991, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a memory decoding system, and particularly to a memory decoding system for use on a portable data terminal.
2. Discussion of the Related Art
A portable data terminal is restricted in its board size, and therefore, all the circuits of the terminal have to be simplified as much as possible. Further, as a dc power source is used, the number of the circuit components (integrated circuit elements) has to be reduced to a minimum in order to prevent the unnecessary consumption of power. The memory decoding system of a portable data terminal includes a separate ROM as the main memory device and a plurality of RAMs together with a microprocessor. These components are provided in such a manner to form the main internal device, internal and external peripheral devices, and a data terminal.
The ROM is primarily used to store the system program, and the plurality of the RAMs are used for carrying out jobs and for operating the programs. Therefore, if the ROM and RAM are assigned with separate addresses, the system program becomes complicated, and can lower the processing performance of the microprocessor owing to the inherent characteristics of the portable data terminal. Therefore, it is required that the ROM and RAM be assigned with addresses in an integrated form.
Generally, the memory decoding system for the portable data terminal uses customized chips as in ASIC (Application Specific Integrated Circuit), and therefore, its construction and operating principles may be difficult to determine. For example, circuit No. 75 which is disclosed in a technical reference manual for Model-20, which is a product of Norland Company of England, includes a memory decoding system for a portable data terminal. The large numbers of gates and logic ICs in the system make it difficult to form compact products.
In that memory decoding system, the memory banks can be selected by a switch capable of three settings for selecting three modes of the memory banks by means of the system program, and the ROM and the RAM are connected to the memory decoding system. However, more detailed exact operating principles of the system cannot be determined.
In forming the memory section as the main memory device for the portable data terminal, if the ROM and the RAM are assigned with independent addresses, as in the conventional cases, the program for operating them becomes complicated, and as a result the processing capability of the microprocessor is reduced. Also, due to the restriction in the board size, all the circuits have to be compactly designed. Further, the number of chips used has to be reduced as much as possible.
SUMMARY OF THE INVENTION
The present invention is intended to overcome the above described disadvantages of the conventional technique. Therefore, it is the object of the present invention to provide a memory decoding system which can be used in a portable data terminal in a convenient manner by mapping the memory in such a manner that the RAMs and the ROM forming the memory section are assigned with addresses in an integral form.
In achieving the above object and in accordance with the purpose of the invention, as embodied and broadly described herein, the system of the present invention includes a microprocessor for generating address signals having a required bit number, data signals having a required bit number, memory request signals, and memory read/write signals; a memory section having a ROM and a plurality of RAMs, an address map having a system ROM region, a reserve region, a user RAM region, and a system RAM region in an integral form for the whole system, and connected through a common bus (for address and data) to the microprocessor; an OR gate for OR-computing the uppermost two address signals; a RAM selection signal generating section for outputting a predetermined number of RAM selecting signals after receipt of a predetermined number of the uppermost address signals (excluding the uppermost two addresses), and using the output signals of the OR gate, the memory request signals, and the power-on driving voltage as the enabling signals; a NAND gate section for receiving a predetermined number of the uppermost address signals (including the uppermost two addresses inputted into the OR gate computing section); and a ROM selection signal generating section having an OR gate for OR-computing the output signals of the NAND gate and the memory request signals, and for outputting the computed signals as the ROM selecting signals.
BRIEF DESCRIPTION OF THE DRAWINGS
The manner by which the above object and other objects, features, and advantages of the present invention are attained will become fully apparent from the following detailed description of the present invention when considered with reference to the attached drawings in which:
FIG. 1 is a block diagram showing an embodiment of the conventional portable data terminal;
FIG. 2 illustrates an embodiment of a memory address map according to the present invention; and
FIG. 3 illustrates a circuit of the memory decoding system of a portable data terminal according to the present invention.
DETAILED DESCRIPTION
FIG. 1 is a block diagram showing an embodiment of the conventional portable data terminal, and is provided to assist in the understanding of the apparatus of the present invention. As shown in FIG. 1, the data terminal includes an LCD (liquid crystal display) module 1 for displaying characters and graphs after receipt of data based on the system program, a key entry section 2 including a plurality of letter keys and numeral keys, and a key board control section 3 for scanning and decoding the key state of the entry section 2 in order to send the letter and numeral key signals from the key entry section to the LCD module 1. An RTC section (real time clock section) 4 generates the timing signals required in the portable data terminal, and is capable of showing year, month and date, including leap year, automatically.
A print interface section 5 sends the data to be printed to a separate external printer, and a data communication section 6 (e.g. RS-232 or uPD-4711) transmits the data (to be transmitted and received) to an external host computer in series.
A bar code interface section 7 may be provided for inputting bar codes (including black and white bars) through a separate scanner, and a voltage checking section 8 displays a low voltage state upon finding the voltage to be lower than a reference voltage by checking the state of a battery used as the driving power source for the portable data terminal.
A power control section 9 supplies the power source of an adaptor to the respective sections of the memory decoding system, the adaptor being used for converting the respective outputs of a main battery, a back-up battery, and an external ac power source to the appropriate dc power. A reset signal generating section 10 supplies reset signals to the microprocessor key board control section 3 and to the LCD module 1 in accordance with the selections by the user.
Various memories are provided including a ROM 11 for storing the system program and a memory section 12 including a plurality of RAMs for operating user programs. A microprocessor 13 controls the system operations by using the system program stored in the ROM 11, and a control signal generating section 14 is connected through an address/data bus to the microprocessor 13 and generates various control and memory selection signals in order to operate the system after receipt of address signals from the microprocessor 13.
In order to prevent the squandering of the power for purposes other than the above described functions, the power control section 9 is automatically turned off if the system remains unused for a predetermined period of time.
The ROM 11, memory section 12, microprocessor 13, and the control signal generating section 14 form an integral system called by the general name of memory decoding system 15. According to the present invention, the memory decoding system 15 is properly adapted to the portable data terminal with the minimum number of chips, and the preferred embodiment of the present invention based on this principle will be illustrated in FIGS. 2 and 3.
FIG. 2 illustrates an address map structure of the ROM 11 and the memory section 12 including a plurality of RAMs according to the present invention. The addresses that can be designated by the microprocessor 13 range from OOOOO 16 through FFFFF 16 as represented in the hexadecimal number system according to the present embodiment. Further, the total number of addresses are divided into a system ROM region "a," a reserve ROM region "b," a system RAM region "c," and user regions "d 1 -d 3 ."
FIG. 3 illustrates the memory decoding system 15 of the portable data terminal employing the memory address map of FIG. 2. As shown in this drawing, the memory decoding system 15 includes a memory section 16 including a ROM 1 (64 Kbit may be used) including the addresses of the system ROM region "a" and the reserve ROM region "b," and 4 RAMs (RAM 1 -RAM 4 ) (32 Kbit SRAMs may be used) having the addresses of the system RAM region "c" and the user RAM regions "d 1 -d 3 ." A microprocessor 17 (for example, model V25 of NEC may be used) is included for generating internal 16-bit and external 8-bit signals containing address signals A o -A 19 , memory request signal MREQ, 8 data signals D o -D 7 and a memory read/write signal R/W. A first selection signal generating section 18 is included having a NAND gate G 2 receiving the four uppermost address signals A 16 -A 19 of the address signals outputted from the microprocessor 17, and an OR gate G 3 receiving the output of the NAND gate G 2 and the memory request signal, /MREQ, from the microprocessor 17. The output signal of the OR gate G 3 is transmitted to ROM 1 of the memory section 16 in the form of a chip selecting signal CS o .
The memory decoding system further includes a second selection signal generating section 20 including an OR gate G 1 and a decoder 19. The OR gate G 1 receives the uppermost two address signals A 18 -A 19 and the decoder 19 receives three of the upper address signals A 15 -A 17 . The decoder 19 receives the following signals as the enabling signals: memory request signal/MREQ, output signal of the OR gate G 1 and the system turning-on driving voltage B + . Also, the decoder 19 generates chip selecting signals CS 1 -CS 4 for the 4 RAMs (RAM 1 -RAM 4 ) of the memory section 16. Further, the microprocessor 17 is connected to the memory section 16 by supplying the memory read/write signal R/W as write enabling signals WE to ROM 1 and RAMs (RAM 1 -RAM 4 ) of the memory section 16, and by supplying the memory read/write signal R/W through an inverting device G 4 as an output enabling signal OE.
The apparatus of the present invention constituted as described above will now be described as to its operations.
As shown in FIG. 3, the memory decoding system generates internal 16-bit signals and external 8-bit signals including the memory request signal /MREQ, the memory read/write signal R/W, the address signals A o -A 19 and the data signals D o -D 7 through the microprocessor 17. The four uppermost address signals A 16 -A 19 of the addresses A o -A 19 are supplied to the NAND gate G 2 of the first selection signal generating section 18, and the output signals of the NAND gate G 2 are inputted into one of the input terminals of the OR gate G 3 . The other input terminal of the OR gate G 3 receives the memory request signal /MREQ, and, after carrying out the logic operation in this state, the OR gate G 3 supplies a chip selecting signal CS o to ROM 1 of the memory section 16.
In addition to the address signals A o -A 19 generated by the microprocessor 17, the two uppermost address signals A 18 and A 19 are supplied to the two input terminals of the OR gate G 1 of the second selection signal generating section 20, and the three address signals A 15 -A 17 are inputted into the input terminal of the decoder 19 (3×8). Under this condition, the decoder 19 outputs chip selecting signals CS 1 -CS 4 to the respective RAMs (RAM 1 -RAM 4 ) of the memory section 16 upon receipt of the enabling signals.
More specifically, when the logic values of the address signals A 16 -A 19 are all "1," the output signals of the NAND gate G 2 of the first selection signal generating section 18 will have the value of "0." Under this condition, if the memory signal /MREQ is in the active low state, the output signals of the OR gate G 3 will have the logic value of "0." Accordingly, an active low signal as the chip selecting signal CS o is supplied to ROM 1 of the memory section 16, and it becomes possible for the microprocessor 17 to access the data in ROM 1 .
If the address signals A 18 and A 19 and the memory request signal MREQ have the logic value of "0," and if the driving voltage B + has the logic value of "1," the decoder 19 will be placed in a chip enable state, so that the chip selecting signals CS 1 -CS 4 are supplied to the memory section 16 after combining and mixing the address signals A 15 -A 17 which are the input signals. Under this condition, only one of the chip selecting signals CS 1 -CS 4 is placed in an active low state, and only one of the RAMs (RAM 1 -RAM 4 ) is placed in a chip enable state. Accordingly, the microprocessor 17 can access the required data from the enabled RAM. Consequently, depending on the logic values of the address signals A 18 and A 19 , only one of the RAMs (RAM 1 -RAM 4 ) and the ROM of the memory section is enabled. Further, if the read/write signal R/W of the microprocessor 17 is in a low state, ROM 1 and the RAMs (RAM 1 -RAM 4 ) are placed in a write enable state, while, if the read/write signals R/W are in a high state, ROM 1 and the RAMs (RAM 1 -RAM 4 ) are placed in an output enable state.
The present invention achieves the following results. First, the longitudinal address of the system is divided into a plurality of address regions in accordance with the uses of the ROM and a plurality of the RAMs (forming the memory section), thus alleviating the load for the microprocessor. Therefore, the utilization of the memory section of the portable data terminal is maximized. Second, the memory decoding system is constituted with the minimum number of elements by utilizing an efficient memory map structure. Accordingly, the memory decoding system is sufficiently compact to fit into the characteristics of the portable data terminal, and the otherwise unnecessary squandering of the dc power source can be prevented.
The foregoing description of the preferred embodiment of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiment was chosen and described in order to explain the principles of the invention and its practical application to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents. | A memory decoding system for a portable data terminal includes a memory controller, a memory storage, a first selection signal generator, and a second selection signal generator. The memory controller generates address signals and data signals. The memory storage is divided into a plurality of memory regions, and is controlled in such a manner as to write and read for the specified uses through the memory controller. The first selection signal generator outputs memory selecting signals to select one memory type of the memory storage. The second selection signal generator generates memory selecting signals to select another memory type of the memory storage. The portable terminal can be formed into a more compact type. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is commencing national stage examination pursuant to 35 U.S.C. §371 from International patent application No. PCT/US2008/003640 filed in the U.S. PCT receiving office on Mar. 20, 2008, which international application claims the priority of U.S. provisional patent application Ser. No. 60/919,666 filed Mar. 22, 2007. Each of the aforementioned PCT and Provisional applications is incorporated by reference in its entirety as if fully set forth herein.
FIELD OF THE INVENTION
This application discloses a novel process for the preparation of 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds, which have utility, for example, as NK-1 receptor antagonist compounds, and intermediates useful in the synthesis thereof.
BACKGROUND OF THE INVENTION
Identification of any publication, patent, or patent application in this section or any section of this application is not an admission that such publication is prior art to the present invention.
The preparation of diazaspirodecan-2-ones for example, 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one, for example, (5S,8S)-8-[{(1R)-1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diazaspiro[4.5]decan-2-one (the compound of Formula I) has been described in U.S. Pat. No. 7,049,320 (the '320 patent), issued May 23, 2006, the disclosure of which is incorporated herein in its entirety by reference.
The compounds described in the '320 patent are classified as tachykinin compounds, and are antagonists of neuropeptide neurokinin-1 receptors (herein, “NK-1” receptor antagonists). Other NK 1 receptor antagonists and their synthesis have been described, for example, those described in Wu et al, Tetrahedron 56, 3043-3051 (2000); Rombouts et al, Tetrahedron Letters 42, 7397-7399 (2001); and Rogiers et al, Tetrahedron 57, 8971-8981 (2001) and in published international application no. WO05/100358, each of which are incorporated herein in their entirety by reference.
“NK-1” receptor antagonists have been shown to be useful therapeutic agents, for example, in the treatment of pain, inflammation, migraine, emesis (vomiting), and nociception. Among many compounds disclosed in the above-mentioned '320 patent are several novel diazaspirodecan-2-ones, including the compound of Formula I, which are useful in the treatment of nausea and emesis associated with chemotherapy treatments (Chemotherapy-induced nausea and emesis, CINE).
The synthesis method for preparing the compound of Formula I described in the '320 patent generally follows Scheme I in the provision of 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxyl}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds.
The process for the preparation of the compound of Formula I described in the '320 patent is carried out in 18 individual steps from commercially available starting materials (see the '320 patent at col. 43, line 55 to col. 45, line 20; col. 75. line 55 to col. 80, line 21; col. 90 lines 35 to 63; and col. 98, line 1 to col. 99. line 24). In many steps of the process described in the '320 patent, intermediate compounds must be isolated or isolated and purified before use in a subsequent step, often utilizing column chromatography for this purpose. In general, the synthetic scheme described in the '320 patent consumes a larger than desirable percentage of starting and intermediate compounds in the production of unwanted isomers.
OBJECTIVES AND SUMMARY OF THE INVENTION
In view of the foregoing, what is needed is a synthetic scheme for the preparation of 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds which has a reduced number of steps, improves the percentage of intermediate compounds which are converted to the desired stereoisomer, and provides a reaction scheme affording practical scale up to a batch size suitable for commercial scale preparation.
These and other objectives are advantageously provided by the present invention, which in one aspect is a process of making 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds of Formula I in accordance with Scheme II.
the process comprising:
(a) reacting the protected enamine of Formula III with a nitrating agent to form the corresponding protected nitro-enamine and subsequently reducing the product to a protected piperidine of Formula IV; (b) deprotecting the protected piperidine of Formula IV from step “a” by reacting it with hydrogen in the presence of a palladium catalyst to form the compound of Formula V; (c) alkylating the compound of Formula V by reacting it with a Michael acceptor under Michael addition conditions with an acrylate to form the compounds of Formulae 27a and 27b; (d) selectively precipitating a sulfonate salt of the free base compound of Formula 27a formed in alkylating Step “c” by reacting the reaction mixture from Step “c”, containing the compound of Formula 27a, with a sulfonic acid of the formula R 5 —SO 3 H to form the precipitate of Formula 27a-sulfonate; (e) reducing and cyclizing the compound of Formula 27a-sulfonate to form the lactam of Formula I; and (f) optionally, precipitating a hydrochloride salt form of the compound of Formula I by reacting the free-base compound of Formula I with HCl.
One aspect of the present invention is the provision of a process for synthesizing the lactam compound of Formula I, the process comprising reducing and cyclizing the compound of the Formula 27a-sulfonate in a one-pot reaction. In some embodiments, it is preferred to carry out the reaction by treating the compound of Formula 27a-sulfonate with acetic acid in the presence of zinc metal. In some embodiments, preferably the compound of Formula 27a is dissolved in concentrated acetic acid and the solution is introduced into a zinc powder/acetic acid suspension. Without wanting to be bound by theory, it is believed that the reaction conditions provided by the zinc metal/acetic acid reaction environment first reduce the nitro group to an amino-group and then form the lactam by acid-catalyzed displacement of the acyl portion of the ester group, thereby cyclizing the compound of Formula 27a and forming the lactam of Formula I.
Another aspect of the present invention is the provision of compound of Formula 27a from the compound of Formula V using a Michael addition reaction yielding at least about 60% of the compound of Formula 27a based on the amount of the compound of Formula V employed. In some embodiments it is preferred to select a basic alumina to carry out the Michael addition. In some embodiments it is preferred to select the acrylate used as a Michael acceptor from in step “c” from acrylates having the structure of the compound of Formula 28a:
wherein R 1 is a linear, branched, or cyclic alkyl having up to 6 carbon atoms, phenyl, 2-methoxy-ethyl, 2-(dimethylamino)ethyl, (L)-menthyl, (D)-menthyl, dimethylamide, (R)-benzyl-oxazolidinonamide, (S)-benzyl-oxazolidinonamide, isobornyl, cis-pinan-2-yl, isopinocampheyl, adamantylmethyl, 2-adamantyl, 1-adamantyl, and (−)-8-phenylmenthyl, more preferably R 1 is selected from methyl, (−)-8-phenylmenthyl, isobornyl, 1-adamantanyl, 2-adamantanyl, adamantane methanyl, and (+)-isopinocamphenyl, more preferably R 1 is selected from methyl and isobornyl. In some embodiments it is preferred to carry out the Michael addition using basic alumina, more preferably a basic alumina with Brockman activity level IV. In some embodiments it is preferred to carry out the Michael addition using an R 1 -acrylate Michael acceptor wherein “R 1 ” is selected from methyl- and -isobornyl, more preferably R 1 is methyl.
In some embodiments, in Step “d”, precipitation step, it is preferred to employ a sulfonic acid of the formula R 5 —SO3H or oxalic acid, for example, methylsulfonic acid, to precipitate the sulfonate salt of the compound of Formulae 27a-sulfonate. In some embodiments it is preferred to select R 5 from, methyl, alkyl, benzyl, and p-tolyl, more preferably R 5 is methyl.
Other aspects and advantages of the invention will become apparent from following Detailed Description.
DETAILED DESCRIPTION OF THE INVENTION
Terms used in the general schemes herein, in the examples, and throughout the specification, include the following abbreviations, together with their meaning, unless defined otherwise at the point of their use hereinafter; Me (methyl); Bu (butyl); t-Bu (tertiary butyl); Et (ethyl); Ac (acetyl); t-Boc or t-BOC (t-butoxycarbonyl); DMF (dimethylformamide); THF (tetrahydrofuran); DIPEA (diisopropylethylamine); MTBE (methyltertiarybutyl ether); RT (room temperature, generally 25° C.); TFA (trifluoroacetic acid); TEA (triethyl amine).
As used herein, the following terms, unless otherwise indicated, are understood to have the following meanings:
The term “substituted” means that one or more hydrogens on the designated atom or group of atoms in a structure is replaced with a selection from the indicated group, provided that the designated atom's normal valency under the existing circumstances is not exceeded, and that the substitution results in a stable compound. Combinations of substituents and/or variables are indicated when such combinations result in stable compounds. By “stable compound” or “stable structure” is meant a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture, and formulation into an efficacious therapeutic agent.
The term “optionally substituted” means optional substitution with the specified groups, radicals or moieties.
“Patient” includes both humans and animals.
“Mammal” means humans and other mammalian animals.
“Alkyl” means an aliphatic hydrocarbon group which may be linear straight or branched and comprising about 1 to about 10 carbon atoms in the chain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and n-pentyl.
“Alkenyl” means an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched and comprising about 2 to about 10 carbon atoms in the chain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkenyl chain. Non-limiting examples of suitable alkenyl groups include ethenyl, propenyl, n-butenyl, 3-methylbut-2-enyl and n-pentenyl.
“Alkylene” means a difunctional group obtained by removal of an additional hydrogen atom from an alkyl group, as “alkyl” is defined above. Non-limiting examples of alkylene include methylene (i.e., —CH 2 —), ethylene (i.e., —CH 2 —CH 2 —) and branched chains, for example, —CH(CH 3 )—CH 2 —.
“Aryl” means an aromatic monocyclic or multicyclic ring system comprising about 6 to about 14 carbon atoms, preferably about 6 to about 10 carbon atoms. The aryl group can be optionally substituted with one or more “ring system substituents” which may be the same or different, and are as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.
“Cycloalkyl” means a non-aromatic mono- or multicyclic ring system comprising about 3 to about 10 carbon atoms, preferably about 3 to about 6 carbon atoms. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Non-limiting examples of multicyclic cycloalkyls include, but are not limited to 1-decalin, norbornyl and cognitors, adamantyl and cognitors.
“Halo” means a halogen selected from fluoro, chloro, bromo, or iodo groups.
“Aminoalkyl” means an alkyl as defined above having at least one hydrogen atom on the alkyl moiety replaced by an amino functional (i.e., —NH 2 ) group. Alkylamino means an amino functional group having one or both hydrogens replaced by an alkyl functional group, as “alkyl” is defined above.
With reference to the number of moieties (e.g., substituents, groups or rings) in a compound, unless otherwise defined, the phrases “one or more” and “at least one” mean that there can be as many moieties as chemically permitted, and the determination of the maximum number of such moieties is well within the knowledge of those skilled in the art.
A wavy line appearing on a structure and joining a functional group to the structure in the position of a bond generally indicates a mixture of, or either of, the possible isomers, e.g., containing (R)- and (S)-stereochemistry. For example,
means containing either, or both of
A wavy line which terminates a bond indicates that the portion of the structure depicted is attached to a larger structure at the indicated bond, for example,
implies that the nitrogen of the substituted piperidyl group depicted is bonded to an undepicted structure on which it is a substituent.
Lines drawn into ring systems, for example the substituted aryl group:
indicates that a substituent (R 1 ) may replace a hydrogen atom of any of the ring carbons otherwise bonded to a hydrogen atom. Thus, as illustrated, R 1 can be bonded to any of carbon atoms 2, 4, 5, or 6, but not 3, which is bonded to a methyl substituent or 1, through which the substituted aryl group is bonded.
As well known in the art, a bond drawn from a particular atom wherein no moiety is depicted at the terminal end of the bond indicates a methyl group bound through that bond to the atom, unless stated otherwise. For example:
represents
However, sometimes in the examples herein, the CH 3 moiety is explicitly included in a structure. As used herein, the use of either convention for depicting methyl groups is meant to be equivalent and the conventions are used herein interchangeably for convenience without intending to alter the meaning conventionally understood for either depiction thereby.
The term “isolated” or in “isolated form” for a compound refers to the physical state of said compound after being isolated from a process. The term “purified” or “in purified form” for a compound refers to the physical state of said compound after being obtained from a purification process or processes described herein or well known to the skilled artisan, in sufficient purity to be characterizable by standard analytical techniques described herein or well known to the skilled artisan.
When any variable (e.g., aryl, heterocycle; R 2 , etc.) occurs more than one time in any constituent or in a formula, its definition on each occurrence is independent of its definition at every other occurrence.
As mentioned above, a process for preparing the compound of Formula I from the compound of Formula IIIa via intermediate compound of Formula III is described in the '320 patent.
Preparation of the compound of Formula IIIa from commercially available (S)-α-phenylglycine is described by M. J. O'Donnel; Fang; X. Ma: and J. C. Huffman in “NEW METHODOLOGY FOR THE SYNTHESIS OF α,α-DIALKYLAMINO ACIDS USING THE ‘SELF-REGENERATION OF STEREOCENTERS’ METHOD: α-ETHYL-α-PHENYLGLYCINE”, Heterocycles, Vol 46. 1997, pp 617 to 630, (see pages 618 through 619 therein), which is incorporated herein by reference in its entirety.
In the process described in the '320 patent for the preparation of the compound of Formula I, the compound of Formula III is converted to the compound of Formula IIIb (in two steps by oxidation of a corresponding alcohol intermediate). Compound IIIb is then converted in one step to the compound of Formula 20 shown in Scheme I above. Accordingly, the '320 patent describes preparation of the compound of Formula I from the compound of Formula III in 13 individual process steps.
The inventors have surprisingly found that the compound of Formula I can be prepared, as shown in Scheme II, below, from the compound of Formula III in 4 process steps. Accordingly, the process of the present invention eliminates at least half of the number of steps employed in previous preparation processes. Moreover, as will be described below, various of the steps of the present invention process provide improved yield of intermediate compounds for an overall increase in the amount of the compound of Formula I provided from a given amount of the compound of Formula III initially employed in the process. As shown in Scheme II the compound of Formula III utilizes benzyl carbamate as a protecting group for the enamine nitrogen. It will be appreciated that other protecting groups may alternatively be employed and still be within the scope of the present invention.
Optionally, after Step “d”, the compound of Formula I can be precipitated from the reaction mixture as a salt by treatment of the reaction mixture workup with an acid. Accordingly, in some embodiments it is preferred to react the free-base compound of Formula I present in the reaction workup with an acid, for example, HCl, to precipitate a salt form of the compound of Formula I, for example, a hydrochloride salt form. Next, each step of the process of Scheme II will be described in greater detail.
Nitration Step
Step “a” of the process of the present invention, provision of the nitro-substituted intermediate compound of Formula IV from the corresponding enamine compound of Formula III, can be carried out in accordance with Scheme IIa, wherein the substrate is first nitrated and then the double bond of the six-membered ring is reduced.
In general, nitration is carried out in a non-protic, low polarity solvent, for example THF and DME using a nitrating reagent, for example nitronium tetrafluoroborate (nitronium-TFB), optionally in the presence of potassium phosphate tribasic. In some embodiments it is preferred to run the reaction without K 3 PO 4 in the reaction mixture and thereby minimize impurities which may otherwise be formed when K 3 PO 4 is present in the reaction mixture. In some embodiments it is preferred to carry out the nitration using nitronium-TFB in DME (in which nitronium-TFB has acceptable solubility). Nitration of the compound of Formula III using nitronium-TFB in THF solvent is described in published international application no. WO05/100358 (the '358 publication), albeit not in the course of synthesizing the compound of Formula I (see the '358 publication, page 66, step “a” of preparative Example 5). The '358 publication is incorporated herein by reference in its entirety. Once the nitrated intermediate compound has been prepared, it may be used as prepared n the reaction workup directly in subsequent steps, or optionally, isolated from the reaction workup prior to using in subsequent steps.
Following nitration, the nitrated compound is treated with a hydride reducing agent, for example lithium borohydride and sodium borohydride, to reduce the protected enamine double bond of the nitrated intermediate to yield the compound of Formula IV. In some embodiments using DME as the solvent in which the compound of Formula III is nitrated, it is preferred to strip off the reaction solvent by distillation and replace it with THF prior to carrying out the reduction step. This provides the nitrated intermediate in a solvent suitable for carrying out the reduction with a metal hydride without the need to isolate the nitrated intermediate. In some embodiments, it is preferred to carry out the reduction using lithium borohydride in THF.
Although it is preferred to use the above-described method for the preparation of the compound of Formula IV, it will be appreciated that other means may be selected to prepare the compound of Formula IV for use in the process of Scheme II and be within the scope of the present invention.
Step B—Deprotection
Step “b” of the present invention process, deprotection of the piperidine nitrogen in the compound of Formula IV to yield the compound of Formula V, can be carried out using metal-catalyzed hydrogenation or by treating the intermediate of Formula IV under acid conditions. Examples of suitable acid deprotection conditions include, but are not limited to trifluoroacetic acid (TFA) and a mixture of HBr/acetic acid. It will be appreciated that other deprotection schemes may also be employed, for example, iodotrimethylsilane (TMS-iodide) and deprotection using thiols. The inventors have surprisingly found that when TMS-iodide is employed, the byproduct benzyliodide can be efficiently trapped with triphenylphoshine to suppress benzylamine formation with the piperidine nitrogen of the deprotected product. In some embodiments it is preferred to use hydrogen and a hydrogenation catalyst, for example, a palladium metal catalyst, to mediate the deprotection reaction in Step “b”, more preferably the catalyst employed is Pd supported on carbon black. In some embodiments it is preferred to carry out deprotection in an alcohol solvent, for example, methanol. In some embodiments, it is preferred to work up the previous reduction step by adding methanol and distilling off the reaction solvent until suitably concentrated, and using the crude concentrated methanol solution directly in the subsequent deprotection reaction.
Step C—Alkylation
After the deprotection step “b”, the piperidine of Formula V is coupled to an acrylate under base-catalyzed Michael addition conditions. In some embodiments it is preferred to carry out the Michael addition in a solvent selected from n-hexane, MTBE, cyclohexane, toluene, methanol, dimethyl formamide (DMF), and THF. In some embodiments it is preferred for the solvent to be n-hexane. In some embodiments, the reaction mixture from the deprotection step “b” is worked up by successive additions of toluene, followed by azeotropic distillation, and then successive additions of n-hexane, followed by distillation maintaining the still pot between 30° C. and 60° C. until distillation ceases, thus, the residual mixture will have the lowest possible volume at this still temperature. In some embodiments it is preferred to employ the resulting concentrate directly in the Michael addition step which follows, Step “c”.
In some embodiments it is preferred to select a Michael acceptor from compounds having the structure of Formula 28a:
wherein “R 1 ” is selected from alkyl, cycloalkyl (including multicyclicalkyls), and aryl, more preferably “R 1 ” is selected from methyl, t-butyl, phenyl, 2-methoxy-ethyl, 2-(dimethylamino)ethyl, (L)-menthyl, (D)-Menthyl, Dimethylamide, (R)-Benzyl-oxazolidinonamide, (S)-benzyl-oxazolidinonamide, isobornyl, cis-pinan-2-yl, isopinocampheyl, adamantylmethyl, 2-adamantyl, 1-adamantyl, and (−)-8-phenylmenthyl, more preferably R is selected from methyl, (−)-8-phenylmenthyl, isobornyl, 1-adamantanyl, 2-adamantanyl, adamantane methanyl, and (+)-isopinocampheyl, more preferably R 1 is methyl.
In some embodiments it is preferred to carry out the Michael addition reaction in the presence of a base. In some embodiments the base is selected from: an organic base, for example, a homogeneous base, for example triethylamine, and a heterogeneous base, for example, basic polymer resin having amine functionality, for example Amberlyst A-21® from Rohm and Haas; and a heterogeneous, inorganic base, for example an aluminum oxide (neutral or basic), a metal alkoxide (for example, Mg(OEt) 2 , and magnesium oxide. In some embodiments it is preferred to employ a basic aluminum oxide to catalyze the Michael addition reaction, more preferably, basic aluminum oxide having a Brockman activity of I, II, III, or IV, available as an article of commerce, more preferably a basic aluminum oxide having a Brockman activity of IV having a 5 wt. % to 10 wt. % water content.
Several metal oxides have been found useful for catalyzing the Michael addition reaction, for example, magnesium oxide (MgO) and aluminum oxide (alumina). It will be appreciated that the Michael addition reaction can result in two different isomers being produced, shown in the reaction Scheme C-IIa as the compounds of Structures 27a (S-isomer, desired isomer) and 27b (R-isomer, an undesired isomer). Although the ratio of the isomers produced in the Michael addition reaction can be varied by altering the reaction solvent, the steric demand of the Michael acceptor, and other reaction conditions, the inventors have surprisingly found that the choice of base can greatly influence the ratio of S-isomer to R-isomer produced in the addition reaction. The inventors have surprisingly found that magnesium oxide base produces proportionately more of the R-isomer than the desired S-isomer. Additionally, the inventors have surprisingly found that the use of basic alumina as a base in the Michael addition reaction selectively produces more of the desired S-isomer over the R-isomer. Moreover, the inventors have surprisingly found that selecting Bookman activity level IV basic alumina as the base in the Michael reaction produces substantially more of the S-isomer than R-isomer, for example, using basic alumina of activity level IV, the inventive process can produce a reaction product with a ratio of S-isomer to R-isomer that exceeds 3:1 (75% S-isomer) even when it is used in reactions employing a sterically undemanding Michael acceptor, for example, methyl acrylate.
Moreover, the inventors have found that the inventive Michael addition reaction, when run with both a base providing maximum yield of the desired isomer, and employing a sterically demanding Michael acceptor, provides a reaction product comprising in some embodiments from about 84% to about 86% of the S-isomer, and in some embodiments up to about 90% S-isomer. Suitable sterically demanding Michael acceptors are, for example, compounds containing a bornyl structure and compounds containing an adamantly structure. Additional examples of suitable sterically demanding Michael acceptors include, but are not limited to, with reference to the structure of Compound 28a (above), compounds wherein the “R 1 ” group is selected from:
which are isobornyl, cis-pinan-2-yl, (+)-isopinocampheyl, adamantly-methyl, 2-adamantyl, 1-adamantyl, and (−)-8-phenylmenthyl substituents, respectively.
In some embodiments, to maximize the amount of desirable “S-isomer” produced in the Michael addition reaction it is preferred to use n-hexane for the reaction solvent, select aluminum oxide (basic) having Brockman activity level IV as the base catalyst, and use isobornylacrylate as a Michael acceptor (thus “R 1 ” is isobornyl-).
The inventive Michael addition reaction can be carried out using the compound of Formula IV (the protected precursor to the compound of Formula V, see for example, deprotection Step B, above) to provide an acylated product which, upon deprotection of that product in accordance with deprotection Step “b”, yields the compounds of Formula 27a and Formula 27b. Accordingly, the compound of Formula I can be produced by reversing the order of deprotection step b and alkylation step c. However, the inventors have surprisingly found that when used in the alkylation Step “c”, the protected compound of Formula IV yields a greater proportion of the undesirable R-isomer compound of Formula 27b relative to the amount of desired S-isomer compound of Formula 27a formed in the inventive Michael addition reaction under substantially the same reaction conditions as were used for carrying out the inventive Michael addition using the compound of Formula V (deprotected compound). Accordingly, to maximize the amount of the desired S-isomer compound of Formula 27a provided by the inventive Michael addition in the alkylation step, it is preferred to deprotect the compound of Formula IV first to form the compound of Formula V and then carry out the alkylation step rather than carry out the alkylation step on the compound of Formula IV and deprotect the product to provide the compound of Formula 27a.
In some embodiments, the product of the Michael addition is preferably isolated as a solution of the product by filtering the reaction mixture to remove solids and concentrating the solution under vacuum. In some embodiments, preferably the concentrated solution is then reacted directly with a sulfonic acid of the formula R 5 —SO 3 H or oxalic acid, where R 5 is selected from methyl, benzyl, and p-toluyl groups, to provide the ester compound of Formula 27a as a crystalline precipitated sulfonate salt of Formula 27a-sulfonate, see Scheme C-IIb (where R 5 is a methyl group, thus, the methylsulfonate salt is precipitated). It will be appreciated that other salts, including other sulfonate salts, may be precipitated without departing from the scope of the invention.
Although some amount of the unwanted “R” isomer is coprecipitated with the desired isomers of Formula 27a (27b-sulfonate), the precipitation in accordance with Scheme C-IIb provides a solid comprising substantially the compound of Formula 27a-sulfonate. In some embodiments precipitation using Scheme C-IIb provides a precipitated material containing more than about 96% the compound of Formula 27a-sulfonate (S-isomer) with less than 4% of the undesirable compound of Formula 27b-sulfonate (unwanted R-isomer) precipitated.
With reference to Scheme C-IIb, in some embodiments it is preferred to precipitate the methane sulfonate salt of the free-base compound as a crystalline material from the reaction mixture prepared above by treating the reaction mixture in a suitable solvent (for example, MTBE, or a mixed solvent, for example, toluene and isopropanol) with an excess of methanesulfonic acid, and crystallizing the resulting methansulfonate salt from the mixture, either by cooling, seeding the mixture, or a combination of the two. In some embodiments it is preferred to avoid using an alcohol solvent to suppress ester exchange reactions in the product which could lead to the formation of unwanted impurities. The precipitate is preferably isolated by vacuum filtration for use in the subsequent lactam formation step “d”.
Step D—Lactam Formation
Formation of the lactam of Formula I from the compound of Formula 27a-sulfonate is carried out by treating the sulfonate salt formed in alkylation step “c” (containing substantially only the compound of Formula 27a-sulfonate) with suitable reagents to effect reduction of the nitro-group with simultaneous, contemporaneous, or sequential cyclization to form the lactam of Formula I. Without wanting to be bound by theory, it is believed that the reaction conditions provided by employing zinc metal and acetic acid results in reduction of the nitro-group of the compound of Formula 27a-sulfonate to the corresponding amine (however transiently) with formation of the lactam of Formula I by intermolecular acylation (using the ester group present) of the newly formed amine, thereby cyclizing the substituents to form the lactam of Formula I. In some embodiments it is preferred to carry out the lactam forming step “d” by reacting the compound of Formula 27a-sulfonate with zinc metal in the presence of acetic acid. In some embodiments it is preferred to dissolve the sulfonate salt from Step “c” in concentrated acetic acid and combine that solution with a suspension of zinc powder in concentrated acetic acid to carry out the lactam-forming reaction.
After formation of the compound of Formula I, optionally, the compound of Formula I is extracted from the reaction mixture into toluene, and the toluene solution is treated with hydrochloric acid to precipitate the hydrochloride salt of the compound of Formula I. In some embodiments it is preferred to recrystallize the hydrochloride salt thus precipitated from mixed ethanol/isopropanol solvent.
In some embodiments, Step d is carried out under conditions in which a substantial portion of the compound of Formula Ia1 is formed.
When reactor conditions favor slow reduction of the nitro group, for example, when low intensity agitation is used in the reactor, the intermediate formed during reduction of the nitro group has sufficient lifespan to participate in the ring closing reaction in accordance with Scheme IIIa,
Accordingly, the formation of the compound of Formula Ia1 is increased when closing proceeds faster than reduction during the nitro-reduction/lactam formation Step d of the process.
The inventors have surprisingly found that once formed, the Compound of Formula Ia1 can be converted in good yields to the compound of Formula I using Raney nickel as a hydrogenation catalyst to reduce the compound, in accordance with Scheme IIIb shown below.
Accordingly, when preparation of the compound of Formula Ia1 is not desired, the product can be converted to the compound of Formula I in good yields by reducing the compound of Formula Ia1 using hydrogen and Raney nickel as a hydrogenation catalyst. When such a reaction is desired, preferably the reaction is carried out at a temperature of about 50° C.
EXAMPLES
Unless otherwise specified, all reagents are articles of commerce, laboratory grade, and used as received. The following solvents and reagents may be referred to by their abbreviations in parenthesis:
tertiary-butoxycarbonyl: t-BOC tetrahydrofuran: THF Dimethylformamide: DMF methyl-tertiarybutyl ether: MTBE mole: mol.
Following are general and specific methods for the preparation of compounds having formula I, III, IIIb, IV, V, 27a and 27b described above. There follows non-limiting examples illustrative of the present invention but not limiting the present invention.
Example 1
Preparation of Compound IIIb: Benzyl (2S)-2-({(1-R)-1-[3,5-bis(trifluoromethyl)phenyl]ethoxy}methyl)-5-nitro-2-phenyl-3,4-dihydropyridine-1(2H)-carboxylate
Into a vessel equipped with a stirring apparatus was placed 1,2-dimethoxyethane (DME, 200 liters) at 20° C. to 25° C. Compound III (20.0 kg, 34.5 moles) was dissolved in the DME. The solution was then cooled and maintained at a temperature of −50° C. to −55° C. Nitronium tetrafluoroborate (5.52 kg, 41.6 moles) was slowly added to the cold solution in aliquots sized to maintain the batch temperature between −55° C. and −48° C. The reaction mixture was maintained at −50 to −55° C. until HPLC analysis of the reaction mixture indicated that less than 2% of the amount of the compound of Formula III initially used remained in the reaction mixture.
At the end of the reaction, sodium carbonate solution (12 Kg Na 2 CO 3 dissolved in 50 L water) was added while allowing the temperature of the reaction mixture to rise. The reaction mixture temperature was maintained at between −20° C. and 0° C. during the addition of the sodium carbonate solution. After approximately 50 L of sodium carbonate solution had been added, the pH of the mixture was evaluated using pH paper and found to be pH 5.5. Solid sodium carbonate was added until the mixture had a pH of greater than pH 7.0 but not exceeding pH 10. During the addition of sodium carbonate, the temperature of the mixture was maintained between −20° C. and 0° C. When the the pH had been adjusted to a value between pH 7.0 and pH 10, it was warmed to ambient temperature (between 20° C. and 25° C.). After warming, the reaction mixture was filtered and the filter cake washed with DME, which was combined with the filtrate.
The filtrate was concentrated by distilling off the volatiles under vacuum 80 mbar to 150 mbar) to the lowest possible volume while maintaining the filtrate at a temperature between 30° C. and 50° C. Two aliquots of MTBE (20 L each) were added to the concentrate in sequence. After each addition of MTBE to the concentrate, the mixture was again concentrated by distilling under vacuum (from sufficient vacuum to induce boiling up to 520 mbar) to the lowest possible volume while maintaining the filtrate at a temperature between 30° C. and 50° C. After the second distillation, MTBE (60 L) was added to the residue. The mixture was agitated, and permitted to settle, the layers of the mixture were split. The organic layer was washed with water (3 aliquots of 20 L each) and concentrated under vacuum (80 mbar to 200 mbar), to the lowest possible volume while maintaining the organic layer at a temperature between 30° C. and 50° C. THF was added to the concentrate (20 L), and distilled off under vacuum (80 mbarr to 150 mbar) to achieve the lowest possible volume while maintaining the mixture at a temperature between 30° C. and 50° C. A second aliquot of THF was added to the concentrate (60 L) and the water content was determined by Karl Fischer titration to be less than 0.2%. The solution thus obtained was analyzed by HPLC, and the yield of the compound of Formula IIIb was determined to be 90%.
Example 2
Preparation of Compound IV: Benzyl(2S)-2-({(1R)-1-[3,5-bis(tri-fluoro-methyl)-phenyl]ethoxy}-methyl)-5-nitro-2-phenylpiperidine-1-carboxylate
To the reaction mixture comprising the Compound IIIb solution (152.34 kg, 53.3 kg active, 87.6 moles) produced in Example 1 was added tetrahydrofuran (295 liters), and the mixture was cooled and maintained at a temperature between −22° C. to −18° C. A solution of lithium borohydride (7.92 kg, 10% in THF, 35.6 moles) was added to the mixture at a rate permitting the mixture to be maintained at a temperature between −22° C. and −18° C. The reaction was maintained at −22 to −18° C. until HPLC analysis indicated that the reaction was complete. At the completion of the reaction water (104 L) was added at a rate that maintained the temperature of the reaction mixture below 20° C. Concentrated hydrochloric acid was added to the mixture until the pH of the mixture was between pH 3.5 and pH 4.5. The mixture was concentrated at 30° C. to 50° C. under vacuum (80 mbar to 120 mbar) until distillation of the solvent ceased. Additional methyl tert-butyl ether (86 L) was added to the concentrated reaction mixture and 43 L distilled off at 30° C. to 50° C. under sufficient vacuum to maintain distillation, reducing the THF level to less than 10 vol. %. MTBE (302 L) was added into the concentrate. The mixture was agitated, then left quiescent to settle. The layers were split, and the organic layer was washed with 3 aliquots of water (42 L each aliquot).
After washing, the organic layer was concentrated at 30° C. to 55° C. under vacuum (80 mbar to 120 mbar) until distillation ceased. Methanol (130 L) was added to the concentrate. The mixture was heated to 30° C. to 50° C. under slight vacuum (80 mbar to 120 mbar) and 43 L of methanol was distilled off. The solution thus obtained was evaluated by HPLC and found to contain an amount of the compound of Formula IV equal to a 72% yield based on the amount of the compound of Formula III employed in the reaction.
Example 3
Preparation of Compound V: (2S)-2-({(1R)-1-[3,5-bis(trifluoromethyl)phenyl]ethoxy}methyl)-5-nitro-2-phenylpiperidine
The solution containing the compound of Formula IV prepared in the previous step (53.8 kg, 18.8 kg active, 30.7 moles of Formula IV) was diluted with methanol (90 liters). Aqueous concentrated hydrochloric acid (5.1 liters) was slowly added to the agitated solution while maintaining the mixture at a temperature of between 20° C. to 30° C. Into a separate vessel containing palladium on charcoal catalyst (1.5 kg, 10% on charcoal, 54% water) was slowly added Methanol (19 liters) while the mixture was slowly agitated to form a catalyst suspension. While continuing to slowly agitate the suspension, the solution of compound IV was slowly added to the suspension while maintaining the mixture at a temperature of from 20° C. to 25° C. After all of the solution of compound IV had been added, the mixture was placed under 1-3 bar of hydrogen pressure and agitated vigorously while maintaining the reaction mixture at a temperature of between 20° C. and 25° C. until the reaction was complete as determined by HPLC. The reaction mixture was filtered through Dicelite® (0.5 kg) and the filter cake washed with methanol, which was combined with the filtrate. The filtrate was placed under vacuum (500 mbar) and concentrated while maintaining the temperature of the filtrate between 20° C. and 30° C. until distillation ceased. During the concentrating procedure, when the mixture was concentrated to about 20% of the initial volume, the mixture was analyzed by HPLC.
After the mixture had been concentrated, toluene (113 L) was added to the concentrate. The pH of the residue was adjusted by addition of sodium carbonate solution (7.8 Kg sodium carbonate dissolved in 79 L of water) to a value between pH 9 and pH 10. When the desired pH range had been achieved, the mixture was settled and split. The organic layer was washed with a sodium chloride solution (11.3 Kg sodium carbonate dissolved in 102 L of water) and concentrated under vacuum (80 mbar to 120 mbar) while maintaining it at a temperature of 30° C. to 60° C. until distillation ceased. To the concentrate was added toluene (57 L) which was distilled off azetropically at 30° C. to 60° C. under vacuum. A second aliquot of toluene (57 L) was added and distilled off azetropically at 30° C. to 60° C. under vacuum. Karl Fischer titration indicated that the concentrate contained less than 0.2% water.
To the concentrate was added 2 aliquots of n-hexane (57 L each). Each of the hexane aliquots was subsequently distilled off under vacuum maintaining the mixture at 30° C. to 60° C. until distillation ceased. The resulting solution was evaluated by HPLC and found to contain an amount of the compound of Formula V equal to a 93% yield based on the amount of compound IV initially used. This solution was used in the subsequent step.
Example 4
Preparation of Compounds 27a and 27b
Methyl 3-[(3R/S,6S)-6-({(1R)-1-[3,5-bis(trifluoromethyl)phenyl]ethoxy}methyl)-3-nitro-6-phenylpiperidin-3-yl]propanoate
Into a vessel was placed N-hexane (106 liters). With stirring, 135.8 Kg of basic aluminum oxide was added (Brockmann IV, water content 9-14%, Camag, used as received) to form a suspension. The solution containing 29.2 kg (13.5 kg active, 28.4 moles) of the compound of Formula V prepared in the previous step was added to the suspension while stirring was continued and the mixture temperature was maintained at a temperature between 20° C. and 25° C. The equipment was rinsed with additional hexane and agitation of the reaction mixture was continued for 20 to 30 minutes after all of the solution had been added to the suspension. Into the reaction mixture was added 14.74 kg (171.2 moles) methyl acrylate maintaining the reaction mixture at a temperature between 20° C. and 25° C. The equipment was rinsed with additional n-hexane and the mixture was maintained at ambient temperature until the reaction was completed as determined by HPLC. At the end of the reaction, the reaction mixture was filtered and the filter cake was washed with toluene. The combined filtrate and wash were concentrated by applying a vacuum and maintaining the temperature of the filtrate between 30° C. and 60° C. until the filtrate is concentrated to the smallest volume that permits it to maintain a free-flowing characteristic. The concentrate was evaluated by HPLC and found to contain an amount of the compounds of Formulae 27a and 27b equivalent to a yield of 71% based on the amount of the compound of Formula V used initially. In determining yield it was found that the product contained both diastereomers in a 2:1 ratio of the compound of Formula 27a (S-diastereomer) to the compound of Formula 27b (R-diastereomer) and the yield of the desired S-diastereomer (compound 27a) was 48% based on the amount of compound V initially used, (solution yields). The solution was used directly to prepare the methylsulfonate salt in the next step.
Example 5
Preparation of Sulfonate Salts of Compounds of Formula 27a/27b
To the solution containing compounds of the Formulae 27a and 27b free base prepared in Step 5 (containing 22.78 kg of both diastereomers, including 15.6 kg (27.7 moles) of the S-isomer) was added 62 liters of MTBE maintaining the temperature of the mixture at 20° C. to 25° C. The solution was passed through a fine filter and the filter was rinsed with MTBE. The clear filtrate thus obtained was concentrated to about 3× at 30° C. to 55° C. under slight vacuum (500 mbar). The concentrate was diluted with toluene and the temperature of the mixture was adjusted to 20° C. to 25° C. Methane sulfonic acid (2.0 Kg, 0.75 eq) was added to the mixture over 20 to 30 minutes while maintaining the reaction mixture at a temperature between 20° C. and 25° C. After acid addition the reaction mixture was agitated for 15 to 20 minutes. An additional 2.1 Kg (0.79 eq) of methanesulfonic acid was added to the suspension while maintaining the temperature and agitation. The reaction mixture was agitated at 20° C. to 25° C. for an additional 50 to 60 minutes following addition and then cooled to a temperature between 0° C. and 5° C., then agitated for an additional 50 to 60 minutes. At the end of the agitation period the reaction mixture was filtered, the wet cake was washed with a 1:1 mixture of MTBE/toluene at 0° C. to 5° C. The filter cake (wet) was suspended in MTBE and agitated for 50 to 60 minutes while maintaining the suspension temperature at a temperature between 20° C. and 25° C. At the end of the agitation time, the suspension was cooled and maintained at a temperature between 0° C. and 5° C. and agitated for an additional 50 to 60 minutes.
The batch was filtered and washed with 0° C. to 5° C. MTBE. The wet cake was maintained at a temperature of between 30° C. and 40° C. and dried under vacuum (150 mbar to 200 mbar), and then for an additional 4 to 5 hours at 45° C. to 50° C. under vacuum. The solids thus obtained were evaluated by HPLC and found to contain an amount of the compound of Formula 27a-sulfonate (S-isomer) equivalent to a yield of 88% based on the amount of S-isomer initially present in the mixture. HPLC analysis indicated also that the salt precipitated had an isomeric ratio of 98% S-enationmer (27a-sulfonate, desired):2% R-enantiomer (27b-sulfonate, undesired). The solid thus obtained was used directly in the next step.
Example 6
Preparation of Formula I Compound Salt: (5S,8S)-8-({(1R)-1-[3,5-Bis(trifluoromethyl)phenyl]ethoxy}methyl)-8-phenyl-1,7-diazaspiro[4.5]decan-2-one hydrochloride monohydrate
Example 6A
Preparation of the Compound of Formula I from 27a-Sulfonate
A suspension was made by adding zinc powder (12.2 Kg, 186.6 moles) to 42 liters of concentrated acetic acid with vigorous stirring. In a separate vessel was placed 4.04 Kg of the starting material prepared in Example 5, above, and 4.1 Kg of a compound 27a-sulfonate compound prepared in a similar reaction which yielded a salt comprising 88.2% S-enantiomer and 7.8% R-enantiomer (total 8.14 kg of the sulfonate salts, about 95% S-enantiomer). The sulfonate salts were dissolved in 82 liters of concentrated acetic acid heated to 45° C. to obtain a solution. When all of the solids had dissolved the solution temperature was adjusted and maintained at a temperature between 20° C. and 30° C. The solution containing the compound of Formula 27a-sulfonate was added to the stirring zinc suspension while maintaining the mixture at a temperature below 60° C. After all of the solution was added, the reaction mixture temperature was adjusted and maintained at a temperature of from 55° C. to 60° C. until the reaction was complete, as determined by HPLC. At the end of the reaction the reaction mixture was then cooled and maintained at a temperature of from 20° C. to 30° C.
The reaction mixture was filtered through Hyflo (4.12 kg) and the wet cake was washed with toluene. The wash was combined with the filtrate and the mixture was concentrated under vacuum (80 mbar to 120 mbar) by maintaining the reaction mixture temperature between 30° C. and 60° C. until distillation ceased. To the concentrate was added 41 L of toluene. The resulting organic solution was washed successively with aliquots of 2N hydrochloric acid solution (45 L), sodium carbonate solution (2 aliquots of 82 L each, 8% solution) and sodium chloride solution (22 L, 10% solution). The washed solution was filtered and the filter rinsed with toluene which was combined with the filtrate. The filtrate was seeded with seed crystals of the compound of Formula I maintaining the filtrate at a temperature between 20° C. and 25° C. Concentrated hydrochloride acid was slowly added to the filtrate followed by fine spirit (95:5 ethanol/isopropanol) maintaining the mixture at a temperature between 20° C. and 25° C. The mixture was agitated at 20° C. to 25° C. for 25 to 35 minutes and then cooled to 0° C. to 5° C. and agitated for 25 to 35 minutes. The mixture was filtered and the wet cake washed with an aliquot of a 1:1 mixture of toluene/MTBE (10 L), followed by a second aliquot of MTBE (10 L) maintained at 20° C. to 25° C. The wet cake was dried at 40° C. to 45° C. under vacuum. The yield of crude Compound I was 88%.
The crude crystals of compound I (14.54 kg, 25.6 moles) were recrystalized by dissolving the crude compound in a mixture of fine spirit (35 liters; 95:5 ethanol/isopropanol), water with endotoxin control (35 liters) and hydrochloride acid (0.3 liter, 37%), and heating the solution to reflux with agitation. The refluxing solution was cooled and maintained at a temperature of between 74° C. to 77° C., and filtered through a preheated pipe and in-line filter. The apparatus was rinsed with a mixture of fine spirit (95:5 ethanol/isopropanol) and water with endotoxin control maintained at 60° C. to 70° C. and combined with the filtrate. The temperature of the solution thus provided was adjusted and maintained at a temperature between 72° C. and 74° C. and Compound I seed crystals were added. The seeded solution was maintained at this temperature for 15 to 20 minutes and then cooled to a temperature between 0° C. and 5° C. at the rate of 0.5° C. per minute. The seeded solution was maintained at a temperature between 0° C. and 5° C. and agitated for 30 to 40 minutes. At the end of the time the resulting mixture was filtered and washed with a 40:60 mixture of fine spirit (95:5 ethanol/isopropanol)/water with endotoxin control at 0° C. to 5° C. The wet cake was dried under vacuum (150 mbar to 200 mbar) at 35° C. to 40° C. under vacuum. The yield of the compound of Formula I was determined by HPLC to be 97% based on the amount of the S-isomer present in the solids used initially.
A second run was carried out in accordance with the foregoing, however, at the end of the reaction period the reaction mixture was extracted with aqueous sodium carbonate solution and the phases were split. The organic phase was added to dilute HCl to provide spontaneous crystallization. In a subsequent run, when spontaneous crystallization did not occur, seed crystals were charged to seed crystal formation. Once crystalline product had precipitated, the product was filtered and the cake washed successively with aliquots of water, a 1:1 mixture (vol.) of toluene:MTBE, and MTBE. The cake thus obtained was dried under vacuum at 40°-45° C. for approximately 8 h.
Example 6B
Reduction of the Compound of Formula Ia1
Preparation of the compound of Formula I with co-production of a significant amount of the compound of Formula Ia1 was carried out using the procedure described in Example 6A but starting with 47 Kg of the compound of Formula 27a-sulfonate and utilizing an industrial scale reactor. The product of the reaction was found to contain 35 mole % of the compound of Formula I and 46 mole % of the compound of Formula Ia1. At the end of the reaction the reaction mixture was was filtered through Hyflo (4.12 kg) and the wet cake was washed with toluene. The wash was combined with the filtrate and the mixture was concentrated under vacuum (80 mbar to 120 mbar) by maintaining the reaction mixture at a temperature of less than about 60° C. until a residue which was capable of being stirred was obtained. The residue was azeotropically distilled with denatured ethanol until distillation ceased then diluted with an additional aliquot of ethyl alcohol. Into a separate reactor, with stirring, was charged Raney Nickel (ca. 25 kg) and ethanol denatured with toluene. The reactor was stirred for 20 min and the liquid decanted off. The Raney Nickel was re-slurried with ethanol and the liquid decanted until the moisture content of the residue was acceptable for running a hydrogenation reaction. When the moisture content was acceptable, the reactor was charged with additional ethanol and the catalyst was transferred to an autoclave with agitation as an ethanol slurry. The product mixture prepared as described above was added to the autoclave and the batch hydrogenated at 5 bar H 2 pressure at ca. 50° C. until a mixture of 81.5 mole % of the compound of Formula I and 1.9 mole % of the compound of Formula Ia1 was observed in the reaction mixture. The reaction mixture thus obtained was filtered and the resulting filter cake rinsed with ethanol and combined with the filtrate. The filtrate was concentrated under vacuum to a stirrable residue, azeotropically distilled with ethanol, and when distillation ceased, the residue was diluted with an additional aliquot of ethanol. A dilute solution of aqueous HCl was added to the ethanol solution with stirring over 20 minutes and the mixture was stirred for an additional 15 minutes. The resulting reaction mixture was filtered, and the cake washed successively with aliquots of water, a 1:1 mixture of MTBE:toluene, and MTBE. The washed cake was dried under vacuum at 40°-45° C. for about 8 hours and sampled for residual solvent and water content. The hydrogenation reaction over Raney nickel yielded about 60% of the compound of Formula I based on the amount of compound of Formula V employed.
Example 7
Isomer Ratio Control by Varying Michael Addition Reaction Conditions
The Michael addition reaction shown was carried out by dissolving a weighed amount of the compound of Formula V (reactions were run using from about 200 mg to about 10 g of Formula V, depending upon the acrylate employed) into the solvent shown in the tables below. The solution was stirred at a selected temperature while adding approximately 56 equivalents of Brockmann activity IV alumina obtained from Aldrich or Camag (residual water content 7 wt. % to 12 wt. %, used as received). After 10 minutes of additional stirring, 5 equivalents of the R-acrylate indicated in the tables below was added and stirring was maintained for 20 hours. At the end of the reaction time the reaction mixture was analyzed by HPLC for the combined amount of the compounds of Formulae 27a and 27b and ratio of the compounds of Formulae 27a and 27b produced in the reaction.
TABLE I
Effects of: (i) Varying oxide catalyst; (ii) Running Michael addition in the presence or absence of
a piperidine nitrogen protecting group; and (iii) Varying the “R” group of the acrylate.
Isomer Ratio (S:R) -
Isomer Ratio (S:R) -
Base = Brockman
Isomer Ratio (S:R) -
Base = Brockman
Isomer Ratio (S:R) -
“R” group of
Activity I
Base = MgO
Activity I
Base = MgO
No.
R 1 -acrylate
R 2 = H
R 2 = H
R 2 = Cbz
R 2 = Cbz
1
Methyl
63/37
20/80
2
(−)-8-Phenylmenthyl
78/22
25/75
15/85
3
Phenyl
66/34
4
t-Butyl
69/31
34/66
30/70
25/75
5
Isobornyl
84/16
23/77
18/82
6
1-adamantanyl
69/31
7
2-adamantanyl
85/15
8
adamantane methanyl
86/14
9
cis-Pinan-2-yl
66/34
10
(+)-isopinocampheyl
73/27
The reactions run for Table I were carried out using a weight of n-hexane 14× the weight of the acrylate employed in the reaction. Reactions were run at ambient temperature (about 20° C. to 25° C.). The data shown in Table 1 indicates that, for some acrylate acceptors, the presence of a protecting group on the piperidine nitrogen can reverse the selectivity of the Michael addition reaction for the preferred isomer. It indicates also that basic alumina is the preferred base catalyst for promoting formation of the preferred isomer, and that selecting a sterically demanding acrylate, for example adamantane methanyl-acrylate, promotes preferentially the formation of the desired isomer.
TABLE II
Effect of Solvent on Isomer Produced in the Michael Addition Step
Run
Isomer Ratio Produced
No.
Solvent
(S-isomer:R-isomer)
1
n-Hexane
79:21
2
Toluene
84:16
3
Methanol
48:52
4
Dimethylformamide
38:62
5
Tetrahydrofuran
51:49
The data in Table II were generated using the above-described addition reaction employing Brockman activity IV basic alumina and (−)-8-phenylmenthyl acrylate as the Michael acceptor with the deprotected substrate compound of Formula V (thus “R 2 ”═H). All runs were conducted at ambient temperature (about 20° C. to 25° C.). These results indicate that non-polar solvents, for example n-hexane, or low polarity non-protic solvents, for example toluene, promote formation of the desired isomer.
TABLE III
Influence of Alumina Activity Stage
on Selection of Preferred Isomer
Run
Isomer Ratio
No.
Base
(S-isomer:R-isomer
1
Neutral Alumina Brockman Activity I
63:37
2
Basic Alumina Brockman Activity I
51:49
3
Basic Alumina Brockman Activity II
4
Basic Alumina Brockman Activity III
5
Basic Alumina Brockman Activity IV
70:30
These reactions were run using methyl acrylate as the Michael acceptor, with a deprotected substrate (therefore “R*”═H) in n-hexane at 20° C. to 25° C. The data in Table III indicates that the best selectivity for the desired S-isomer is observed utilizing basic alumina having a Brockman activity level of IV. It was also found that conversion yields on Brockman activity I material were very low, typically 37% conversion after reactions times comparable to those yielding complete conversion with Brockman activity level IV alumina.
The above description of the invention is intended to be illustrative and not limiting. Various changes or modifications in the embodiments described herein may occur to those skilled in the art. These changes can be made without departing from the scope or spirit of the invention | This application discloses a novel process to synthesize 8-[{1-(3,5-Bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds, which may be used, for example, as NK-1 inhibitor compounds in pharmaceutical preparations. | 2 |
FIELD OF THE INVENTION
[0001] The invention concerns a process for the renaturation of recombinant, eukaryotic proteins containing disulfide bonds after expression in prokaryotes.
BACKGROUND AND PRIOR ART
[0002] In case of the production of recombinant proteins in heterologous expression systems like e.g. Escherichia coli , these proteins often form inactive, insoluble aggregates (so-called “retractile bodies” or “inclusion bodies”). Additionally, these inclusion bodies are contaminated by host cell components like host cell proteins, nucleic acids, endotoxins and low molecular weight contaminants. It is assumed that the formation of these inclusion bodies is a result of the very high local concentration of the heterologous protein in the cell during induction and protein biosynthesis. However, the primary amino acid sequence of the heterologous protein in question is also of great importance as well as the presence of cysteine-residues that form covalent disulfide bonds during oxidative refolding. Before these target proteins can be used, e.g. for therapeutic purposes, the inclusion bodies have to be purified and, subsequently, the three-dimensional structure has to be renatured to convert the protein into the biologically active conformation.
[0003] A commonly applied sequence of process steps involves, first, the solubilization of the inclusion bodies by the addition of high concentrations of chaotropic, denaturing agents (e.g. guanidinium hydrochloride or urea), or by the addition of strongly acidic agents like, e.g. glycine/phosphoric acid mixtures. Concurrently, intramolecular disulfide bonds present in the inclusion bodies may be either reduced chemically or cleaved by the so-called sulfitolysis procedure involving sulfite and an oxidizing agent. Secondly, the solubilized protein mixture may be further purified by either chromatographic means or filtration methods, both of which are well known procedures for those skilled in the art.
[0004] Subsequently, the linearized, monomeric protein solution in the presence of high concentrations of chaotropic agent is highly diluted in order to allow for the formation of the biologically active form. This can be performed either rapidly (by simple dilution into a large volume of refolding buffer) or slowly by diafiltration or by dialysis against the refolding buffer. Other techniques described in the literature involve the adsorption of the target protein onto a chromatographic resin and, subsequently, lowering the concentration of chaotropic agent allowing refolding to take place, or size exclusion chromatography in order to separate the protein chains thereby circumventing the tendency to form aggregates. In every case, the concentration of the chaotropic salt has to be decreased below a certained limit, which is dependent on the target protein, e.g. usually below 0.5 M guanidinium hydrochloride.
[0005] The major side reaction during refolding is the formation of insoluble aggregates, which is dependent on the local concentration of folding intermediates. In the literature, a broad range of folding aids are described, effectively suppressing this formation of insoluble protein aggregates, like e.g. chaperone proteins, other types of proteins (e.g. bovine serum albumin), and several types of non-protein materials, including sugars and cyclic sugars, short chain alcohols like e.g. glycerol, pentanol, hexanol, enzyme substrates, synthetic polymers, detergents, and chaotropic salts (de Bernardez Clark, E (1998): Curr. Opinion Biotechnol. 9: 157-163 and citations therein; Lilie H, Schwarz E, Rudolph R (1998): Curr. Opinion Biotechnol. 9: 947-501 and citations therein; Sharma A, Karuppiah N (1998): U.S. Pat. No. 5,728,804 filed Jun. 2, 1995). A different approach has recently been published where so-called artificial chaperones are used to keep hydrophobic folding intermediates in solution (Gellmnan S, Rozema D B (1996): U.S. Pat. No. 5,563,057 filed Oct. 31, 1994). In a first step, hydrophobic folding intermediates are trapped into detergent micelles leading to a suppression of protein aggregation. The trapped folding intermediates cannot fold to the native conformation. In a second step, a “stripping agent”, like e.g. different cyclodextrins or linear dextrins, are added in considerable molar excess to the remove the detergent again allowing the protein to refold into its biologically active conformation. There are several drawbacks to this approach like 1. Large molar excess of the expensive “stripping agent”, 2. Protein aggregation occurring during the “stripping” phase, 3. Difficulty to remove residual detergent bound to the target protein, 4. Limitations in protein capacity and solubility of cyclodextrins and 5. Sensitivity of the artificial chaperone system with respect to process variations (limited robustness). Moreover, artificial chaperone systems are specific with respect to the target protein, the type of detergent and “stripping agent” and the experimental conditions employed. Hence, there is no generic artificial chaperone system available (Daugherty D L, Rozema D, Hanson P E, Gellman S H (1998): J. Biol. Chem. 273: 33961-33971; Rozema D, Gellman SH (1996): J. Biol. Chem. 271: 3478-3487).
[0006] Most of the above mentioned aggregation suppressors only work with a limited number of proteins. One exception is the amino acid L-arginine, which was shown to be generally applicable to a wide range of different proteins like e.g. t-PA, Fab fragments, lysozyme and other enzymes (Rudolph R, Fischer S, Mattes R (1997): Process for the activating of gene-technologically produced, heterologous, disulfide bridge-containing eukaryotic proteins after expression in prokaryotes. U.S. Pat. No. 5,593,865; Rudolph R, Pischer S, Mattes R (1995): Process for the activation of T-PA or ING after genetic expression in prokaryotes. U.S. Pat. No. 5,453,363; de Bernardez Clark, E (1998): Curr. Opinion Biotechnol. 9: 157-163 and citations therein).
[0007] L-arginine was shown for a number of proteins to be effective only in high molar excess with respect to the molarity of the protein to be refolded. The mechanism by which L-arginine suppresses the formation of protein aggregates is still unknown (Lilie H et al. (1998): Curr. Opinion Biotechnol. 9: 497-501). Moreover, L-arginine is an expensive, chiral fine chemical.
[0008] Hence, there is still a need to develop strategies for protein refolding using conventional techniques. From the state of the art, no generally useable, chemically simple and inexpensive aggregation suppressor is known, which can be applied in a commercially attractive refolding process of proteins at high concentrations of up to 0.5-1 g/L.
SUMMARY OF THE INVENTION
[0009] Starting from insoluble protein aggregates (so-called inclusion bodies) as obtained by overexpression in Escherichia coli , it is the task of the present invention to make available a commercially attractive route for the renaturation of proteins like, e.g., Interleukin-4 and its derivatives, at high protein concentrations employing a suitable, chemically simple and readily available aggregation suppressor. Due to its unspecificity, the aggregation suppressor(s) as described in the present invention may be applied to a wide range of different proteins.
[0010] The method described herein comprises adding a solution of denatured, chemically modified or reduced protein, into a refolding buffer containing a primary, more preferably secondary or tertiary amines having the formula
with substitutions R 1 , R 2 , and R 3 , where R 1 and R 2 can be any combination of the ligands H, O═C—NH 2 , (CH 2 ) 4 —NH 2 , (CH 2 ) 3 —COOH, (CH 2 ) 2 —CHOH—CH 3 , CH 2 —CH 2 —OH, CH 2 —CH 3 , CH 3 , NH 2 . The residue R 3 can be C(NH 2 )═NH, C(CH 2 OH) 3 , CH 2 —CH 2 —OH or H.
[0012] In a preferred embodiment, the refolding buffer contains a further solubility enhancer like, e.g. additional ions, like e.g. chloride or, more preferably, sulfate ions, which aid in suppressing the formation of protein aggregates synergistically.
[0013] It is known for a large number of proteins from prior art that, for renaturation, certain limiting values of protein concentration should not be exceeded. The level of these concentration limits are depending on the nature of the protein to be refolded. Now is the recognition that comparatively large amounts of denatured protein do not require larger amounts of solution volume in order to achieve larger amounts of refolded protein due to the excessively high solubilization capacity of the above mentioned amine(s) or a combination of the above mentioned amines and another solubility enhancer.
[0014] The objective of the present invention therefore include providing:
a) a method of the above kind for refolding an inactive protein into a native conformation thereby effectively suppressing the formation of protein aggregates causing loss of refolding yield and recovery of soluble protein; b) a method of the above kind that allows the refolding at high protein concentrations; and c) a method of the above kind that can be used with inexpensive non-chiral commodity chemicals.
[0018] These and still other objects and advantages of the present invention will be apparent from the description that follows. It should be understood that the following is merely a description of the preferred embodiments, and is not intended as a description of all possible embodiments. The claims should be looked to do determine the full scope of the invention.
[heading-0019] Definitions
[0020] As used herein, the term “Interleukin-4 derivative” refers to muteins of human Interleukin-4 with exchanged amino acid residues at different sites of the polypeptide chain according to Sebald, W (1992): U.S. Pat. No. 5,723,118 and EP-Patent 613499B1 dated 13. Nov. 1992 and Domingues et al. (1999): PCT patent application PCT/IB00/00769.
[0021] As used herein, the term BPTI refers to bovine pancreatic trypsin inhibitor (also called aprotinin).
[0022] As used herein, “correctly folded protein” refers to the target protein in its native structure exhibiting the native disulfide bonding.
[0023] The “refolding yield”, as used herein, is defined as the concentration of correctly folded, unmodified target protein (e.g., [mg/L]) in the renaturation mixture.
[0024] The “overall refolding yield”, as used herein, is defined as the concentration of correctly folded, unmodified target protein (e.g., [mg/L]) divided by the amount of total protein in the renaturation mixture. The overall refolding yield is expressed in [%].
[0025] The terms “protein recovery” or “recovery of soluble protein”, as used herein, refer to the ratio of soluble protein recovered after refolding and the initial total protein. The protein recovery is expressed in [%].
[0026] The term “purity” ([%]), as used herein, is calculated on the basis of the refolding yield of the target protein and the concentration of soluble protein in the renaturation mixture as determined by RP-HPLC (see example 1).
[0027] The term TRIS, as used herein, refers to the basic buffering substance Tris-(hydroxymethyl)-aminomethane. The term TEA, as used herein, refers to the basic buffering substance triethanolamine. The term GndHCl, as used herein, refers to the chaotropic salt guanidinium hydrocloride.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] The subject of the present invention is a process for the reactivation of recombinant, disulfide bridged proteins after heterologous expression in prokaryotes leading to insoluble inclusion bodies, which are, subsequent to purification of these protein aggregates, denatured in high concentrations of a suitable chaotropic salt, chemically modified (formation of a mixed disulfide between protein-SH groups and a suitable mercaptane or introduction of a sulfite group into the protein-SH groups to form S—SO 3 groups), and renatured in a refolding buffer using high concentrations of a primary, more preferably secondary or tertiary amines with substitutions R 1 , R 2 , and R 3 , where R 1 and R 2 can be any combination of the ligands H, O═C—NH 2 , (CH 2 ) 4 —NH 2 , (CH 2 ) 3 —COOH, (CH 2 ) 2 —CHOH—CH 3 , CH 2 —CH 2 —OH, CH 2 —CH 3 , CH 3 , NH 2 . The residue R 3 can be C(NH 2 )═NH, C(CH 2 OH) 3 , CH 2 —CH 2 —OH or H. Additionally, combinations with other solubility enhancers, like e.g. chloride or, more preferably, sulfate ions, are effective in preventing protein aggregation.
[0029] The production of recombinant Interleukin-4 derivative employing Escherichia coli as host organism has been already described in detail (Apeler H, Wehlmann H (1999) Plasmids, their construction and their use in the manufacture of Interleukin-4 and Interleukin-4 muteins. EP 10 22 339, 2000-07-26).
[0030] Methods for cell harvest, cell disruption, inclusion body purification, solubilization and chemical modification of SH-groups are well known procedures to those persons skilled in the art (Creighton T E (ed.) (1989): Protein structure—A Pratical Approach. IRL Press, Oxford, New York, Tokyo).
[0031] From prior art it is well known that chemical agents of low molecular weight may suppress the formation of aggregates during refolding. Therefore, a wide range of chemicals was screened in order to find a suitable aggregation suppressor to be employed in the refolding process of Interleukin-4 derivative, but also other proteins like, e.g., BPTI.
[0032] As indicated in example 1 (Table 1), a number of chemicals effectively aids in the solubilization of folding intermediates resulting in a significant increase of the recovery of soluble protein. However, this does not necessarily mean that these compounds also lead to a significant increase in yield of the correctly folded, biologically active disulfide isoform (see column “relative refolding yield” in Table 1). For example, the detergent cetyl triethylammonium chloride (CTAC) effectively solubilizes folding intermediates leading to an increase in protein yield of 735% compared to the phosphate control. However, CTAC fails to increase the yield of correctly folded disulfide isoform resulting in a low refolding yield and a low purity. Several agents listed in Table 1 are well known from prior art for their ability to aid as aggregation suppressor during refolding, like e.g. L-Arginine, Urea, guanidinium hydrochloride, poly(ethylene)glycols, acetamide and short chain alcohols. However, most of these failed in case of Interleukin-4 derivative with the exception of L-arginine and, to a lesser extend, guanidinium hydrochloride.
[0033] Guanidinium hydrochloride effectively solubilizes folding intermediates at optimal concentrations of 750 mM. The N-methylated or N-ethylated derivatives and bis(-1-aminoguanidinium)-sulfate are more effectively solubilizing folding intermediates at lower concentrations (200-600 mM) as compared to guanidinium hydrochloride. However, the purity of the refolded protein (18.4 to 27.1%) is much lower compared to the phosphate control.
[0034] Surprisingly, the buffer agent Tris(hydroxymethyl)-aminomethane (TRIS) in the combination with sulfuric acid at high concentrations positively affected the solubilization of folding intermediates (850%) and the refolding yield (677%) while moderately decreasing the purity compared to the phosphate control. TRIS is widely used at very low concentrations (<0.1 M) as a buffering substance in refolding mixtures, but not at high concentrations as aggregation suppressor. Ethanolamine, which is structurally related to TRIS, also positively affected the solubilization of folding intermediates (pH-titration with HCl), resulting in comparable refolding and protein yields and purities. Comparison of TRIS titrated with sulfuric acid versus hydrochloric acid shows the positive additional effect of sulfate ions on the protein yield, refolding yield and the purity. However, ethanolamine titrated with sulfuric acid did not result in synergistic effects on the refolding and protein yield.
[0035] For example, Interleukin-4 derivative and BPTI, as shown in examples 4 and 6, can be effectively refolded in a combined buffering system consisting of TRIS and sulfate ions (sulfuric acid titration). In case of Interleukin-4 derivative, protein concentrations of preferably 250 to 1000 [mg/L] can be employed, more preferably 400 to 700 [mg/L] and, even more preferably, 450 to 550 [mg/L]. L-cysteine should be included into the refolding mixture in order to allow for the formation of stabilizing disulfide bonds, preferably at 1 to 4 [mM], more preferably at 2.5 to 3.5 [mM]. TRIS/H 2 SO 4 should be present preferably at 1 to 3 [M], more preferably at 1.4 to 2.4 [M]. The pH of the buffer is adjusted to about 7-9, more preferably 7 to 8, and most preferably 7.5.
[0036] In case of BPTI, protein concentrations of preferably 500 to 1000 [mg/L] can be employed, more preferably 600 to 800 [mg/L] and, even more preferably, 700 to 800 [mg/L]. L-cysteine should be included into the refolding mixture in order to allow for the formation of stabilizing disulfide bonds, preferably at 2.5 to 4 [mM], more preferably at 3.0 to 3.5 [mM]. TRIS/H 2 SO 4 should be present preferably at 0.2 to 1.4 [M], more preferably at 0.3 to 1.0 [M]. The pH of the buffer is adjusted to about 7-9, more preferably 7 to 8, and most preferably 7.5.
[0037] Even more surprisingly, triethanolamine effectively solubilizes folding intermediates (800%), does not affect the purity of the refolded protein (44.1% which is' comparable to the phosphate control), resulting in the best refolding yield (1039% compared to the phosphate control).
[0038] For example, Interleukin-4 derivative, as shown in examples 5, can be effectively refolded in a combined buffering system consisting of TEA and sulfate ions (sulfuric acid titration). Protein concentrations of preferably 250 to 1000 [mg/L] can be employed, more preferably 400 to 700 [mg/L] and, even more preferably, 450 to 550 [mg/L]. L-cysteine should be included into the refolding mixture in order to allow for the formation of stabilizing disulfide bonds, preferably at 0.4 to 4 [mM], more preferably at 0.8 to 2 [mM]. TEA/H 2 SO 4 should be present preferably at 0.5 to 2 [M], more preferably at 0.8 to 1.5 [M]. The pH of the buffer is adjusted to about 7-9, more preferably 7 to 8, and most preferably 7.5.
[0039] Taking the data listed in Table 1 together, a structure-function relationship can be deduced, revealing a general chemical principle: The most effective aggregation suppressors are primary, more preferably secondary or tertiary amines with substitutions R 1 , R 2 , and R 3 , where R 1 and R 2 can be any combination of the ligands H, O═C—NH 2 , (CH 2 ) 4 —NH 2 , (CH 2 ) 3 —COOH, (CH 2 ) 2 —CHOH—CH 3 , CH 2 —CH 2 —OH, CH 2 —CH 3 , CH 3 , NH 2 . The residue R 3 can be C(NH 2 )═NH, C(CH 2 OH) 3 , CH 2 —CH 2 —OH or H.
[0040] The central role of the amine function was demonstrated with canavanine-sulfate, where the central amine group is exchanged for an oxygen group, resulting in a complete loss of recovery of soluble protein (equal to the control without the addition of any aggregation suppressor) and loss of correctly refolded Interleukin-4 derivative. The data listed in Table 1 also show that the counter ion may also play a significant role. Sulfate ions are superior to chloride ions with regard to the refolding yield and inhibition of protein aggregation. Therefore, a combination of an amine as described above and a sulfate salt of sulfuric acid most effectively inhibits the formation of protein aggregates and allows the protein to refold into its native conformation.
EXAMPLE 1
[heading-0041] Analytical Methods
[0042] Analytical RP-HPLC is carried out on a YMC C4 column (5μ, 200 Å, 4.6×250 mm) at a flow rate of 1.0 ml/min. Detection is performed at 210 nm. The optional pre-column (20 mm×4 mm) is packed with Source 15 RPC (Pharmacia, Sweden). Buffer A is 0.1% TFA, buffer B is 0.1% TFA with 70% acetonitrile. The gradient is performed as follows: 0-2 min, 40% B; 2-19.5 min, 40%-85% B; 19.5-20 min, 85%-100% B; 20-21 min, 100% B, 21-22 min, 100%-40% B, 22-25 min, 40% B (re-equilibration). Correctly folded Interleukin-4 elutes at a retention time of 16 min employing a Hewlett-Packard LC 1100 system. Correctly folded BPTI elutes at a retention time of 12.8 min. Samples of refolding mixtures are sterile filtered (0.22μ cut-off) before analysis.
[0043] The peak eluting at the retention time of the native form is integrated giving the refolding yield expressed in [mg/L] units and corresponds to the concentration of correctly folded protein (calculated based on external standard curves). The total area counts correspond to the concentration of soluble protein present in the refolding mixture expressed in [mg/L] units. The ratio of these two values give the purity of the refolded protein expressed in [%] units.
[0044] The total protein concentration was determined after trichloroacetic acid precipitation, which was performed according to biochemical standard methods, using the commercially available BCA-assay (Pierce, USA) and bovine serum albumin (Boehringer-Mannheim, Germany) as calibration standard.
EXAMPLE 2
[heading-0045] Preparation of Starting Materials for Refolding Experiments
[0046] Proteins were solubilized in the presence of 0.2 M Tris-HCl, pH 9 containing 8 M Guanidinium hydrochloride to give a final protein concentration of 10 [g/L]. The SH-groups were then sulfitolyzed by the addition of 30 [g/L] sodium sulfite and 60 [g/L] potassium tetrathionate. After the addition of sulfite, the solution was stirred at room temperature for 30 min in order to allow completeness of the reaction of sulfite with any disulfides present in the solubilized proteins. Subsequently, tetrathionate was added and the solution is stirred for further 90 min in order to allow the conversion of SH-groups to disulfides and the cleavage to S-sulfite-groups to run to completion. Finally, the solution was filtered through a 1.2 g-cut off depth filter (e.g. Sartopure PP2, 1.2μ, Sartorius AG, Germany). The solution was then diafiltered against 5 volumes of diafiltration buffer consisting of 0.2 M Tris-HCl, pH 9 containing 4 M Guanidinium hydrochloride employing an ultrafiltration membrane (cut-off 10.000 MW, e.g. Hydrosart 10 kD, Sartorius AG, Germany). The retentate harvested from the ultrafiltration apparatus contained a final protein concentration of approx. 10 [g/L] and was stored at 2-8° C. for up to 2 weeks.
EXAMPLE 3
[heading-0047] Effects of Different Chemicals on the Refolding of Interleukin-4 Derivative
[0048] The protein solution from Example 2, containing denatured, sulfitolyzed protein, is diluted into refolding buffer to give a final protein concentration of 250 [mg/L] as determined by the BCA-assay (Pierce, USA). The refolding buffer consisted of the following ingredients:
50 mM sodium phosphate buffer, pH 7.5 1 mM Ethylenediamine tetraacetic acid, tetrasodium salt (EDTA) 0.8 mM L-cysteine A certain amount of aggregation suppressor as indicated in Table 1.
[0053] The total final volume of the refolding solution was 50 mL (glass vials, Schott, Germany). The glass vials were capped with parafilm. Refolding was allowed to run to completion within 24-36 hours with stirring on a magnetic bar stirrer (100-200 rpm). At intervals, samples were withdrawn and analyzed by RP-HPLC (see Example 1).
TABLE 1 Results of the screening for aggregation suppressors Relative Relative Protein Concentration Concentration Refolding Yield Solubility range optimum [%] of phosphate [%] of phosphate Group Compound [mM] [mM] control control Purity [%] Control Phosphate 50 0 100 100 44.7 Amino L-Lysine 0-1500 400 386 315 32.8 acids L-Asparagine 0-200 200 107 93 37.8 L-Glutamine 0-150 75 99 89 37.4 D,L-Norleucine 0-100 50-100 106 93 37.2 L-Arginine 0-1200 600 873 845 32.5 Arginine χ-Guanidino-butyric acid 0-250 250 283 472 20.0 derivatives 4-Guanidino-butane-2-ol 0-1000 600 299 740 13.8 4-Guanidino-butylamine-sulfate 0-1000 200 177 456 20.6 Canavanine-sulfate 0-1200 600 0 100 0 Chaotropic Urea 0-1500 1500 285 209 37.6 agents GuHCl 0-1000 750 609 915 18.4 N-Methylguanidinium-sulfate 0-1000 600 720 1063 19.9 N,N-Dimethylguanidinium- 0-1000 200 645 700 27.1 sulfate N,N-Diethylguanidinium-sulfate 0-1000 400 691 963 21.1 Bis-(1-Aminoguanidinium)- 0-1000 400 798 1037 22.7 sulfate Detergents Tween 80 0.1-100 100 169 221 21.1 Zwittergent 3-14 0.01-10 0.01 85 76 30.3 Zwittergent 3-12 0.1-100 0.1 110 168 18.3 CHAPS 0.5-500 5 120 167 28.9 Triton X-100 0.1-100 1 140 570 6.8 CTAC 0.1-100 100 57 735 1.2 Solvents Ethanol 1-100 50 104 112 37.1 1-Propanol 1-100 10 96 103 37.6 1-Butanol 1-100 5 102 107 38.5 1-Hexanol 1-100 1 88 80 44.1 Salts NaCl 0-1000 800-1000 495 575 41.4 NH 4 Cl 0-1000 800-1000 504 635 37.2 Na 2 SO 4 0-1000 200 456 505 41.2 (NH 4 ) 2 SO 4 0-1000 400 540 600 41 Buffers Phosphate 0-1000 200 182 175 41.5 TRIS-HCl 0-1000 1000 489 505 24.6 TRIS-H 2 SO 4 0-1000 1000 677 850 37.8 Ethanolamine-HCl 0-1000 400 431 760 25.8 Ethanolamine-H 2 SO 4 200-600 400 61 81 25.7 Triethanolamine-H 2 SO 4 0-2000 1500 1039 800 44.1 Others Acetamide 0-2000 800-1500 136 126 34.9 PEG 200 0-1 0.5-1.0 102 89 38.5 PEG 400 0-1 1.0 111 93 41.2 PEG 600 0-1 0.05-0.25 111 114 33.1 PEG 1000 0-1 0.25 101 89 38.8 PEG 2000 0-1 0.5-1.0 132 122 35.2 PEG 3000 0-1 0.1-0.5 122 104 35 PEG 4000 0-1 0.1 153 133 37.6 Control: Refolding conditions: 50 mM sodium phosphate buffer, pH 7.5, 1 mM EDTA, 0.4 mM L-cysteine, 250 mg/L total protein concentration. Refolding yield: 8 mg/L correctly folded Interleukin-4 R121D Y124D (˜3% of total protein), 23.5 mg/L recovery of soluble protein (˜9% of total protein).
EXAMPLE 4
[heading-0054] Multifactorial Optimization of the Refolding of Interleukin-4 Derivative Employing the TRIS-Sulfuric Acid Based System
[0055] An attractive combination of aggregation suppressors is the TRIS-base/H 2 SO 4 -system. Therefore, this system was chosen for further optimization employing a multifactorial analysis.
[0056] The total final volume of the refolding solution was 50 mL (glass vials, Schott, Germany). The glass vials were capped with parafilm. Refolding was allowed to run to completion within 24-36 hours with stirring on a magnetic bar stirrer (100-200 rpm). At intervals, samples were withdrawn and analyzed by RP-HPLC (see Example 1).
[0057] The protein solution from Example 2, containing denatured, sulfitolyzed protein, is diluted into refolding buffer to give a final protein concentration indicated in Table 3. The following aspects of refolding buffer composition were investigated: concentration of TRIS-base (0.5 to 3 [M]), H 2 SO 4 (depending on TRIS-concentration; 0.4 to 1.4 [M]), residual guanidinium hydrochloride concentration (80-400 mM), L-cysteine concentration (0.4 to 4 [mM]), and initial protein concentration (50 to 1000 [mg/L]). The pH of the refolding buffer was adjusted to 7.5. All refolding mixtures contained 1 mM EDTA.
[0058] The experiments described in this example was designed to allow multifactorial statistical analysis of correctly folded Interleukin-4 derivative yield data in order to assess the importance of all single factors and all two-factor interactions. A partial cubic experimental design was generated and the resulting data were also analyzed employing a partial cubic model. The coefficients of the polynoms of the partial cubic model are given in Table 2.
TABLE 2 Partial cubic model employed for the experimental design of the refolding optimization of Interleukin-4 R121D Y124D
[0059]
TABLE 3
Effect of solution conditions (TRIS-H 2 SO 4 -system) on Interleukin-4
R121D Y124D refolding yield, recovery of soluble protein, overall
refolding yield and purity
Overall
Protein
refolding
Ref. Yield
recovery
yield
Purity
Trial #
TRIS-base
Cysteine
Protein
[mg/L]
[%]
[%]
[%]
1
3
4
50
9
81.3
18.00
22.1
2
3
0.4
1000
2.92
10.65
0.29
2.7
3
0.5
4
525
90.45
48.55
17.23
35.5
4
0.5
2.2
1000
137.7
46.34
13.77
29.7
5
1.75
4
1000
199.72
54.77
19.97
36.5
6
1.75
0.4
1000
25.05
27.23
2.50
9.2
7
3
2.2
50
11.3
60.79
22.60
37.2
8
0.5
4
50
10.37
53.54
20.73
38.7
9
3
0.4
525
68.32
55.36
13.01
23.5
10
0.5
0.4
525
81.82
36.66
15.58
42.5
11
1.75
0.4
50
13.6
62.08
27.21
43.8
12
0.5
0.4
1000
15.8
18.89
1.58
8.4
13
3
4
1000
176.31
43.94
17.63
40.1
14
1.75
4
525
131.19
68.94
24.99
36.2
15
1.3333
1.6
366.667
93.63
68.21
25.54
37.4
16
2.1667
1.6
366.667
91.95
69.77
25.08
35.9
17
3
2.8
683.333
134.38
55.72
19.67
35.3
18
0.5
1.6
683.333
110.68
48.94
16.20
33.1
20
2.1667
2.8
50
12.49
71.59
24.98
34.9
1
3
4
50
9.38
52.32
18.76
35.9
2
3
0.4
1000
8.94
18.32
0.89
4.9
3
0.5
4
525
97.16
50.43
18.51
36.7
4
0.5
2.2
1000
140.29
45.63
14.03
30.7
5
1.75
4
1000
197.53
56.85
19.75
34.7
6
1.75
0.4
1000
19.75
27.61
1.97
7.2
7
3
2.2
50
15.08
72.5
30.15
41.6
[0060] The yields obtained with selected combinations of these components are shown in Table 3. Inspection of these results shows that, under the experimental conditions employed, the following trends were apparent: (1) best refolding yields are obtained at high protein concentrations (750-1000 [mg/L]); (2) best overall refolding yields are obtained at 250 to 650 [mg/L] total protein concentration; (3) the optimal L-cysteine concentration range is 2.5 to 4 [mM]; (4) the optimal Tris-H 2 SO 4 -concentration range is 1.4 to 2.4 [M]; (5) best protein recovery is obtained at low protein concentrations (50 to 250 [mg/L]), high Tris-H 2 SO 4 -concentrations (2-3 [M]) and 2 to 3.5 [mM] L-cysteine; (6) best purity is obtained at high protein concentrations (400-1000 [mg/L]), high L-cysteine concentrations (2.5-4 [mM]). The purity is indepening on the Tris-H 2 SO 4 concentration.
[0061] A compromise between optimal refolding yield, purity and protein recovery was identified employing the following settings: 500 mg/L total protein, 3.3 mM L-cysteine, 2 M Tris-H 2 SO 4 and 1 mM EDTA.
[0062] Checkpoints employing these optimal conditions revealed that the predicted and measured response values fit reasonably well, indicating that the model is adequate.
Overall refolding yield Predicted: 24.9 [%] (±1.84 StdErr) Measured: 25.4 [%] (±0.37 StdErr) Protein recovery Predicted: 65.9 [%] (±6.55 StdErr) Measured: 62.9 [%] (±0.63 StdErr) Purity Predicted: 38.6 [%] (±3.63 StdErr) Measured: 40.4 [%] (±0.45 StdErr) Refolding yield Predicted: 127 [mg/L] (±14.5 StdErr) Measured: 126.9 [mg/L] (±1.85 StdErr)
EXAMPLE 5
[heading-0063] Multifactorial Optimization of the Refolding of Interleukin-4 Derivative Employing the Triethanolamine-Sulfuric Acid Based System
[0064] Another attractive combination of aggregation suppressors is the Triethanolamine (TEA)/H 2 SO 4 -system. Therefore, this system was chosen for further optimization and scale-up of the protein concentration.
[0065] The total final volume of the refolding solution was 50 mL (glass vials, Schott, Germany). The glass vials were capped with parafilm. Refolding was allowed to run to completion within 24-36 hours with stirring on a magnetic bar stirrer (100-200 rpm). At intervals, samples were withdrawn and analyzed by RP-HPLC (see Example 1).
[0066] The protein solution from Example 2, containing denatured, sulfitolyzed protein, is diluted into refolding buffer to give a final protein concentration indicated in Table 5. The following aspects of refolding buffer composition were investigated: concentration of TEA (1 to 2 [M]), H 2 SO 4 (depending on TEA-concentration), residual guanidinium hydrochloride concentration (80-400 mM), L-cysteine concentration (0.4 to 10 [mM]), and initial protein concentration (50 to 1000 [mg/L]). The pH of the refolding buffer was adjusted to 7.5. All refolding mixtures contained 1 mM EDTA.
[0067] The experiments described in this example was designed to allow multifactorial statistical analysis of correctly folded Interleukin-4 derivative yield data in order to assess the importance of all single factors and all two-factor interactions. A partial cubic experimental design was generated and the resulting data were also analyzed employing a partial cubic model. The coefficients of the polynoms of the partial cubic model are given in Table 4.
TABLE 4 Partial cubic model employed for the experimental design of the refolding optimization of Interleukin-4 R121D Y124D
[0068]
TABLE 5
Effect of solution conditions (TEA-H 2 SO 4 -system) on Interleukin-4
R121D Y124D refolding yield, recovery of soluble protein, overall
refolding yield and purity
Protein
Overall
Trial #
TEA
Cysteine
Protein
Ref. Yield
recovery
refolding yield
Purity
[−]
[M]
[mM]
[mg/L]
[mg/L]
[%]
[%]
[%]
1
2
10
0.1
5.91
138.09
5.9
4.3
2
2
0.4
1
135.12
49.49
13.5
27.3
3
0.5
10
0.55
15.23
16.92
2.8
16.4
4
0.5
5.2
1
70.06
19.28
7
36.3
5
1.25
10
1
49.37
18.06
4.9
27.3
6
0.5
5.2
0.1
9.64
66.78
9.6
14.4
7
1.25
0.4
1
167.96
42.5
16.8
39.5
8
2
5.2
0.1
13.66
103.17
13.7
13.2
9
0.5
10
0.1
3.56
76.7
3.6
4.6
10
2
0.4
0.55
45.39
54.66
8.3
15.1
11
0.5
0.4
0.55
68.41
31.3
12.4
39.7
12
1.25
0.4
0.1
30.09
77.34
30.1
38.9
13
0.5
0.4
1
90.11
21.55
9
41.8
14
2
10
1
63.75
22.94
6.4
27.8
15
0.5
0.4
0.1
24.18
59.26
24.2
40.8
16
1.25
10
0.55
43.47
31.42
7.9
25.2
17
1
3.6
0.4
107.54
61.7
26.9
43.6
18
1.5
3.6
0.4
118.95
70.26
29.7
42.3
19
2
6.8
0.7
115.96
45.83
16.6
36.1
20
0.5
3.6
0.7
97.81
32.69
14
42.7
21
1.5
6.8
0.1
12.29
75.29
12.3
16.3
1
2
10
0.1
6.51
91.62
6.5
7.1
2
2
0.4
1
136.71
44.08
13.7
31.0
3
0.5
10
0.55
17.13
13.98
3.1
22.3
4
0.5
5.2
1
68.29
17.34
6.8
39.4
5
1.25
10
1
53.25
16.96
5.3
31.4
6
0.5
5.2
0.1
10.75
44.69
10.8
24.1
7
1.25
0.4
1
170.11
39.82
17
42.7
8
2
5.2
0.1
18.01
81.64
18
22.1
9
0.5
10
0.1
4.92
43.65
4.9
11.3
[0069] The yields obtained with selected combination of these components are shown in Table 5. Inspection of these results shows that, under the experimental conditions employed, the following trends were apparent: (1) best refolding yields are obtained at high protein concentrations (750-1000 [mg/L]); (2) best overall refolding yields are obtained at 100 to 550 [mg/L] total protein concentration; (3) the optimal L-cysteine concentration range is 0.4 to 4 [mM]; (4) the optimal TEA-H 2 SO 4 -concentration range is 1 to 1.6 [M]; (5) best protein recovery is obtained at low protein concentrations (50 to 250 [mg/L]), high TEA-H 2 SO 4 -concentrations (1.5-2 [M]) and 4 to 10 [mM] L-cysteine; (6) best purity is obtained at high protein concentrations (600-1000 [mg/L]), L-cysteine concentrations ranging between 0.4 and 4 [mM]) and at the TEA-H 2 SO 4 concentrations ranging between 0.8 and 1:5 [M]. A compromise between optimal refolding yield, purity and protein recovery was identified employing the following settings: 500 mg/L total protein, 0.8 mM L-cysteine, 1.4 M TEA-H 2 SO 4 and 1 mM EDTA.
[0070] Checkpoints employing these optimal conditions revealed that the predicted and measured response values fit reasonably well, indicating that the model is adequate.
Overall refolding yield Predicted: 24.6 [%] (±4.1 StdErr) Measured: 24.3 [%] (±0.8 StdErr) Protein recovery Predicted: 52.8 [%] (±10.5 StdErr) Measured: 58.2 [%] (±4.5 StdErr) Purity Predicted: 43.2 [%] (±5.3 StdErr) Measured: 41.8 [%] (±3.9 StdErr) Refolding yield Predicted: 106.8 [mg/L] (±16.9 StdErr) Measured: 121.6 [mg/L] (±2.0 StdErr)
Example 6
[heading-0071] Refolding of Bovine Pancreatic Trypsin Inhibitor (BPTI, Aprotinin) Employing the TRIS-Sulfuric Acid Based System
[0072] In order to demonstrate that the TRIS/H 2 SO 4 -system can also be employed for the refolding of other proteins than Interleukin-4 derivatives, the TRIS/H 2 SO 4 -system was also optimized for BPTI.
[0073] The total final volume of the refolding solution was 50 mL (glass vials, Schott, Germany). The glass vials were capped with parafilm. Refolding was allowed to run to completion within 24-36 hours with stirring on a magnetic bar stirrer (100-200 rpm). At intervals, samples were withdrawn and analyzed by RP-HPLC (see Example 1).
[0074] The protein solution from Example 2, containing denatured, sulfitolyzed protein, is diluted into refolding buffer to give a final protein concentration indicated in Table 7. The following aspects of refolding buffer composition were investigated: concentration of TRIS (0 to 2 [M]), H 2 SO 4 (depending on the concentration of TRIS-base), residual guanidinium hydrochloride concentration (80-400 mM), L-cysteine concentration (0.1 to 4 [mM]), and initial protein concentration (50 to 1000 [mg/L]).
[0075] The pH of the refolding buffer was adjusted to 7.5. All refolding mixtures contained 1 mM EDTA.
[0076] The experiments described in this example was designed to allow multifactorial statistical analysis of correctly folded BPTI yield data in order to assess the importance of all single factors and all two-factor interactions. A partial cubic experimental design was generated and the resulting data were also analyzed employing a partial cubic model. The coefficients of the polynoms of the partial cubic model are given in Table 6.
TABLE 6 Partial Cubic model employed for the experimental design of the refolding optimization of BPTI
[0077]
TABLE 7
Effect of solution conditions on BPTI refolding yield, recovery of
soluble protein and overall refolding yield
Overall
Protein
refolding
Trial #
TRIS-base
Cysteine
Protein
Ref. Yield
recovery
yield
Purity
[−]
[M]
[mM]
[mg/L]
[mg/L]
[%]
[%]
[%]
1
2
4
50
20.43
85.69
40.86
47.7
2
2
0.1
1000
0
0
0
0
3
0
4
525
159.29
61.05
30.34095
49.7
4
0
2.05
1000
275.45
70.84
27.545
38.9
5
1
4
1000
256.9
71.75
25.69
35.8
6
0
2.05
50
35.67
136.48
71.34
52.3
7
1
0.1
1000
0
2.59
0
0
8
2
2.05
50
19.45
80.85
38.9
48.1
9
0
4
50
8.51
39.92
17.02
42.6
10
2
0.1
525
0
0
0
0
11
0
0.1
525
0
0.4
0
0
12
1
0.1
50
15.71
69.04
31.42
45.5
13
0
0.1
1000
0
1.05
0
0
14
2
4
1000
158.93
36.23
15.893
43.9
15
0
0.1
50
5.03
14.13
10.06
71.2
16
1
4
525
18.64
89.48
3.550476
4
17
0.6667
1.4
366.667
107.29
83.34
29.26088
35.1
18
1.3333
1.4
366.667
104.5
82.6
28.49997
34.5
19
2
2.7
683.333
97.4
41.66
14.25367
34.2
20
0
1.4
683.333
149.44
51.46
21.86928
42.5
21
1.3333
2.7
50
14.08
76.21
28.16
36.9
1
2
4
50
16.15
69.37
32.3
46.5
2
2
0.1
1000
1.47
3.44
0.147
4.3
3
0
4
525
162.49
58.91
30.95048
52.5
4
0
2.05
1000
273.77
68.91
27.377
39.7
5
1
4
1000
265.9
78.2
26.59
34
6
0
2.05
50
9.73
39.56
19.46
49.2
7
1
0.1
1000
0
0.94
0
0
8
2
2.05
50
19.18
77.88
38.36
49.3
[0078] The yields obtained with selected combination of these components are shown in Table 7. Inspection of these results shows that, under the experimental conditions employed, the following trends were apparent: (1) best refolding yields are obtained at high protein concentrations (750-1000 [mg/L]); (2) best overall refolding yields are obtained at 500 to 1000 [mg/L] total protein concentration; (3) the optimal L-cysteine concentration range is 2.5 to 4 [mM]; (4) the optimal TRIS-H 2 SO 4 -concentration range is 0.2 to 1.0 [M]; (5) best protein recovery is obtained at low protein concentrations (50 to 100 [mg/L]), moderate TRIS-H 2 SO 4 -concentrations (0.9-1.4[M]) and 1.8 to 3.3 [mM] L-cysteine; (6) best purity is obtained at low protein concentrations (50-100 [mg/L]), L-cysteine concentrations ranging between 0.1 and 0.4 [mM]) and at the TRIS-H 2 SO 4 concentrations ranging between 0.1 and 0.5 [M].
[0079] A compromise between optimal refolding yield, purity and protein recovery was identified employing the following settings: 700 mg/L total protein, 3.3 mM L-cysteine, 0.3 M TRIS-H 2 SO 4 and 1 mM EDTA. | A method for renaturation of proteins comprising adding to a solution of denatured, chemically modified or reduced proteins a refolding buffer containing a primary, secondary or tertiary amine. Said method has been applied, for example, to interleukin-4 and bovine pancreatic trypsin inhibitor (BPTI), wich were previously (i) solubilized in the presence of guanidinium hydrochloride as chaotronic agent, and (ii) subjected to sulfitolysis. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority under 35 USC 119 from Japanese Patent Application No. 2005-217657, the disclosure of which is incorporated by reference herein.
BACKGROUND
1. Technical Field
The present invention relates to an optical scanning device and an image forming apparatus, and more particularly relates to an optical scanning device at which plural optical systems and a heat-generating component are disposed in a single container, the optical systems respectively guiding plural light beams which have been deflectingly scanned by a light-deflecting element, and to an image forming apparatus which is equipped with this optical scanning device.
2. Related Art
An electrophotographic-system color image forming apparatus deflectingly scans plural light beams corresponding to the colors Y (yellow), M (magenta), C (cyan) and K (black), or the like, with an optical deflector which is mounted at an optical scanning device, and forms a color image by focusing the respective colors through plural optical systems onto a photosensitive drum. In such a color image forming apparatus, image formation timings of the colors are regulated in accordance with a device temperature, which is measured by an environment sensor (a temperature sensor). Thus, color shifts between color images (reading registration errors) that are caused by temperature variations of the device are corrected for (“color registration correction”).
In recent years, in order to suppress costs, housings of optical scanning devices have come to be made of molded resin components, and as optical deflectors, inexpensive general purpose unitized components formed as units are being used. In such units, a polygon mirror and a motor are disposed on a circuit board, which serves as a base for the optical deflector, and a motor-driving IC, for controlling rotary driving of the motor, and the like are also mounted at the circuit board.
However, with an optical deflector which is formed as a unit in this manner, because the whole of the optical deflector is accommodated in the housing of the optical scanning device, heat which is generated by heat-generating components, such as the motor-driving IC and the like, tends to accumulate within the housing. Hence, with a housing made of resin, which has lower thermal conductivity (heat absorption and heat dissipation characteristics) than a metal model made of die-cast aluminum or the like, interior heat is less easily propagated through the housing and dissipated. Therefore, particularly just after the device starts to operate, when the amount of temperature increase is large, there is a difference in temperature gradient between an interior temperature of the optical scanning device (the housing) and the temperature that is measured by an environment sensor. Thus, there is a problem in that color registration errors will occur.
As is shown in FIG. 14 , when, for example, the temperature variation of a color image forming apparatus is observed over a 30-minute period after startup, the motor-driving IC of the optical deflector rapidly rises in temperature for about 3 minutes after startup, and then gradually stabilizes. Meanwhile, the interior of the optical scanning device (housing) gradually rises in temperature for about 25 minutes after startup, and substantially stabilizes at an increase of about 3.5° C.
On the other hand, because propagation of heat through the housing is low and propagation of heat through the air is dominant after startup, a rate of heat conduction to the environment sensor is slow, and the environment sensor has no observable rise in temperature for about 8 minutes after startup, thereafter rises only gradually, and does not match the temperature in the optical scanning device until about 30 minutes has passed.
Thus, just after the device starts operation, there is a difference between a gradient of the temperature in the optical scanning device and a gradient of the device temperature that is measured by the environment sensor, and the rise of the environment sensor is slower than the temperature rise of the optical scanning device interior. Therefore, when a reading registration difference between, for example, the color C and the color K is observed, as is shown in the graph for an IOT (Image Output Terminal) in FIG. 15 , a registration error just before input of a registration control cycle is large. Furthermore, when the polygon mirror of the optical scanning device (ROS: Raster Output Scanner) is rotated and laser light sources are illuminated, a graph showing the reading registration difference between the color C and the color K at the optical scanning device (‘ROS unit body’) is similar to the above-mentioned graph for the IOT. From this, it is understood that effects of heat sources other than the optical scanning device on deterioration in color registration at the IOT just after startup are small, and the deterioration in color registration is mainly determined by characteristics of the optical scanning device.
Further, as shown in FIG. 16 , reading registration offsets of the color C and the color K are set in relatively opposite directions, with the color C at a minus side, and the color K at a plus side. Thus, offset amounts are large. Note that differences between offset amounts of the color C and offset amounts of the color K in FIG. 16 constitute the graph of reading registration errors of the ROS unit body shown in FIG. 15 .
FIG. 17 shows a schematic diagram of the structure of the optical scanning device at which the various data shown in FIGS. 14 to 16 have been measured. At an optical scanning device 110 CK shown in FIG. 17 , two different optical systems corresponding to the color C and the color K are provided at a single housing (optical casing) 112 , which is made of resin. A light beam K corresponding to the color K, which is deflectingly scanned by a polygon mirror 54 of an optical deflector, passes through f-θ lenses 56 and 58 , is reflected by a total of four mirrors—a cylindrical mirror 60 K, a reflection mirror 62 K, a cylindrical mirror 64 K and a reflection mirror 66 K—and is focused on a photosensitive drum 24 K. Similarly, a light beam C corresponding to the color C, which is deflectingly scanned by the polygon mirror 54 , passes through the f-θ lenses 56 and 58 , is reflected by a total of three mirrors—a cylindrical mirror 60 C, a reflection mirror 62 C and a cylindrical mirror 64 C—and is focused on a photosensitive drum 24 C.
Now, just after startup of the device, besides the motor-driving IC of the optical deflector, a driving IC at which a laser light source driver (LDD) or the like is mounted also rapidly rises in temperature at the time of startup. Air inside the optical scanning device 110 CK is warmed by these heat-generating components, and the air is agitated by rotation of the polygon mirror 54 . Consequently, a distribution of temperature in the optical scanning device 110 CK alters or a hot air flow impinges on the optical system (for example, on a reflection mirror directly or on a support of a reflection mirror), and a temperature thereof is increased. Thus, when, for example, the light beams C and K pass through the f-θ lenses 56 and 58 and are initially incident on the cylindrical mirrors 60 C and 60 K and are inclined in the same direction, the light beams C and K that have been reflected by the cylindrical mirrors 60 C and 60 K are shifted as shown by the broken lines, and the reading registrations on the photosensitive drums 24 C and 24 K are offset to respectively opposite sides (see FIG. 16 ). Thus, the difference which is a color registration error becomes large.
As countermeasures for the color registration error which is generated in this manner, for example, reducing a time interval between temperature measurements by the environment sensor and increasing a number of registration control cycles have been considered. However, in such cases, while the color registration error described above can be avoided, the number of down-times, at which image output operations are stopped, increases and usability deteriorates.
SUMMARY OF THE INVENTION
According to an aspect of the present invention, an optical scanning device includes a light source that emits a light beam, an optical deflector at which a light beam emitted from the light source is incident, the optical deflector deflecting the incident light beam, an optical system that guides the deflected light beam to surface to be scanned by the deflected light beam, a driving device that drives at least a portion of the optical deflector, a thermal storage member mounted on the driving device, the thermal storage member absorbing and storing heat generated by the driving device, thereby controlling a temperature gradient of the driving device, and a casing body that accommodates the light source, the optical deflector, the optical system, the driving device, and the thermal storage member.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the present invention will be described in detail based on the following figures, in which:
FIG. 1 is a schematic view showing the structure of an image forming apparatus relating to a first exemplary embodiment of the present invention;
FIG. 2 is a perspective view showing optical scanning devices relating to the first exemplary embodiment of the present invention;
FIG. 3 is a plan view showing principal structural components of an optical scanning device relating to the first exemplary embodiment of the present invention;
FIG. 4 is a perspective view showing the principal structural components of the optical scanning device relating to the first exemplary embodiment of the present invention;
FIG. 5 is a diagram showing light paths of the optical scanning devices relating to the first exemplary embodiment of the present invention;
FIG. 6 is a front view showing an optical deflector at which a thermal storage member relating to the first exemplary embodiment of the present invention is provided;
FIG. 7 is a perspective view showing a vicinity of an optical deflector mounting portion of a housing relating to the first exemplary embodiment of the present invention;
FIG. 8 is a graph showing comparative results of temperature gradients of a motor-driving IC with and without presence of the thermal storage member;
FIG. 9 is a graph showing comparative results of temperature gradients of an ROS interior with and without presence of the thermal storage member;
FIG. 10 is a graph showing comparative results of reading registration differences between a color C and a color K at a ROS unit body with and without presence of the thermal storage member;
FIG. 11 is a graph showing comparative results of reading registration differences between the color C and the color K at an IOT with and without presence of the thermal storage member;
FIG. 12 is a front view showing an optical deflector at which a thermal storage member relating to a second exemplary embodiment of the present invention is provided;
FIG. 13 is a front view showing an optical deflector at which a thermal storage member relating to a third exemplary embodiment of the present invention is provided;
FIG. 14 is a graph showing differences between temperature gradients of a conventional motor-driving IC, ROS interior and environment sensor;
FIG. 15 is a graph showing reading registration differences between the color C and the color K at a conventional ROS unit body and IOT;
FIG. 16 is a graph showing a difference between reading registration offset directions of the color C and the color K at a conventional ROS unit body; and
FIG. 17 is an explanatory view for explaining light paths of a conventional optical scanning device and directions of offsetting of light beams of the color C and the color K.
DETAILED DESCRIPTION
Herebelow, exemplary embodiments of the present invention will be described in detail with reference to the drawings.
First Exemplary Embodiment
An image forming apparatus 10 according to this exemplary embodiment is provided with an optical scanning device 28 CK and an optical scanning device 28 YM, as shown in FIG. 1 . The optical scanning device 28 CK scans for exposing a photosensitive drum 24 C and a photosensitive drum 24 K, and is provided with optical systems corresponding to the colors C (cyan) and K (black). The optical scanning device 28 YM scans for exposing a photosensitive drum 24 Y and a photosensitive drum 24 M, and is provided with optical systems corresponding to the colors Y (yellow) and M (magenta).
The image forming apparatus 10 is also provided with electrophotographic units 12 Y, 12 M, 12 C and 12 K, which form toner images of the four colors Y (yellow), M (magenta), C (cyan) and K (black). The electrophotographic unit 12 Y is structured with a charging device 26 Y, the optical scanning device 28 YM, a developing device 30 Y, a first transfer device 14 Y and a cleaning device 32 Y disposed around the photosensitive drum 24 Y. The electrophotographic units 12 M, 12 C and 12 K have similar structures thereto.
The image forming apparatus 10 is also provided with an intermediate transfer belt 16 , a second transfer device 20 and a fixing device 22 . Respective toner images are layered by the first transfer devices 14 Y to 14 K to form a color toner image on the intermediate transfer belt 16 . The second transfer device 20 transfers the color toner image that has been transferred onto the intermediate transfer belt 16 to paper, which is supplied from a tray 18 . The fixing device 22 fuses and fixes the color toner image that has been transferred onto the paper.
As shown in FIG. 2 , the optical scanning devices 28 CK and 28 YM are provided with rectangular box-form housings 34 made of resin (which are molded components). Herein, because internal structures of the optical scanning devices 28 CK and 28 YM are substantially the same, only the optical scanning device 28 CK will be described.
As shown in FIGS. 3 and 4 , a light source portion 40 K, which emits a light beam K corresponding to the color K, and a light source portion 40 C, which emits a light beam C corresponding to the color C, are disposed in the housing 34 such that emission directions thereof are substantially at 90° to one another. In this exemplary embodiment, surface emission-type semiconductor lasers are employed as the emitting light sources. As shown in FIG. 4 , the light source portions 40 C and 40 K are structured with surface emission laser chips 41 C and 41 K and retaining members 43 C and 43 K. The surface emission laser chips 41 C and 41 K are formed to be capable of simultaneously emitting plural optical lasers. The retaining members 43 C and 43 K are members for retaining the surface emission laser chips 41 C and 41 K, are referred to with the usual term ‘LCC’ (leadless chip carrier), and ceramics are employed as materials thereof herein. The surface emission laser chips 41 C and 41 K are electrically connected, through the retaining members 43 C and 43 K, to circuit boards 45 C and 45 K, respectively, at which electrical circuits are mounted.
The light source portion 40 C which emits the light beam C is disposed to be offset in a height direction relative to the light source portion 40 K which emits the light beam K, and the light beam C and the light beam K are arranged so as to be a predetermined distance apart in the height direction.
A collimator lens unit 42 K, for making light of the light beam K parallel, is disposed on an optical path of the light beam K emitted from the light source portion 40 K. The light beam K that has passed through the collimator lens unit 42 K passes beneath a reflection mirror 44 , is incident at a slit plate 46 K and is incident on a half-mirror 48 , which is disposed on the optical path. The half-mirror 48 divides the light beam K into a transmitted light beam K and a reflected light beam BK in a predetermined ratio. The light beam BK is reflected and is incident at an optical power monitor 50 . Because a surface emission optical laser is employed in this exemplary embodiment, it is not possible to obtain light for light amount control from a backbeam. Therefore, a portion of the light beam emitted in a forward direction is utilized by this division with the half-mirror 48 . The light beam K that has been transmitted through the half-mirror 48 passes through a cylindrical lens 52 K and is incident at a polygon mirror 54 of an optical deflector 70 which is disposed on the optical path, as shown in FIG. 3 .
Meanwhile, a collimator lens unit 42 C, for making light of the light beam C parallel, is disposed on an optical path of the light beam C emitted from the light source portion 40 C. The light beam C that has passed through the collimator lens unit 42 C is deflected by the reflection mirror 44 , is incident at a slit plate 46 C and is incident on the half-mirror 48 disposed on the optical path. The half-mirror 48 divides the light beam C into a transmitted light beam C and a reflected light beam BC in a predetermined ratio. The light beam BC is reflected and is incident at the optical power monitor 50 . The light beam C that has been transmitted through the half-mirror 48 passes through a cylindrical lens 52 C and is incident at the polygon mirror 54 of the optical deflector 70 which is disposed on the optical path as shown in FIG. 3 .
Plural reflection mirror faces are provided at the polygon mirror 54 . As shown in FIG. 5 , the light beams C and K that are incident at the polygon mirror 54 are deflectingly reflected by the reflection mirror faces and enter f-θ lenses 56 and 58 . The polygon mirror 54 and the f-θ lenses 56 and 58 are of sizes which are capable of scanning the light beams C and K simultaneously.
The light beams for the two colors C and K which have passed through the f-θ lenses 56 and 58 are separated and are reflected at respective cylindrical mirrors 60 C and 60 K, which have power in a sub-scanning direction. The light beam K that has been reflected by the cylindrical mirror 60 K is doubled back to a reflection mirror 62 K, is then deflected by a cylindrical mirror 64 K and a reflection mirror 66 K, and is focused at the photosensitive drum 24 K to form an electrostatic latent image.
Meanwhile, the light beam C that has been reflected by the cylindrical mirror 60 C is doubled back to a reflection mirror 62 C, is then deflected by a cylindrical mirror 64 C, and is focused on the photosensitive drum 24 C to form an electrostatic latent image.
Thus, at the optical scanning device 28 CK (or 28 YM) of this exemplary embodiment, plural (two) different optical systems are provided in one of the housings 34 .
FIG. 6 shows the optical deflector 70 relating to this exemplary embodiment as described above. FIG. 7 shows a state in which the optical deflector 70 has been assembled to be accommodated inside the housing 34 of the optical scanning device 28 CK or the optical scanning device 28 YM.
This optical deflector 70 is a commercially available product (a general purpose component). As shown in FIG. 7 , a printed circuit board 72 , with a rectangular shape in plan view, is provided to serve as a base of the optical deflector 70 . The polygon mirror 54 , which rotates about an axis L, and a motor 74 , which drives to rotate the polygon mirror 54 , are disposed to be offset to one side relative to a central portion of the printed circuit board 72 . The polygon mirror 54 is made of aluminum and is formed in a polygonal column shape, and a mirror face is machined at the surface of each side of the polygon mirror 54 .
As shown in FIG. 6 , a driving IC 78 for controlling rotary driving of the polygon mirror 54 and the motor 74 is mounted toward the other side of an upper face of the printed circuit board 72 . A connector 76 , at which power source and signal cables are connected, is mounted at an end portion of this other side. The driving IC 78 is an electronic component in the form of a package, with a package portion 78 A being formed of a resin material.
A thermal storage member 80 is mounted at an upper face of the driving IC 78 , via an adhesion member 82 with high thermal conductivity, such as a thermally conductive adhesive agent, a thermally conductive adhesive tape or the like.
The thermal storage member 80 is fabricated of an aluminum alloy, is formed in a cuboid shape (a block shape) which is larger than the driving IC 78 , and has a larger thermal capacity than the package portion 78 A of the driving IC 78 . Further, because the thermal storage member 80 is formed in this cuboid shape, surfaces with planar form which are free of protrusions can be smoothly formed at all (six) faces thereof.
In the state in which the thermal storage member 80 has been mounted at the driving IC 78 , an upper face 80 A of the thermal storage member 80 is disposed at a lower side in an axial direction (the direction of arrow Z) relative to a lower face 54 A of the polygon mirror 54 , and a predetermined gap H is provided between the upper face 80 A and the lower face 54 A.
As shown in FIG. 6 , this optical deflector 70 is placed on a bottom face (an optical deflector mounting portion 84 ) of the housing 34 with a length direction of the printed circuit board 72 oriented in a width direction of the housing 34 (the direction of arrow W), and the optical deflector 70 is mounted by fixing the four corners of the printed circuit board 72 with four screws 86 . In this manner, the overall structure, including the driving IC 78 which is a heat-generating component, is accommodated in the housing 34 . Because the housing 34 is a resin-molded component and the optical deflector 70 employs an inexpensive general purpose component formed as a unit, costs of the optical scanning devices 28 YM and 28 CK of this exemplary embodiment are suppressed.
Next, operations of this exemplary embodiment will be described. After startup of the image forming apparatus 10 , when an image formation operation commences, at the optical deflector 70 , which is mounted at the optical deflector mounting portion 84 of the housing 34 of the optical scanning device 28 YM or 28 CK as described above, the two light beams emitted from the two light source portions 40 are incident on the polygon mirror 54 , and the two light beams are deflected for scanning by the polygon mirror 54 being rapidly rotated. Here, because two different optical systems are provided in the one housing 34 , directions and amounts of shifts (displacements) in reading registration differ due to differences in numbers of mirrors (particularly subsequent to the optical deflector 70 ), arrangements of optical components, and incidence angles of the light beams at the respective mirrors.
Herein, in a stage just after startup of operations, in which the driving IC 78 rises in temperature, heat generated from the driving IC 78 is absorbed at the thermal storage member 80 , via the adhesion member 82 , and is stored (heat sinking/thermal storage). Consequently, a temperature gradient is restrained such that the temperature increase is slowed. This thermal storage member 80 differs from, for example, a heat sink which is cooled to promote dissipation of heat from the driving IC 78 or the like. Because the thermal storage member 80 stores the absorbed heat, amounts of heat dissipated to air in the housing 34 from the thermal storage member 80 just after startup of the device are suppressed. As the amount of heat stored in the thermal storage member 80 increases and the temperature gradually rises, the heat is gradually released. Therefore, the temperature gradient of the temperature in the housing 34 is restrained such that the increase is gentler. Hence, positional shifts due to thermal effects on the optical systems disposed in the housing 34 are mitigated, and gradients of registration variations at scanning-object surfaces which are scanned by the light beams (the photosensitive drums 24 Y, 24 M, 24 C and 24 K) are moderated.
FIGS. 8 to 11 show comparative results of various measured values with and without the presence of the thermal storage member 80 . When the thermal storage member 80 is mounted at the driving IC 78 , then as shown in FIG. 8 , the temperature gradient of the driving IC 78 is made gentler, and accordingly, as shown in FIG. 9 , the temperature gradient of the housing 34 interior is made gentler. Hence, as shown in FIGS. 10 and 11 , gradients of color registration variations are also slowed, and color registration variations after corresponding amounts of time have passed can be substantially reduced by half.
Thus, with the above-described image forming apparatus 10 which is provided with the optical scanning devices 28 YM and 28 CK, it is possible, with a simple structure in which the thermal storage member 80 is mounted at the driving IC 78 of each optical deflector 70 , to suppress reading registration errors of respective colors that occur in the formation of color images just after startup of the device, and it is possible to form high-quality images.
Further, because the thermal storage member 80 of this exemplary embodiment is formed with smooth surfaces which are free of protrusions, a heat dissipation suppression effect of the thermal storage member 80 is enhanced, and it is possible to control the temperature gradient to further make the temperature increase inside the housing 34 gentler.
Further again, because the thermal capacity of the thermal storage member 80 is larger than that of the package portion 78 A of the driving IC 78 which is formed of a resin material, it is possible to adequately store heat dissipated from the surface of the driving IC 78 with the thermal storage member 80 , and it is possible to suppress conduction amounts (heat dissipation amounts) which are directly propagated to the air in the housing 34 from the driving IC 78 .
Further yet, when the polygon mirror 54 of the optical deflector 70 is driven by the motor 74 and rotates, air currents are generated in radial directions around the polygon mirror 54 . However, in this exemplary embodiment, because the upper face 80 A of the thermal storage member 80 mounted at the driving IC 78 is disposed at the axial direction lower side relative to the lower face 54 A of the polygon mirror 54 , amounts of airflow impinging on the thermal storage member 80 are kept small, and amounts of heat dissipated from the thermal storage member 80 are suppressed.
Further still, because the thermal storage member 80 is formed of an aluminum alloy, it is possible to fabricate a thermal storage member with small size and large thermal capacity at low cost. Furthermore, because molding, mechanical machining or the like thereof is simple, it is possible to fabricate the thermal storage member in a desired shape with ease.
Second Exemplary Embodiment
Next, a second exemplary embodiment of the present invention will be described. The second exemplary embodiment is a variant example in which a mounting structure of the thermal storage member is altered. Portions that are the same as in the first exemplary embodiment are assigned the same reference numerals and descriptions thereof are omitted, and only portions that differ from the first exemplary embodiment will be described.
As shown in FIG. 12 , a thermal storage member 90 relating to the second exemplary embodiment is provided with a leg portion 92 , which protrudes downward from an outer side end portion (a left side end portion in the drawing) of a lower face of the thermal storage member 90 . A plate-like fixing portion 94 protrudes to an outer side direction from a lower end portion of an outer side face of the leg portion 92 . Further, an unillustrated hole formed at a distal end portion of this leg portion 92 is fastened together with the optical deflector 70 by one of the screws 86 that fix the optical deflector 70 to the housing 34 . Thus, the thermal storage member 90 is in a state in which a lower face thereof is in contact with the upper face of the driving IC 78 , and the thermal storage member 90 is mounted on the driving IC 78 .
Thus, in this exemplary embodiment, because both the thermal storage member 90 and the optical deflector 70 are fixed using the screw 86 which is for fixing the optical deflector 70 to the housing 34 , the thermal storage member 90 is indirectly mounted at the driving IC 78 . Because fixing means constituted by such a screw member is utilized, it is possible to mount the thermal storage member 90 at the driving IC 78 simply and firmly. Further, in comparison with a structure for directly mounting a thermal storage member as in the first exemplary embodiment, it is possible to reduce loads that are applied to lead portions (solder portions) at the driving IC 78 which is formed as a package as in this exemplary embodiment. Moreover, because there is no need to interpose an adhesive member or the like between the driving IC 78 and the thermal storage member 90 , efficiency of thermal conduction from the driving IC 78 to the thermal storage member 90 is enhanced.
Third Exemplary Embodiment
Next, a third exemplary embodiment of the present invention will be described. The third exemplary embodiment is also a variant example in which the mounting structure of the thermal storage member is altered. Portions that are the same as in the first exemplary embodiment are assigned the same reference numerals and descriptions thereof are omitted, and only portions that differ from the first exemplary embodiment will be described.
As shown in FIG. 13 , a thermal storage member 100 relating to the third exemplary embodiment is provided with a pair of leg portions 102 , which protrude downward from end portions at two sides of a lower face of the thermal storage member 100 (left and right side end portions in the drawing). A protrusion-like fixing portion 104 protrudes to an outer side direction from a lower end portion of the outer face of each leg portion 102 . These fixing portions 104 are fixed with solder 106 to unillustrated copper foil lands which are formed at the upper face of the printed circuit board 72 . Thus, the thermal storage member 100 is also in a state in which a lower face thereof is in contact with the upper face of the driving IC 78 , and the thermal storage member 100 is mounted on the driving IC 78 .
Thus, in this exemplary embodiment, because the thermal storage member 100 is soldered to be fixed to the printed circuit board 72 of the optical deflector 70 , the thermal storage member 100 is indirectly mounted at the driving IC 78 . Because solder is employed thus, it is possible to mount the thermal storage member 100 at the driving IC 78 simply and robustly. Further, similarly to the second exemplary embodiment, it is possible to reduce loads that are applied to lead portions (solder portions) of the driving IC 78 and, because there is no need to interpose an adhesive member or the like between the driving IC 78 and the thermal storage member 100 , efficiency of thermal conduction from the driving IC 78 to the thermal storage member 100 can be enhanced.
Although in the foregoing embodiments, the present invention has been applied to color image forming apparatus, it is to be understood that the present invention is equally applicable to monochrome image forming apparatus.
Hereabove, specific embodiments of the present invention have been exemplified and described in detail. However, the present invention is not limited to these exemplary embodiments, and is to be understood as encompassing various changes and modifications which can be implemented without deviating from the appended claims. | An optical scanning device includes a light source that emits a light beam, an optical deflector at which a light beam emitted from the light source is incident, the optical deflector deflecting the incident light beam, an optical system that guides the deflected light beam to surface to be scanned by the deflected light beam, a driving device that drives at least a portion of the optical deflector, a thermal storage member mounted on the driving device, the thermal storage member absorbing and storing heat generated by the driving device, thereby controlling a temperature gradient of the driving device, and a casing body that accommodates the light source, the optical deflector, the optical system, the driving device, and the thermal storage member. | 6 |
FIELD OF THE INVENTION
[0001] The present invention pertains to a medical device used to extract foreign objects from a patient. More specifically, the invention relates to an endoscopic device used to retrieve, crush, and remove gallstones and the like. The device is designed to traverse through narrow passages within the body and to open within those passages to retrieve the foreign object.
BACKGROUND OF THE INVENTION
[0002] The removal of foreign bodies from patients often requires the use of endoscopic devices. In particular, gastroenterologists commonly use grasping or crushing devices to extract stones from a patient's biliary duct. Additionally, snares are often used when removing stents or other foreign objects.
[0003] Grasping and crushing devices generally take the form of wire baskets that deploy to capture the stone to be extracted. These wire baskets may be used for lithotripsy if the stone is too large to be removed intact. Lithotripsy involves crushing the stone into fragments to facilitate removal from the duct. Effective performance of such devices requires the baskets to have enough flexibility to be inserted into the common bile duct. However, the baskets also must have a certain degree of rigidity to dilate the duct to facilitate stone capture. Often, the baskets are deployed using a retaining cannula. In this case, the cannula retains the basket in a retracted configuration during insertion into the bile duct. Once within the grasping region of a stone, the basket extends from the cannula and opens to capture the stone. In such a case, the basket must have enough stiffness to open the duct when removed from the cannula, without being so stiff that it is permanently deformed due to retention within the cannula.
[0004] Aside from deformation associated with dilating the duct or retention within the cannula, a common failure of conventional baskets occurs during lithotripsy when the baskets are subject to forces often in excess of 50 pounds. Under such force, the basket can become severely deformed, rendering it unsuitable for repeated use. Such repeated use is desirable because of the frequent occurrence of the need to remove more than one stone or other object at a time from the patient. Therefore, design of these devices includes focus on the durability of the basket in repeated use settings.
[0005] To repeatedly crush and retrieve foreign objects, a basket must be flexible enough to traverse tortuous anatomy, yet stiff enough to open within a duct, and strong enough to crush stones. A single wire construction may meet any one of these criteria, but typically cannot meet all three requirements for repeated dilation and lithotripsy. It has been proposed, therefore, to construct a retrieval basket of a stranded cable, such as stainless steel cable. Purely stainless steel cable (the core and strands) may work well for the extraction of a single stone, but is subject to the deformation problems discussed previously when used for repeated dilatation or lithotripsy.
[0006] Other baskets are formed from cable which includes a superelastic, sometimes referred to as shape memory, core wrapped with strands of stainless steel to surround the core. Nitinol is often used as the superelastic core in these devices. Nitinol is a specially heat-treated Titanium-Nickel (Ti—Ni) alloy, preferably approximately 55%/45% Nickel to Titanium (Ni—Ti). These baskets require heat treatment for the core to retain its shape. Such a configuration allows for some improvement in performance when the baskets are used repeatedly and for lithotripsy because the superelastic core better retains its shape.
[0007] However, superelastic materials of this type experience phase transformations when subject to a certain level of stress loading. Lithotripsy often reaches these stress levels. Upon a phase transformation, the core of the cable stretches, rendering the device incapable of transferring force to the stone to complete the crushing process. Furthermore, the superelastic alloy has a greater reversible elongation than do the surrounding stainless steel strands. This results in a difference in deformation between the core and the surrounding strands leading to a permanent deformation of the cable. Such deformation results in an alteration of the basket shape, making it less desirable to use for its intended purpose.
[0008] Moreover, manufacturing both the cable core and strands from superelastic alloy wires results in a cable that unwinds due to the highly elastic nature of the material. Thus, a retrieval basket of such cable also will not retain its desired shape without heat treating.
SUMMARY OF THE INVENTION
[0009] The advantages and purpose of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages and purpose of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
[0010] To attain the advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, the invention includes a medical retrieval device for retrieving foreign objects from within a patient's body. The retrieval device includes a retrieval assembly containing a cable preformed into a configuration for capturing and removing the foreign object. The retrieval cable includes wire made of a precursor alloy to a superelastic material. According to a particularly preferred embodiment of the invention, the cable includes a core wire and surrounding wire strands, each made of the precursor alloy.
[0011] The invention further includes a method of manufacturing the medical retrieval device including the steps of constructing a cable including a wire made of a precursor alloy to a superelastic material and forming a retrieval assembly by preforming the cable into a configuration adapted to capture and remove the foreign objects.
[0012] The precursor alloy according to the present invention exhibits a stress-stain curve having a linear relationship extending through a yield point with no phase transformation point. After the yield point, the stress-strain curve does not exhibit a substantially constant stress plateau as strain increases. Rather, the precursor alloy exhibits plastic deformation properties.
[0013] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying- drawings, which are incorporated in and constitute a part of this specification, illustrate the preferred embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings,
[0015] FIG. 1 a is a stress-strain curve for a superelastic alloy;
[0016] FIG. 1 b is a stress-strain curve for a precursor alloy;
[0017] FIG. 2 a is a cross-sectional view of one embodiment of a stranding configuration according to the present invention, wherein a core of precursor alloy is surrounded by strands of stainless steel wires;
[0018] FIG. 2 b is a cross-sectional view of another embodiment of a stranding configuration according to the present invention, wherein a core of precursor alloy is surrounded by strands of precursor alloy wire; and
[0019] FIG. 3 is a wire basket retrieval device according to an embodiment of the present invention and in a deployed position for retrieving an object.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] The various aspects of this invention generally pertain to a device, and a method for manufacturing such a device, for retrieving foreign objects in a body from locations requiring traversal of narrow passages. In use, such a device must be able to collapse into a relatively narrow space for traversal purposes and to expand in that space for retrieval purposes. The device also must have strength characteristics so that the device can crush objects to facilitate capturing and removal. Additionally, the device must reconfigure to it original shape when expanded and retain its ability to reconfigure to the original shape for repeated deployments without losing strength and without suffering permanent deformation.
[0021] To accomplish these objectives and to overcome the problems associated with existing devices of this kind, a retrieval device of the present invention incorporates a precursor alloy into the stranded cable used for making the device. When subject to heat treatment, a precursor alloy results in the formation of a superelastic alloy. Prior to heat treatment, such a precursor alloy exhibits high elongation and a linear stress-strain relationship with a yield point. Because of these properties, the use of a precursor alloy in the manufacture of the device according to the present invention achieves greater strength, longer life, and ease in manufacture, as will be explained.
[0022] Unlike a superelastic alloy, a precursor alloy used in a medical retrieval device of the present invention exhibits a linear stress-strain relationship with a plastic yield point. For comparison purposes, schematics of the stress-strain curves for a superelastic alloy and a precursor alloy are shown in FIGS. 1 a and 1 b , respectively. As shown in FIG. 1 a , as a superelastic alloy undergoes increased stress, strain increases to phase transformation point X. At X, the superelastic alloy transforms from an austenitic phase to a martensitic phase. Thereafter, stress remains substantially constant as strain increases, forming a substantially constant stress plateau P. Upon releasing the stress on the superelastic alloy, the reversibly deformable nature of the material allows it to return to its original length following curve Y in the Figure. The cycle shown often occurs repeatedly with no appreciable change in dimension or plastic deformation of the wire. Therefore, the superelastic alloy withstands a relatively large strain prior to the phase transformation point, and additional strain during the phase transformation, without plastic deformation. Furthermore, the phase transformation and reversible deformation of the superelastic alloy occurs at relatively low stress levels. During the superelastic alloy phase transformation, applied stress is absorbed by the alloy to facilitate the phase transformation, and is not available to be transferred to another object, such as a stone.
[0023] A precursor alloy material exhibits the stress-strain characteristics shown in FIG. 1 b . Up to the plastic yield point Z, strain increases in a reversible manner as stress increases. That is, the precursor alloy returns to its normal configuration upon release of stresses prior to reaching plastic yield point Z. Moreover, the precursor alloy does not pass through a substantially constant stress plateau as does the superelastic alloy. At stresses above yield point Z, the precursor alloy becomes plastically and irreversibly deformed, unlike the superelastic alloy. As shown in FIGS. 1 a and 1 b , yield point Z of the precursor alloy generally occurs at higher stress levels than does phase transformation point X of the superelastic material. This enables the device of the present invention to transfer greater stress to stones during lithotripsy, as well as facilitating dilation of ducts. Accordingly, the inventive devices facilitate retrieval and removal, while maintaining shape and strength over repeated uses.
[0024] In addition to requiring heat treatment of the precursor alloy to produce the superelastic material, a conventional retrieval device also requires heat treatment during the formation of the basket so that the superelastic wires maintain their shape. In contrast, a result of the plastic yield point associated with a precursor alloy, the basket of the present device forms easily by mechanically bending the precursor alloy wire beyond its yield point and into shape. Sophisticated heat treatments are thus unnecessary in the manufacture of the inventive device.
[0025] Moreover, because of the superelastic nature of the heat-treated alloys used in conventional devices, a stranded cable made entirely of a superelastic material is ineffective due to phase transformation deformation and unwinding problems, as mentioned above. However, precursor alloys are highly elastic but also can be plastically deformed. Thus, in a preferred embodiment of the present invention, a cable for a retrieval device is made entirely of a precursor alloy core and precursor alloy strands. It is contemplated that the strands and the core can be made of identical precursor alloy or different precursor alloys. If different precursor alloys are used, it is preferred to select wire dimensions and types such that the wires exhibit similar deformations when subjected to a given load. In either case, the cable will experience neither unwinding nor excessive deformation as would a cable that includes superelastic strands. Furthermore, using a consistent material configuration for both the strands and the core would eliminate problems associated with elongation of the core relative to the surrounding strands leading to permanent damage to the basket. Finally, a cable made entirely of wires of the same precursor alloy material facilitates the manufacturing process.
[0026] Reference will now be made in detail to the present exemplary embodiments of the invention, examples of which are illustrated in FIGS. 2 and 3 . Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
[0027] In accordance with embodiments of the present invention, an endoscopic retrieval device 5 is formed from a stranded cable having the basic configuration shown in either FIG. 2 a or FIG. 2 b . FIG. 2 a shows a cross-section of cable of a first embodiment of the device 5 . A cable 1 includes a core monofilament wire 2 made of precursor alloy. Surrounding core wire 2 are strands 3 of stainless steel wire. Due to the presence of the precursor alloy core wire 2 , device 5 suffers from less deformation problems than does a conventional device of this type that includes a superelastic core. This is because, as previously discussed, precursor alloys exhibit less elongation than do superelastic materials and therefore differences in the elongation between surrounding strands 3 and core wire 2 will be minimized.
[0028] FIG. 2 b shows a more preferred embodiment of a stranded cable for use in the endoscopic retrieval device 5 . In this embodiment, a cable 1 ′ includes a core wire 2 ′ made of a precursor alloy, as in FIG. 2 a . However, surrounding strands 3 ′ in this embodiment also are formed of precursor alloy, either of identical or different precursor alloy material as core wire 2 ′. As discussed previously, this embodiment is preferred because the cables made entirely of precursor alloy wires (core and strands) will not unwind and are capable of transferring greater stress to objects without deforming. Additionally, cables made of entirely of the same precursor alloy alleviate deformation problems associated with different rates of elongation between the core and strands. When selecting wires of different precursor alloys, it is preferable to impart consistent mechanical properties to the cable. A person having ordinary skill in the art would realize that such consistency can be achieved by varying such factors as, for example, the nature of the alloys of the surrounding strands and core wire, relative dimensions of the core wire and the surrounding strands, the winding pattern of the strands around the core wire, and the post processing of the cable.
[0029] FIGS. 2 a and 2 b show six surrounding wire strands 3 and 3 ′, respectively. Preferably, there are at least five surrounding wire strands 3 or 3 ′. However, it is contemplated that the number of surrounding strands can be varied in accordance with the particular use for the device or the desired characteristics of the cable.
[0030] In both FIGS. 2 a and 2 b , the precursor alloy is in a martensitic phase at room temperature to body temperature. The precursor alloy can be a precursor Nitinol or other material exhibiting like properties and known to those having ordinary skill in the art. Such other precursor alloys that may be used include, for example, Silver-Cadmium, Gold-Cadmium, Gold-Copper-Zinc, Copper-Zinc, Copper-Zinc-Aluminum, Copper-Zinc-Tin, Copper-Zinc-Xenon, Iron-Beryllium, Iron-Platinum, Indium-Thallium, Iron-Manganese, Nickel-Titanium-Vanadium, Iron-Nickel-Titanium-Cobalt, and Copper-Tin.
[0031] In one preferred form of the invention, the overall diameter of the cable is approximately 0.017 inches. The materials used for the precursor alloy, the number of strands forming the cable, and the overall diameter of the cable can be modified according to the particular use or desired characteristics of the device. The selection of these parameters would be obvious to one having ordinary skill in the art.
[0032] FIG. 3 shows the overall construction of endoscopic retrieval device 5 . Typically, four cables 1 or 1 ′ form basket 6 . However, any number of cables can be used and would be obvious to one having ordinary skill in the art depending on the use or desired characteristics of the basket. A bullet-shaped nosepiece 7 can be attached to a distal end of device 5 to improve guidance of device 5 during use, as well as to secure cables 1 or 1 ′ to each other. A coupling tube 8 , attached to a proximal end of basket 6 , also facilitates manipulation of device 5 during the retrieval process. Coupling tube 8 also could take the form of a cannula, in which case basket 6 would retract into the cannula prior to retrieval.
[0033] Laser welding represents one preferred mode of attachment of bullet-shaped nosepiece 7 and coupling tube 8 to basket 6 . However, other suitable attachment methods known to those skilled in the art are within the scope of the present invention. Device 5 is used to traverse narrow passages to retrieve, crush, and remove foreign objects within the body. Device 5 can be deployed from a cannula or traverse independently through the body, collapsing and deploying as necessary. Device 5 also may be used repeatedly to retrieve, crush, and remove foreign objects.
[0034] The manufacture of device 5 first involves forming cables 1 , 1 ′. To form these cables, a precursor alloy wire is supplied as the core wire and surrounding strands of wire are placed approximately evenly-spaced around the perimeter of the core wire. Surrounding strands wrap around the core in an essentially helical fashion along its length. The strands can be wrapped clockwise, counterclockwise, or any combination thereof, depending on the desired properties of the cable. A preferred embodiment has strands wrapping clockwise around the core wire, similar to threads of a right-hand screw. The cable can then be rotary swaged, which helps to straighten it and increase its column strength. As discussed with reference to FIGS. 2 a and 2 b , the surrounding strands can be made of stainless steel, or other like, suitable material, or most preferably precursor alloy.
[0035] Several cables, preferably approximately four cables 1 or 1 ′, are then bent past the yield point of either the precursor alloy or stainless steel to form basket 6 . After forming basket 6 , cables 1 or 1 ′ are joined together at one end, through welding or other suitable joining method known to those skilled in the art. Laser welding cables 1 or 1 ′ to coupling tube 8 or, if desired, to the retractable portion of a retaining cannula, represents another method to connect and secure the cables to each other. As discussed with reference to FIG. 3 , a nosepiece can be laser welded, or otherwise attached in any suitable manner, to the end of basket 6 to guide device 5 through the body. It is important that during welding or other connecting operations involving heat, that temperature is controlled to prevent heat treating the cable such that the precursor alloys are converted to superelastic materials.
[0036] The stranded cable configuration used in the retrieval device according to the present invention provides the durability necessary to perform lithotripsy and dilation and be repeatedly employed for retrieval processes. Incorporating precursor alloy wire into the cable as opposed toga superelastic material such as Nitinol enables the device to be manufactured without heat treatment processes. Additionally, because precursor alloys do not exhibit the extreme elongation characteristic of superelastic materials, problems of permanent deformation are alleviated when surrounding stainless steel wire strands are used to form the cable. Using precursor alloys also allows for the manufacture of a cable comprised entirely of precursor alloy wire, including the surrounding strands and the core. Whether identical precursor alloy is used for both, or the precursor alloy used for the strands differs from that used for the core, the device will be capable of transferring greater stress to objects without deformation and will not unwind. Additionally, using the same precursor alloy for both the strands and the core facilitates overall manufacture of the device and provides a device of consistent characteristics that will not deform due to disparate elongation properties within the cables.
[0037] Although the use of a basket type retrieval device has been discussed and shown in the Figures, it is contemplated that the device can be of the snare type. A share made of the precursor alloys discussed above would retain its shape better than conventional stainless steel snare devices. Furthermore, although most of the above discussion pertains to using the inventive device to remove gallstones, it should be appreciated that the devices can be used for removing a variety of other foreign objects having various locations within the body.
[0038] It will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein that various modifications and variations can be made in the endoscopic retrieval device formed of precursor alloy cable of the present invention. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative examples shown and described in the specification. It is intended that departures may be made from such details without departing from the true spirit or scope of the general inventive concept as defined by the following claims and their equivalents. | A medical retrieval device for retrieving foreign objects from a patient and the method of constructing the device are disclosed. The device incorporates a wire cable composed of a precursor alloy to a superelastic material to improve durability of the device. Because precursor alloys exhibit a linear stress-strain relationship and a yield point associated with a relatively high stress level, the device transfers greater stresses before experiencing deformation. Thus, greater crushing forces can be achieved using a device of this type. These crushing forces may be needed when the foreign object is too large to remove intact. This property also facilitates the device in dilating ducts to retrieve foreign objects. Using the precursor alloy additionally eliminates the need for heat treatment of the cables used in constructing the device. A retrieval device made of precursor alloy cable also is less susceptible to permanent deformation and unwinding during use. | 0 |
This is a Continuation-in-Part of National Appln. No. 09/748,861 filed Dec. 28, 2000 abandoned.
FIELD OF THE INVENTION
The present invention relates to a system for cooling components which in use, experience high temperatures. The invention has particular efficacy in the gas turbine field, and may be incorporated in gas turbine engines of the kinds used to power aircraft or ships, or to pump oil overland.
BACKGROUND OF THE INVENTION
Air impingement cooling of gas turbine engine combustion equipment and other structures therein, is well known. However, known systems, wherein cooling air flowing over the surface of one member, passes through holes and crosses a gap, to impinge on a surface of an adjacent hot member, fail to achieve their full cooling potential. This is because the jet of air, on striking the surface of the hot member, spreads over the surface, effectively in a layer of constant thickness. It follows, that the outer portion of the layer never touches the hot member, and consequently, cannot make an efficient contribution to the cooling effect of the air flow.
A further drawback to known impingement cooling systems, is that, having impinged on the hot surface, and spread through 360° over the hot surface, the respective air flows collide with each other, and form a turbulent mix with poor heat transfer performance, and which sometimes displaces incoming air jets. Hot spots are thus formed.
SUMMARY OF THE INVENTION
The present invention seeks to provide an improved air impingement cooling system.
According to the present invention, an air impingement cooling system comprises superimposed, spaced apart members, one perforated, the other having a surface portion directly under each respective perforation, each said surface portion being of fluctuating shape, so as to cause air received thereby via respective perforations, and deflected laterally there across, to flow over said fluctuations, said fluctuating shape being such that the boundary layer of said air flow over said surface portion is caused to separate from said surface portion in the region of said fluctuations and subsequently reform downstream of said separation.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described, by way of example, and with reference to the accompanying drawings in which:
FIG. 1 is a diagrammatic view of a gas turbine engine having combustion equipment which incorporates the present invention.
FIGS. 2 to 6 are examples of alternative configurations of the present invention.
FIG. 7 is a view in the direction of arrow 7 in FIG. 6 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1. A gas turbine engine 10 has a compressor 12 , combustion equipment 14 , a turbine section 16 , and an exhaust nozzle 18 , all arranged in flow series in known manner. The operation of the gas turbine engine 10 is well known and will not therefore be described herein.
The combustion equipment comprises flame tubes 20 , surrounded by a casing 22 , which is spaced therefrom. The space is numbered 24 . Casing 22 is itself spaced from an outer engine casing 26 , that space being numbered 28 .
Space 28 is connected to receive a flow of air from compressor 12 , which air flows over the outer surface of casing 22 , some air thus by-passing the flame tubes 20 , the remainder passing through a large number of holes 19 in casing 20 (FIGS. 2-6) to impinge on the outer surface of respective flame tubes 20 , so as to cool them. The air is in the form of individual jets, numbered 30 . (FIGS. 2 - 6 ).
Referring to FIG. 2, in this example, when an air jet 30 strikes the outer surface portion of flame tube 20 which is directly under it, the air spreads laterally of the jet, over 360° across that surface portion, until it meets a barrier defined by wall 32 , which totally bounds the surface portion struck by and expanded over by the air jet, up to the limit where, without the presence of the wall 32 , the spreading flow would collide with those flows spreading from immediately adjacent jets. Thus, the wall 32 completely surrounds the surface portion as is the case in the FIGS. 3, 4 and 5 examples. Additionally, each surface portion bounded by a wall 32 is impinged by an air jet 30 from a single hole 19 the axis 21 of which intercepts the surface portion substantially at the center of each surface portion. Also, as shown in FIG. 2, the following dimensional relationships may be employed where d is the diameter of the hole 19 and h is distance from the casing 22 to the surface portion 34 bounded by the wall 32 which may slope at an angle α from the surface portion and the distance from the point of interception of the axis 21 of the hole 19 to the boundary wall 32 is L: L≧d; α≧30°; the height of the wall 32 should be≦0.3h.
On striking the wall 32 , the boundary layer of the cooling air flow, that is, the portion of the flow immediately adjacent the surface portion, separates from the surface portion in the region 34 . This causes mixing of the boundary layer and the remainder of the cooling air flow, before the boundary layer reforms and attaches itself to the wall. However the reformed boundary layer is cooler than the previous boundary layer due to this mixing and so provides more effective cooling of the wall 32 .
On perusal of FIGS. 2 to 5 , it will be clear to the expert in the field, that the wall 32 also provides parts of boundaries for those jets immediately surrounding the jet 30 , an example being depicted in FIG. 7, to which reference is made later in this specification.
Referring to FIG. 3 . in which like parts have like numbers. In this example, the centre of the portion bounded by wall 32 is provided with a cone 36 , the apex of which faces into the jet 30 . Such a shape defines a fluctuation in surface shape at its junction with the flame tube 20 outer surface. This fluctuation causes separation of the boundary layer flow in the region 38 . The separated boundary layer, which at this position is hotter than the remainder of the cooling air flow, mixes with, and is thereby cooled, by the remainder of the cooling air flow. A new, cooler and thinner boundary layer then forms which proceeds to flow towards the wall 32 , in turn providing more effective cooling of the outer surface of the flame tube 20 .
Referring to FIG. 4 . In this example, separation of the boundary layer of the cooling air flow is provided in the region 38 by the provision of a rising slope 42 in the surface portion. The separated boundary layer then mixes, and is therefore cooled, by the remainder of the cooling air flow before a new, cooler, boundary layer is formed which flows towards the wall 32 .
Referring to FIG. 5 . This example combines the cone 36 of FIG. 3 with the rising slope 42 of FIG. 4, and produces, in the one arrangement, boundary layer separation which occurs in the regions 34 , 38 and 44 , thereby providing more efficient cooling.
Referring to FIG. 6 . This example utilises the rising slope 42 of FIG. 4, but not the boundary wall 32 thereof. Instead, the rising slope 42 of FIG. 6 meets rising slopes eg 42 a and 42 b of adjacent surface portions, which features are more clearly seen in FIG. 7 . The advantages accrued by the arrangement depicted in FIG. 6 are reduction in weight, and at least a reduction in turbulence, when opposing, spreading air flows meet, by virtue of the flows already having a small directional component, which will serve to generate a resultant direction of flow of the collided air flows, in parallel with the jets.
Referring now to FIG. 7 . When opposing, spreading air flows collide, they tend to form a barrier which approximates a straight line. Thus, ridges 46 represent that line, one such ridge 46 lying between the heads of respective groups of arrows 48 and 50 , which in turn, represent colliding air flows. From this, it will be appreciated that each impingement surface is bounded by a plurality of straight lines which, in the present example, define a pentagon.
However, in practice of the present invention, the actual number of straight lines and therefore, the shape defined, will be dependant on the number of perforations 19 in casing 20 (not shown in FIG. 7) and the pattern in which they are drilled.
Boundaries of circular shape (not shown) may be provided, but the resulting interstices of solid metal would add weight. If they were to be machined out, cut-outs would have to be made in the boundary edges, so as to allow spreading cooling air to flow into the resulting pockets.
The cone 36 in both FIG. 3 and FIG. 5 may be of circular form in cross section. Alternatively, it could be multi-faceted e.g. pyramid-like. | Where gas turbine engine structure eg combustion equipment, is to be air impingement cooled, the surface which receives the air jets is so shaped as to produce boundary layer separation zones 34, 38 and 44 in the cooling air, as it spreads across the surface. Mixing of the boundary layer with the remainder of the air flow results, followed by the re-establishment of the boundary layer. The new boundary layer is cooler than the original layer and so provides more effective cooling. | 5 |
TECHNICAL FIELD
[0001] The present application relates to radio frequency identification (RFID) label applicators, and more particularly, to a RFID label applicator capable of programming RFID labels, detecting defective RFID labels and rejecting the defective RFID labels.
BACKGROUND INFORMATION
[0002] Radio frequency identification (RFID) systems are generally known and may be used for a number of applications such as managing inventory, electronic access control, security systems, automatic identification of cars on toll roads, and electronic article surveillance (EAS). RFID devices may be used to track or monitor the location and/or status of articles or items to which the RFID devices are applied. A RFID system typically comprises a RFID reader and a RFID device such as a tag or label. The RFID reader may transmit a radio-frequency carrier signal to the RFID device. The RFID device may respond to the carrier signal with a data signal encoded with information stored on the RFID device. RFID devices may store information such as a unique identifier or Electronic Product Code (EPC) associated with the article or item.
[0003] RFID devices may be programmed (e.g., with the appropriate EPC) and applied to the article or item that is being tracked or monitored. A RFID reader/programmer may be used to program RFID devices and to detect defective RFID devices. Label applicators have been used to apply programmed RFID labels to items or articles.
[0004] Existing RFID applicators, however, have encountered problems in handling defective labels. In existing RFID applicators, a RFID reader/programmer may be located upstream from the applicator. One problem occurs when tracking a defective label from the point at which it is detected to the point at which it can be rejected. Because of potential differences in the RFID label footprints and web paths through the applicator, the number of labels between the point of detection and the point of rejection may be inconsistent. As a result of this inconsistency, an applicator may reject a good label and may apply a defective label to the product.
[0005] Another problem is that the rejection of defective RFID labels may interrupt the label application process and may result in labels not being applied to items or products. When a defective label is detected using conventional techniques, it may be removed from the process and another label may be re-encoded in its place. Each defective label that is encountered may cut the product application rate by up to an additional 50%. Product lines may need to be run slower so as not to miss a product in the event a defective label is detected.
SUMMARY OF THE INVENTION
[0006] The invention relates to an RFID label applicator. Embodiments of the invention may include a peeler member having a peel end, the peeler member being configured to cause an RFID label to peel away from a web when the web passes around the peel end; and a label tamp assembly having a receiving surface configured to receive the RFID label and to move it into contact with an item on which the RFID label is to be applied, the label tamp assembly having at least one forward opening in a portion of the receiving surface away from the peeler member and a plurality of rearward openings in a portion of the receiving surface proximate the peeler member, wherein at least one of the forward or rearward openings is configured to draw in air such that a leading portion of the RFID label is substantially secured.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The subject matter regarded as the embodiments is particularly pointed out and distinctly claimed in the concluding portion of the specification. The embodiments, however, both as to organization and method of operation, together with objects, features, and advantages thereof, may best be understood by reference to the following detailed description when read with the accompanying drawings in which:
[0008] FIG. 1 is a diagrammatic view of a RFID applicator, consistent with one embodiment of the invention.
[0009] FIG. 2 is a side cross-sectional view of one embodiment of a RFID label that can be used in the RFID applicator, consistent with one embodiment of the invention.
[0010] FIG. 3 is a side view of one embodiment of a RFID applicator peeler member with an integrated RFID programming antenna.
[0011] FIGS. 4A-4C are side views of one embodiment of a label reject assembly in various positions with respect to a RFID applicator peeler member for use in a RFID applicator.
[0012] FIGS. 5A and 5B are side views of another embodiment of a label reject assembly integrated into a RFID applicator peeler member for use in a RFID applicator.
[0013] FIG. 6A is a side view of one embodiment of a label tamp assembly.
[0014] FIG. 6B is a top view of the label tamp assembly shown in FIG. 6A .
[0015] FIG. 7A is a bottom view of one embodiment of a vacuum tamp pad that may be used in a label tamp assembly.
[0016] FIG. 7B is a cross-section view of the vacuum tamp pad shown in FIG. 7A taken along line A-A.
[0017] FIG. 7C is a side view of the vacuum tamp pad shown in FIG. 7A .
[0018] FIG. 8A is a side view of another embodiment of a vacuum tamp pad for use in a RFID applicator.
[0019] FIG. 8B is a bottom view of the vacuum tamp pad shown in FIG. 8A .
DETAILED DESCRIPTION
[0020] Numerous specific details may be set forth herein to provide a thorough understanding of the embodiments of the disclosure. It will be understood by those skilled in the art, however, that various embodiments of the disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components and circuits have not been described in detail so as not to obscure the various embodiments of the disclosure. It can be appreciated that the specific structural and functional details disclosed herein are representative and do not necessarily limit the scope of the disclosure.
[0021] It is worthy to note that any reference in the specification to “one embodiment” or “an embodiment” according to the present disclosure means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
[0022] Referring to FIG. 1 , radio frequency identification (RFID) label applicator 100 , consistent with embodiments of the invention, may be used to apply RFID labels 102 to articles or items 104 . The RFID label applicator 100 may also be used to program RFID labels 102 , to detect defective RFID labels, and to reject the defective labels such that the defective labels are not applied to the items 104 . The articles or items 104 may be products, merchandise, or any other items or articles that may be monitored using RFID techniques.
[0023] The RFID labels 102 may be removably secured to a backing material or web 110 such that the RFID labels 102 are supported on the web 110 during programming and may be removed (e.g., peeled away from the web 110 ) for application. The web 110 supporting the labels 102 may be rolled onto a roll 112 , which is unwound to allow the web 110 to pass through the label applicator 100 . After the RFID labels 102 are removed or rejected, scrap web 110 a may be rewound onto a rewind roll 114 .
[0024] One embodiment of the RFID label applicator 100 may include a web feeding mechanism 120 to feed the web 110 , a RFID programming system 130 to program the RFID labels 102 , a peeler member 140 to peel the RFID labels 102 from the web 110 , a label tamp assembly 150 to apply the RFID labels 102 to the items 104 , and a label reject assembly 160 to reject RFID labels. The RFID label applicator 100 may also include an applicator controller 170 to control operation of the RFID label applicator 100 . The articles or items 104 may be arranged in a line (e.g., a product line) and may be moved, for example, using a conveyor 180 or other similar mechanism. Components in the applicator 100 may be mounted or secured to an applicator frame 108 .
[0025] The RFID label applicator 100 may also include other components not shown in FIG. 1 . Examples of additional components include, but are not limited to, a label sensor to sense and position the labels 102 relative to the RFID programming system 130 , an item sensor to sense and position the items 104 relative to the tamp assembly 150 , and an integrated printer to print indicia on the labels 102 . One example of a label sensor includes a thru-beam that shines a light from beneath the web to a light sensor 110 positioned above the web 110 .
[0026] The web feeding mechanism 120 may include a tensioning roller 122 and an idler roller 124 , which guide the web 110 with the RFID labels 102 to the peeler member 140 . The web feeding mechanism 120 may also include a drive and nip roller assembly 126 that takes up the scrap web 110 a and feeds the scrap web 110 a to the web rewind roll 114 . The drive and nip roller assembly 126 may be driven to pull the scrap web 110 a , thereby causing the web 110 with the RFID labels 102 to pass around the peeler member 140 . The unwind roll 112 and/or rewind roll 114 may also be driven (e.g., with servomotors) to facilitate unwinding of the web 110 and/or rewinding the scrap web 110 a.
[0027] The RFID programming system 130 may include a RFID reader/programmer coupled to one or more RFID programming antennas, as will be described in greater detail below. The RFID programming system 130 may include any RFID reader/programmer known to those skilled in the art for reading and/or programming RFID devices, such as the type known as the Sensormatic® SensorID™ Agile 2 Reader available from Tyco Fire and Security. The RFID programming system 130 may also be capable of detecting defective RFID labels, for example, by attempting to read a RFID label after applying programming signals.
[0028] The peeler member 140 may include a peel tip 142 having a radius and forming an angle such that a RFID label 102 peels away from the web 110 as the web 110 passes around the peel tip 142 . In one embodiment, the radius of the peel tip 142 may be in a range of about 0.030 in. and the angle formed by the peel tip 142 may be in a range of about 90° or less. Other radii and angles are within the scope of the invention and may depend upon the adhesion properties (e.g., the adhesion strength) of the RFID labels 102 on the web 110 . The peeler member 140 may be made of a rigid material such as aluminum. In one embodiment, the peeler member 140 may be in the form of a plate or a bar, although those skilled in the art will recognize other shapes and configurations.
[0029] The label tamp assembly 150 may include a tamp pad 152 coupled to a tamp driving mechanism 154 . The tamp pad 152 contacts the non-adhering side of a RFID label 102 a that has been removed from the web 110 and holds the RFID label 102 a . The tamp driving mechanism 154 drives the tamp pad 152 and the RFID label 102 a toward the item 104 to which the RFID label 102 a is to be applied. One embodiment of the tamp assembly 150 uses a vacuum pressure to retain the RFID label 102 a in contact with the tamp pad 152 . The vacuum pressure may be released and/or air may be blown from the tamp pad 152 to facilitate application of the RFID label 102 a . Although one embodiment of a label tamp assembly 150 is described herein, the label tamp assembly 150 may include any structure or mechanism for moving a label into contact with an item 104 .
[0030] The label reject assembly 160 may include an accumulation pad 162 coupled to a label reject driving mechanism 164 . Upon determining that a RFID label 102 is to be rejected, the reject driving mechanism 164 drives the accumulation pad 162 into the path of the tamp pad 152 . The tamp pad 152 then applies the rejected RFID label to the accumulation pad 162 instead of the item 104 . A RFID label may be rejected when the label is determined to be defective or for other reasons. Although one embodiment of the label reject assembly 160 is described herein, the label reject assembly 160 may include any structure for intercepting or otherwise preventing a RFID label from being applied to an item 104 .
[0031] The tamp driving mechanism 154 and the label reject driving mechanism 164 may include pneumatic actuated air cylinders, such as the type available from PHD, Inc. When air cylinders are used as the driving mechanisms, the RFID label applicator 100 may also include one or more air pressure gauges 168 to monitor and/or adjust operation of the air cylinders, as is known to those skilled in the art. Although the described embodiment uses air cylinders and rods, those skilled in the art will recognize that other linear actuators or driving mechanisms may be used.
[0032] The applicator controller 170 may be a programmable logic controller (PLC), such as the type available from Allen-Bradley, Omron or Mitsubishi, or a general purpose computer, such as a PC, programmed to control one or more operations of the applicator 100 . The controller 170 may be coupled to the web feeding mechanism 120 (e.g., to the motors, sensors, etc.) to control the feeding of the web 110 around the peeler member 140 and/or to control the positioning of the RFID labels 102 relative to the RFID programming system 130 . The controller 170 may also be coupled to the tamp assembly 150 to control application (or tamping) of programmed and removed RFID labels to the items 104 . The controller 170 may also be coupled to the label reject assembly 160 to control the rejection of labels, for example, when the label is determined to be defective. The controller 170 may also be coupled to a user interface/control panel 172 to enable a user to monitor the application process and/or to provide commands and/or operating parameters to the controller 170 .
[0033] The controller 170 and/or user interface 172 may also be coupled to the RFID programming system 130 to control the RFID programming operations. RFID programming operations may be controlled, for example, by allocating Electronic Product Codes (EPC's) and/or other data to be sent to the RFID labels 102 upon receiving an indication that the RFID labels 102 are properly positioned relative to the RFID programming system 130 . The controller 170 may also monitor the detection of defective labels to control the label reject assembly 160 . The controller 170 may further collect programming data and statistics and provide such data to the user.
[0034] According to one method of operation, the web 110 may be advanced around the peeler member 140 , for example, by using the drive and nip roller assembly 126 to pull the web 110 . As the web 110 is advanced, the unwind roll 112 unwinds the web 110 supporting the RFID labels 102 and the rewind roll 114 rewinds the scrap web 110 a after the RFID labels 102 have been applied or rejected. When each RFID label 102 on the web 110 is positioned within a programming range of the RFID programming system 130 , the RFID programming system 130 may program the RFID label 102 by transmitting radio frequency (RF) programming signals to the RFID label 102 and attempting to read the RFID label 102 . The RFID label 102 may then be advanced around the peel tip 142 of the peeler member 140 to remove the RFID label 102 . A removed RFID label 102 a may then be applied to an item 104 using the tamp assembly 150 or may be rejected using the label reject assembly 160 . These operations may be repeated for each of the RFID labels 102 on the web 110 and the items 104 may be advanced such that programmed RFID labels 102 are applied to each of the items 104 .
[0035] One embodiment of a RFID label 102 is shown in greater detail in FIG. 2 . The RFID label 102 may include an integrated circuit (IC) chip 202 coupled to an antenna 204 . The IC chip 202 and antenna 204 may be sandwiched between one or more layers or substrates, such as an adhesive substrate 206 and a printable layer 208 . The adhesive substrate 206 may include a scrim coated on each side with an adhesive, such as an acrylic based adhesive. The printable layer 208 may be made of a thermal transfer paper or other material suitable for printing. One or more additional layers or substrates may also be incorporated into the RFID label 102 , as is known to those skilled in the art. The web 110 may be made of a paper with a release agent such as wax or silicone to allow the RFID label 102 to peel away from the web 110 . The RFID label 102 may have a peel adhesion strength (e.g., about 15 N/inch) that allows the RFID label 102 to be removably adhered to the web 110 and later adhered to the items 104 . Although RFID labels may have various sizes, one example of the RFID label 102 may be about 3 in. by 3 in. and supported on a web 110 having a width of about 4 in.
[0036] One example of a RFID label 102 is the “Combo EAS/RFID Label or Tag” disclosed in U.S. Provisional Patent Application Ser. No. 60/628,303, which is fully incorporated herein by reference. Other examples include the RFID labels commercially available under the name Sensormatic® from Tyco Fire and Security. Those skilled in the art will recognize that the RFID label 102 may include any RFID device capable of being adhered or otherwise secured to articles or items.
[0037] Referring to FIG. 3 , one embodiment of a peeler member 140 a is described in greater detail. The peeler member 140 a may include a RFID programming antenna 132 integrated with the peeler member 140 and connected to a RFID reader/programmer 134 . Each RFID label 102 may thus be programmed and verified just before peeling the label and transferring the label to the tamp pad 152 (see FIG. 1 ). The proximity of the RFID programming antenna 132 to the peel tip 142 allows each defective RFID label to be handled immediately (i.e., without having to track defective labels from a point of detection to a point of application further downstream), which may ensure that defective labels are subject to rejection and programmed labels are applied to items.
[0038] According to one embodiment, the RFID programming antenna 132 may be a near-field probe such as the type disclosed in U.S. Provisional Patent Application Ser. No. 60/624,402, which is fully incorporated herein by reference. The programming range of a near-field probe is generally the near-field zone of the antenna or probe. The near field probe may be implemented by enhancing the magnitude of the induction field within the near-near field zone associated with an antenna structure and decreasing the magnitude of the radiation field within the far-field zone associated with the antenna structure. One embodiment of the near field probe may include a stripline antenna terminated into a 50 ohm chip resistor. In one example, the near field probe may have an operating frequency of 915 MHz and the near-field zone may be approximately 5 cm from the probe. One example of the probe may be about 2 to 3 in. long, although those skilled in the art will recognize that smaller probes may be used to allow programming of labels that are smaller and/or spaced closer together on the web.
[0039] This embodiment of the peeler member 140 a may include a cavity 302 in a body portion 304 of the peeler member 140 a , which is configured to receive the RFID programming antenna 132 . A cover 306 may be used to cover the cavity 302 . The cover 306 may be made of, or at least coated with, a non-reflective material that will not reflect or absorb the radio frequency waves transmitted by the RFID programming antenna 132 and the RFID device antenna 204 . For example, the cover 306 may be made of a plastic material such as the type available under the name Delrin™. A cable 308 may connect the RFID programming antenna 132 to the RFID reader/programmer 134 . The cable 308 may extend from the RFID programming antenna 132 through one side 310 of the body portion 304 of the peeler member 140 a.
[0040] The RFID programming antenna 132 may be positioned within the cavity 302 such that the RFID programming antenna 132 transmits radio frequency (RF) programming signals to a RFID label 102 b positioned over the RFID programming antenna 132 (i.e., within the programming range). The cavity 302 may include an adjustment region 312 that allows the RFID programming antenna 132 to be adjusted laterally within the cavity 302 to accommodate different sizes of labels. For example, the RFID programming antenna 132 may be configured initially to align with the IC in labels having a certain size (e.g., 3 in. by 3 in.) and may need to be adjusted laterally for labels that are smaller or larger. In one example, the lateral adjustment of a probe having a length of about 2 to 3 in. may be in a range of about 1 to 1.5 inches in either direction. An adjustment mechanism, such as a bar or rod 320 , may be coupled to the RFID programming antenna 132 to provide mechanical adjustment.
[0041] Although the described embodiment shows the RFID programming antenna 132 located inside of the cavity 302 in the peeler member 140 a , the RFID programming antenna 132 may also be integrated with the peeler member 140 a in other ways. For example, the RFID programming antenna 132 may be mounted anywhere such that an RFID label 102 b on the peeler member 140 a is within the programming range (e.g., the near field) of the programming antenna 132 .
[0042] According to one method of programming RFID labels, the web 110 may be advanced along the peeler member 140 a until a RFID label 102 b is positioned within a programming range of the RFID programming antenna 132 . The RFID label 102 b may be positioned, for example, by stopping advancement of the web 110 when a label sensor (not shown) senses an edge of the RFID label 102 b . When positioned, RF programming signals may be transmitted to the RFID label 102 b from the RFID programming antenna 132 . RF signals may also be transmitted from the RFID label 102 b to the RFID programming antenna 132 in an attempt to read and validate the RFID label 102 b . If the RFID label 102 b cannot be read or validated, the RFID reader/programmer 134 may indicate that the RFID label 102 b is defective. After the RFID label 102 b is either programmed or determined to be defective, the web 110 is advanced along the peeler member 140 a until the next RFID label 102 is located in the programming range of the RFID programming antenna 132 .
[0043] A programmed RFID label 102 a may be subsequently removed as the web 110 supporting the programmed RFID label 102 a passes around the peel tip 142 . In this described embodiment, the programmed RFID label 102 a is removed when the next RFID label 102 b is positioned in the programming range. The next RFID label 102 b may be programmed after the programmed RFID label 102 a is applied to an item or may be programmed while the programmed RFID label 102 a is applied to an item.
[0044] Referring to FIGS. 4A-4C , one embodiment of the label reject assembly 160 is described in greater detail. The accumulation pad 162 may include at least a substrate that is sufficiently rigid to receive and adhere to a rejected RFID label applied by the tamp pad 152 . The reject driving mechanism 164 may be mounted in any location that enables the accumulation pad 162 to be driven into a path 400 of the tamp apply stroke (i.e., between the tamp pad 152 and the item 104 ) and then withdrawn such that the tamp pad 152 will clear the accumulation pad 162 and the rejected label(s) on the accumulation pad 162 .
[0045] The accumulation pad 162 may be configured to receive multiple rejected RFID labels stacked on previous rejected labels. The accumulation pad 162 may also be configured to receive rejected labels adjacent to other rejected labels (e.g., multiple adjacent stacks). The accumulation pad 162 may be sized according to the size of the labels and the manner in which the labels are accumulated (e.g., one stack or adjacent stacks) on the accumulation pad. For example, an accumulation pad 162 may have a size that is capable of adhering to and receiving at least one label or may have a size that is capable of receiving multiple adjacent stacks of labels.
[0046] The accumulation pad 162 may include a low surface energy medium, such as polytetrafluoroethylene, at least on the surface of the accumulation pad 162 , which allows the accumulated RFID label(s) to be easily removed by peeling away the. bottom label. The accumulation pad 162 may also include a removable layer, such as an index card material, to allow the accumulated RFID label(s) to be removed.
[0047] According to one method of rejecting RFID labels, the RFID labels 102 on the web 110 maybe programmed prior to passing the web 110 around the peel tip 142 of the peeler member 140 , for example, as described above. Programming the RFID labels may include detecting any defective RFID labels that should be rejected. A RFID label 102 a that is properly programmed may be removed and applied to an item ( FIGS. 4A and 4B ). Upon detecting a defective RFID label 102 c , the label accumulation pad 162 may be extended from a retracted position ( FIGS. 4A and 4B ) to an extended position ( FIG. 4C ) into the path 400 between the tamp pad 152 and the item 104 . In the extended position, the label accumulation pad 162 prevents a full tamp apply stroke down to the item 104 and thus intercepts the rejected RFID label 102 c before the rejected RFID label 102 c is applied to an item 104 . The tamp pad 152 may apply the rejected RFID label 102 c to the accumulation pad 162 in the same manner as applying labels to items 104 , as described in greater detail below. The accumulation pad 162 with the rejected RFID label(s) 102 c applied thereto may then be retracted and normal label application may continue.
[0048] The accumulation pad 162 may also be extended to different positions within the path 400 of the tamp apply stroke such that labels are received on the accumulation pad 162 adjacent to other labels. The controller 170 may control the reject driving mechanism 164 to control positioning of the accumulation pad 162 such that labels are positioned in an organized fashion (e.g., spread evenly) on the accumulation pad 162 .
[0049] The accumulated rejected RFID labels may be removed from the accumulation pad 162 after a number of rejected labels accumulate on the accumulation pad 162 . The number of accumulated rejected labels may be monitored. According to one method, a numeric reject number may be printed (e.g., using an integrated printer) on the surface of a rejected label 102 c and a reject label counter (e.g., in the controller 170 ) may be incremented. The controller 170 may provide an indication to the user as to when the accumulated labels should be removed. When the stack of accumulated labels is removed, the last numeric reject number on the top accumulated label will signify the sum of the accumulated labels in the stack, for customer recording purposes.
[0050] In one embodiment, about twenty (20) to thirty (30) labels may be accumulated on the accumulation pad 162 before removing the labels. One embodiment of the RFID label applicator 100 may have a label programming failure rate of about 5%. In other words, about 5 out of every 100 RFID labels may be rejected as defective, which allows about 400 to 600 RFID labels to be applied before the stack of accumulated labels is removed. The label reject assembly 160 thus allows labels, such as defective RFID labels, to be rejected (i.e., not applied to an item 104 ) with minimal or no interruption to the label application process. Alternatively, a rejected RFID label may be removed from the accumulation pad 162 after each rejected label is intercepted by the accumulation pad 162 .
[0051] An alternative embodiment of a label reject assembly may include the extendable path altering mechanism 500 shown in FIGS. 5A and 5B . The extendable path altering mechanism 500 is extendable from a retracted position ( FIG. 5A ) to an extended position ( FIG. 5B ). In the extended position, the extendable path altering mechanism 500 may alter a path of the web 110 around the peel tip 142 , effectively enlarging the radius of the peel tip 142 . As a result, a rejected RFID label 102 d passing around the peel tip 142 does not peel away from the web 110 and continues moving with the scrap web 110 a instead of being applied to an item. Rejected RFID labels, such as defective RFID labels, may thus be handled automatically with minimal or no effect on the application process.
[0052] The extendable path altering mechanism 500 may include an extendable tip 502 coupled to a tip driving mechanism 504 . The extendable tip 502 may be rounded with a larger radius than the peel tip 142 . In one example, the radius of the extendable tip 502 may be in a range of about 0.25 to 0.5 in. The extendable tip 502 may be made of plastic, aluminum or other suitable material that allows the web 110 to slide around the extendable tip 502 . The tip driving mechanism 504 may include a pneumatic actuated air cylinder, although those skilled in the art will recognize that other linear actuators or driving mechanisms may be used.
[0053] In one embodiment, the extendable path altering mechanism 500 may be integrated with another embodiment of the peeler member 140 b . The peeler member 140 b may include a cavity 510 for receiving the extendable path altering mechanism 500 . Alternatively, the extendable path altering mechanism 500 may be located adjacent to the peeler member 140 b as long as the extendable tip 502 can extend to alter the path of the web 110 in a manner that will prevent a label from peeling away. The peeler member 140 b may also include the RFID programming antenna 132 integrated with the peeler member 140 b , for example, as described above.
[0054] According to one method of rejecting RFID labels using the extendable path altering mechanism 500 , a RFID label 102 b on the web 110 may be programmed prior to passing the RFID label around the peel tip 142 of the peeler member 140 b , for example, using the integrated RFID programming antenna 132 . Programming the RFID label 102 b may include detecting whether or not the RFID label 102 b is defective, e.g., by attempting to read information programmed thereon. A RFID label 102 a that is properly programmed is caused to peel away from the web 110 as the web 110 and the RFID label 102 a passes around the peel tip 142 of the peeler member 140 b . Upon detecting a defective RFID label 102 d , the path of the web 110 around the peel tip 142 may be altered using the extendable path altering mechanism 500 , for example, by extending the extendable tip 502 beyond the peeler tip 142 . When the extendable tip 502 is extended, the web 110 may be advanced to position the next RFID label 102 for programming and/or application and the rejected RFID label 102 d passes around the extendable tip 502 and remains on the scrap web 110 a instead of being applied to the tamp pad 152 . The extendable tip 502 may then be retracted and normal label application may continue.
[0055] To allow the path of the web 110 to be altered, the tension in the web 110 may be released such that the scrap web 110 a unwinds and the position of the RFID label 102 b can be maintained on the peeler member 140 b . The tension in the web 110 may be released, for example, by releasing a torque brake on a motor driving the web rewind roll and/or releasing the drive and nip roller assembly.
[0056] Referring to FIGS. 6A and 6B , another embodiment of the tamp assembly 150 a is described in greater detail. The tamp assembly 150 a may include a vacuum tamp pad 600 coupled to an air manifold 602 . The vacuum pad 600 may include one or more vacuum holes 610 extending through the vacuum pad 600 to a label contacting side 612 . The manifold 602 may include an inlet/outlet 620 and at least one air chamber 622 located over the vacuum holes 610 in the vacuum pad 600 . The inlet/outlet 620 may be coupled to an air supply or compressor, which may be switched between compressed air and a vacuum. When a vacuum is applied, air may be drawn through the inlet/outlet 620 and the chamber 622 in the manifold 602 , which causes air to be drawn through the vacuum holes 610 in the vacuum pad 600 . As a result, a vacuum pressure is generated around the vacuum holes 602 on the label contacting side 612 of the vacuum pad 600 , which is sufficient to hold the label 102 against the vacuum pad 600 .
[0057] As shown in FIGS. 7A-7C , the vacuum tamp pad 600 may include slots or channels 614 extending along the label contacting side 612 to promote air discharge when the vacuum is drawn. The slots or channels 614 may also provide for less friction against a label when transferring the label to the tamp pad 600 (e.g., in the label feed direction 604 ). The vacuum tamp pad 600 may also include a relief area 616 configured to receive the portion of the RFID label with the IC chip. The relief area 616 protects the IC chip from stresses due to abrasion during label transfer to the pad 600 and protects the IC chip from compressive stresses during tamp placement of the RFID label onto an item or product. The vacuum tamp pad 600 may further include a chamfer 618 at a leading edge 617 of the vacuum tamp pad 600 to promote easy label transfer to the tamp pad 600 , as the label moves in the label feed direction 604 from the peeler member.
[0058] The embodiment of the vacuum tamp pad 600 shown in FIGS. 7A-7C is designed for a 3 in.×3 in. RFID label. For this example, the vacuum pad 600 may have a length l of about 3.125 in., a width w of about 3.00 in. and a thickness t of about 0.25 in. The tamp pad 600 may be made of a plastic material, such as the type available under the name Delrin, or other suitable materials.
[0059] This described embodiment of the vacuum pad 600 includes four (4) vacuum holes 610 a - 610 d . The vacuum holes 610 a - 610 d may be located to minimize the effect of label bow or curl and to allow each of the vacuum holes 610 a - 610 d to be sealed regardless of the amount of label bow, thereby effectively holding the label on the vacuum pad 600 . For example, the holes 610 a and 610 c may be located in from the leading edge 617 about ¼ of the length of the vacuum pad 600 and the holes 610 b and 610 d may be located in from the leading edge 617 about ¾ of the length of the vacuum pad 600 . The holes 610 a and 610 b may be located in from the side edge 619 about ⅓ of the length of the vacuum pad 600 and the holes 610 c and 610 d may be located in from the side edge 619 about ⅔ of the length of the pad 600 . The holes 610 a - 610 d may have a diameter of about 0.093″.
[0060] The vacuum pad 600 and/or manifold 602 may be mounted to a mounting block 630 with one or more compression springs 632 positioned therebetween ( FIG. 6A ). The compression springs 632 may compress as needed when the vacuum tamp pad 600 contacts a product, allowing the tamp pad 600 to mate parallel with a surface of an item or product to which a label is being applied. The mounting block 630 may include tapered holes 634 that receive shoulder bolts 636 , which secure the compression springs 632 and allow the compression springs 632 to compress. Although the described embodiment shows four (4) compression springs 632 , any number of compression springs may be used to provide the desired compression, as may be determined by one of ordinary skill in the art.
[0061] A proximity sensor 640 may also be mounted to the manifold 602 or to the vacuum tamp pad 600 to detect the surface of the item or product to which the label is to be applied. The proximity sensor 640 may thus enable consistent compression of the compression springs 632 when labels are being applied to items or products having surfaces at different levels.
[0062] The tamp assembly 150 may also include a cylinder 650 , such as a pneumatic actuated air cylinder, and rod 652 for providing the linear driving force. A cylinder mounting block 654 may be used to mount the mounting block 630 to the rod 652 . Those skilled in the art will recognize that other linear actuators or driving mechanisms may also be used.
[0063] According to an alternative embodiment, shown in FIGS. 8A and 8B , a vacuum tamp pad 800 may include only three vacuum holes 810 a - 810 c . A manifold 802 with an inlet/outlet 820 may be coupled to the tamp pad 800 to cause air to pass through the vacuum holes 810 a - 810 c . The vacuum holes 810 a - 810 c may be positioned such that the leading portion of a RFID label 102 is secured by the vacuum force when the RFID label 102 is properly positioned. The trailing portion of the RFID label 102 may be left free (i.e., not subject to a vacuum) to relieve bow in the label 102 . The vacuum hole 810 c near the far edge of the RFID label 102 may act as a label stop. The vacuum holes 810 a - 810 c thus take into account the natural bow that is inherent to RFID labels that are provided in roll format.
[0064] A fixed stop 808 may be positioned adjacent the vacuum pad 800 to allow the label to feed (i.e., in the feed direction 804 ) and orient properly. When the RFID label 102 is being fed to the side of an item (e.g., a box) at a 90 degree angle relative to a vertical plane (i.e., sideways), the fixed stop 808 may prevent a gravity force 806 from misaligning the RFID label 102 with respect to the vacuum pad 800 . The fixed stop 808 may be fixed (e.g., bolted) to a bottom side of the tamp driving mechanism or cylinder.
[0065] The vacuum holes 810 a - 810 c may also be positioned to hold the RFID label 102 in place without subjecting the IC chip 202 in the RFID label 102 to vacuum forces at the holes 810 a - 810 c . The vacuum pad 800 may also be recessed (not shown) in the area receiving the IC chip 202 to provide additional relief. The vacuum pad 800 may also include a compressible material, to avoid damage to the IC chip 202 in the RFID label 102 .
[0066] While the principles of the invention have been described herein, it is to be understood by those skilled in the art that this description is made only by way of example and not as a limitation as to the scope of the invention. Other embodiments are contemplated within the scope of the invention in addition to the embodiments shown and described herein. Modifications and substitutions by one of ordinary skill in the art are considered to be within the scope of the invention, which is not to be limited except by the following claims. | The invention relates to an RFID label applicator ( 100 ) may include a peeler member ( 140 ) having a peel end ( 142 ), the peeler member being configured to cause an RFID label ( 102 ) to peel away from a web ( 110 ) when the web passes around the peel end; and a label tamp assembly ( 150 ) having a receiving surface ( 612 ) configured to receive the RFID label and to move it into contact with an item ( 104 ) on which the RFID label is to be applied, the label tamp assembly having at least one forward opening in a portion of the receiving surface away from the peeler member and a plurality of rearward openings in a portion of the receiving surface proximate the peeler member, wherein at least one of the forward or rearward openings is configured to draw in air such that a leading portion of the RFID label is substantially secured. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of copending provisional application serial No. 60/408,169, filed on Sep. 3, 2002.
FIELD OF THE INVENTION
[0002] This invention relates to a solvent extraction process for the recovery of metals from aqueous solutions.
BACKGROUND OF THE INVENTION
[0003] Solvent extraction is a widely used technology for the recovery of metals from aqueous solutions containing the metals.
[0004] One of the more common staging configurations in metal recovery is two extraction stages in combination with two strip stages for a total of four stages.
SUMMARY OF THE INVENTION
[0005] It has now been discovered that a staging arrangement employing three countercurrent extraction stages with one strip stage is more effective for the recovery of metal than the currently used staging arrangement of two extraction stages and two strip stages.
[0006] This new staging arrangement gives both higher metal recovery and more effective use of the organic phase and the metal extraction reagents present therein when the staging arrangements are compared under the exact same conditions.
[0007] Moreover, the present invention does not increase capital costs since the total number of stages and the size of the plants are exactly the same in both staging arrangements.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] [0008]FIG. 1 shows a known staging arrangement in which two extraction stages are present in combination with two stripping stages.
[0009] [0009]FIG. 2 shows the staging arrangement of the invention in which three extraction stages are present in combination with one strip stage.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term “about”.
[0011] It should be noted that the present invention is not dependent on the particular metals present in the electrolyte solutions from which the metals are to be extracted. Also, different leach solutions can be used with respect to the metal ores. For example, nickel ores are typically leached with ammonia, extracted from the ammonia solutions, and stripped with acid to form an aqueous acidic electrolyte solution used in an electrowinning step.
[0012] The solvent extraction process (SX process) for extracting metals such as copper typically involves the following steps, (plus a wash stage), which result in electrolyte solutions used in electrowinning copper metal. Other processes that include solvent extraction and stripping can be employed in accordance with the invention with other metals such as nickel, zinc and the like to produce an electrolyte from which their respective metals are electrowon:
[0013] 1. Aqueous acid leaching of copper ore using a strong acid to form an aqueous acid leach solution containing copper ions and often relatively small quantities of other metal ions. The aqueous leach acid solution dissolves salts of copper and other metals if present as it is contacted with the ore, e.g. as it trickles through the ore. The metal values are usually leached with aqueous sulfuric acid, producing a leach solution having a pH of 0.9 to 2.0.
[0014] 2. The copper-pregnant aqueous acid leach solution is mixed in tanks with an oxime extraction reagent which is dissolved in a water-immiscible organic solvent, e.g., a kerosene or other hydrocarbons. The reagent includes the oxime extractant which selectively forms a metal-extractant complex with the copper ions in preference to ions of other metals. The step of forming the complex is called the extraction or loading stage of the solvent extraction process. The oxime extractants used in this step are typically oxime extractants of the hydroxyl aryl ketone oxime or hydroxy aryl aldoxime type, or a mixture thereof. Alkylated aryl hydroxyoximes such as alkylated acetophenone oximes and/or alkylated salicylaldoximes can be used e.g. 5-nonyl-2-hydroxy-acetophenone oxime and/or 5-nonyl-salicylaldoxime.
[0015] 3. The outlet of the mixer tank can continuously feed to a large settling tank or equivalent equipment, where the organic solvent (organic phase), now containing the copper-extractant complex in solution, is separated from the partially depleted aqueous acid leach solution (aqueous phase). This part of the process is called phase separation. However, the tanks used in step 2 can be mixer/settler tanks so that step 3 is not required.
[0016] 4. After extraction, the partially depleted aqueous acid leach solution (raffinate) is either recycled for further leaching, or recycled with a bleed, or discharged.
[0017] 5. The loaded organic phase containing the dissolved copper-extractant complex is fed to another mixer tank, preferably a stripper/settler tank, where it is mixed with an aqueous strip solution of more concentrated sulfuric acid. The highly acid strip solution breaks apart the copper-extractant complex and permits the purified copper to pass and concentrate in the strip aqueous phase. The process of breaking the copper-extractant complex is called the stripping stage.
[0018] 6. As in the extraction process described above (steps 2 and 3), the mixture of stripped organic phase and copper pregnant aqueous acid strip solution can be fed to another settler tank for phase separation, or to another type of solvent extraction equipment that replaces the traditional stripper/settler tank. However, phase separation preferably takes place in the stripper/settler tank in step 5.
[0019] 7. From the stripper/settler tank, the regenerated stripped organic phase is recycled to the extraction mixer to begin extraction again, and the copper is recovered from the strip aqueous phase, customarily by feeding the strip aqueous phase to an electrowinning tankhouse, where the copper metal values are deposited on plates by a process of electrodeposition.
[0020] 8. After recovering the copper values from the aqueous solution by electrodeposition, the solution, known as spent electrolyte, is returned to the stripping mixer to begin stripping again.
[0021] In the known process, set forth schematically in FIG. 1, Leach Solution from step 1 above enters Extraction Stage 1 where it is mixed with Organic (the water-immiscible organic solvent containing the oxime extraction reagent) from Extraction Stage 2. Loaded Organic (which is the organic solvent containing the copper-extractant complex in solution) exits Extraction Stage 1 and is sent to Strip Stage 1, where it is contacted with Electrolyte (aqueous acid strip solution) from Strip Stage 2. Pregnant electrolyte (containing the copper) is removed for use in electrowinning the copper. Organic (containing the oxime extraction reagent and remaining copper-extractant complex) exits Strip Stage 1 and enters Strip Stage 2, where it is contacted with Barren Electrolyte (strip electrolyte) for further stripping of copper from the remaining copper-extractant complex. Stripped Organic containing the oxime extractant is sent to Extraction Stage 2 where Aqueous (leach solution still containing some copper in solution) from Extraction Stage 1 is further extracted. Aqueous Raffinate (depleted aqueous acid leach solution) is removed from Extraction Stage 2.
[0022] In the process of the present invention, set forth schematically in FIG. 2, Leach Solution enters Extraction Stage 1, where it is mixed with Organic from Extraction Stage 2. Loaded Organic exits Extraction Stage 1 and enters the Strip Stage where it is contacted with Barren Electrolyte. Pregnant Electrolyte exits the Strip Stage for further processing by electrowinning. Stripped Organic leaves the Strip Stage and enters Extraction Stage 3, where it is contacted with Aqueous (partially extracted leach solution) from Extraction Stage 2. Aqueous Raffinate is removed from Extraction Stage 3. Organic from Extraction Stage 3 is sent to Extraction Stage 2, where it is contacted with Aqueous from Extraction Stage 1.
[0023] In the circuit configuration of the invention, it is to be understood that the circuit configuration shown in FIG. 2 can be used in one or more trains, depending on the size of the plant. Also, the circuit configuration shown in FIG. 2 can be used with one or more wash stages, preferably a single wash stage.
[0024] The invention will be illustrated but not limited by the following examples.
EXAMPLES
Example 1
[0025] This example compares a copper solvent extraction circuit having 2 extraction stages and 2 stripping stages (2E, 2S) with a copper solvent extraction circuit having 3 extraction stages and 1 strip stage (3E, 1 S). An extraction isotherm was generated using an organic solution 0.296 molar in 5-nonyl-2-hydroxyacetophenone oxime (ketoxime) and 0.0964 molar in 5-nonylsalicylaldoxime (aldoxime) in a hydrocarbon diluent. The aqueous copper leach solution contained 6.36 g/l Cu and 150 g/l sulfate ion as sodium sulfate at a pH of 1.67. The above organic solution was first contacted several times with an aqueous solution having about 39 g/l Cu and 168 g/l sulfuric acid to obtain a preliminary stripped organic phase containing 1.37 g/l Cu. This preliminary stripped organic phase was then contacted vigorously with the copper leach solution at various organic to aqueous (O/A) ratios for sufficient time to obtain equilibrium. The resulting equilibrated organic phases were analyzed by atomic absorption for copper and iron while the resulting equilibrium aqueous phases were analyzed by atomic absorption for copper only. The results are given in Table 1 below.
TABLE 1 Approximate Aqueous Phase Organic Phase O/A ratio g/l Cu g/l Cu ppm Fe 10 0.17 1.98 1.0 5 0.20 2.56 3.2 2 0.42 4.27 3.1 1.5 0.53 4.99 2.6 1 0.90 6.61 2.1 0.5 2.24 9.40 1.7 0.2 4.30 11.51 1.1
[0026] The isotherm data was inserted into the Cognis Corporation Isocalc computer program which predicts with great accuracy the results that can be obtained in a continuous copper solvent extraction plant provided correct mixer efficiencies for the extraction stages are used. For this Example 1, the following mixer efficiencies were used: 95 % for traction stage 2 and 92% for extraction stage 1 in the 2E, 2S circuit and 95 % for extraction stage 3, 92% for extraction stage 2 and 89% for extraction stage one in the 3E, 1S circuit. These mixer efficiencies are consistent with mixer efficiencies that are obtained in the 2E, 2S circuit and which can be obtained in a 3E, 1S circuit of the invention in modern copper solvent extraction plants. The stripped organic values that were used in the Cognis Isocalc computer program were obtained by equilibrating the organic with an aqueous solution to give a copper stripped organic value circuit is representative for either one or two stripping stages depending on the particular circuit simulation. In this example two sets of stripping conditions were used. In the first set of results the barren stripping solution had 35 g/l Cu and 180 g/l sulfuric acid building to a pregnant strip solution of about 50 g/l Cu and 157 g/l sulfuric acid. In the second set of results the barren stripping solution had 35 g/l Cu and 150 g/l sulfuric acid building to a pregnant strip solution of about 50 g/l Cu and 127 g/l sulfuric acid. Simulated circuits were run with the computer program at various advance organic/aqueous (O/A) ratios to compare the results obtained with 3 extraction and 1 stripping stage verses the results obtained with 2 extraction and 2 stripping stages.
[0027] The results of the computer simulations are shown below in Table 2.
TABLE 2 Strip Organic g/l Advance O/A Copper Net Transfer Set Staging Cu extraction Recovery g/l Cu/Vol % 1a 2E, 2S 1.42 1.0 95.0% 0.276 1b 2E, 2S 1.42 0.71 90.2% 0.369 1c 2E, 2S 1.42 0.63 86.8% 0.40 1d 3E, 1S 2.16 1.0 96.6% 0.28 1e 3E, 1S 2.16 0.63 90.7% 0.418 2a 2E, 2S 1.83 1.0 94.1% 0.273 2b 2E, 2S 1.83 0.76 90.2% 0.345 2c 2E, 2S 1.83 0.70 88.2% 0.366 2d 3E, 1S 2.84 1.0 95.2% 0.276 2e 3E, 1S 2.84 0.70 90.7% 0.376
[0028] As can be seen from this example a circuit having 3 extraction and 1 strip stage will result in higher copper recovery than a circuit having 2 extraction and 2 strip stages when the circuits are compared under exactly the same conditions. For example compare 1 d (96.6% Cu recovery) with 1 a (95.0% Cu recovery) and 1 e (90.7% Cu recovery) with 1 c (86.8% Cu recovery). Also compare 2d (95.2% Cu recovery) with 2a (94.1% Cu recovery) and 2e (90.7% Cu recovery) with 2c (88.2% Cu recovery). In addition note that the Net Transfer (g/l Cu/vol %) of the reagent is higher in the 3E, 1S staging than in the comparable 2E, 2S staging, showing that the reagent is used more efficiently in the 3E, 1 S staging than in the 2E, 2S staging.
[0029] When taken in the context of large modern copper solvent extraction plants a 1% increase in copper recovery can add substantial revenue. For example consider a copper solvent extraction plant producing 100,000 tons of copper annually. An extra 1% recovery results in an additional 1,000 tons of copper which has a value of about US $1.5 million at a copper price of US $1500 ton. An additional 4% copper recovery adds US $6 million in revenue.
[0030] A second aspect of the 3E, 1 S stage configuration that is a favorable over the 2E, 2S stage configuration is enhanced copper over iron (Cu/Fe) selectivity. This can be noted by comparing the Cu/Fe transfer for the loaded organic for some of the 2E, 2S sets with the Cu/Fe transfer for the loaded organic for similar 3E, 1 S sets. First the iron loading on the organic phase for each isotherm point is plotted against the copper loading for the same point. This gives a graph that can be used to find the iron loading of the organic phase for any copper loading of the same organic phase. For the sets in Table 2 the copper content of the loaded organic is obtained from the computer simulated circuit run and then the iron loading for that copper loaded organic can be obtained from the graph of iron loading against copper loading. This data for some of the sets in Table 2 is given in Table 3.
TABLE 3 Loaded Advance Copper Stripped Organic Cu/Fe O/A Re- Organic ppm Selec- Set Staging Extraction covery g/l Cu g/l Cu Fe tivity 1a 2E, 2S 1.0 95.0% 1.42 7.46 1.98 3050 1c 2E, 2S 0.63 86.8% 1.42 10.18 1.50 5840 1d 3E, 1S 1.0 96.5% 2.16 8.30 1.85 3320 1e 3E, 1S 0.63 90.7% 2.16 11.32 1.17 7830 2a 2E, 2S 1.0 94.1% 1.83 7.81 1.95 3070 2c 2E, 2S 0.7 88.2% 1.83 9.84 1.60 5010 2d 3E, 1S 1.0 95.2% 2.84 8.89 1.80 3360 2e 3E, 1S 0.7 90.7% 2.84 11.08 1.25 6600
[0031] The Cu/Fe selectivity is calculated as follows. The copper transfer of the organic phase is divided by the iron loading of the loaded organic phase [(Loaded Organic Cu—Stripped Organic Cu)/Loaded Organic Fe]. The data in Table 3 shows that for any set of comparable conditions the 3E, 1S stage configuration shows better copper/iron (Cu/Fe) selectivity than the 2E, 2S stage configuration. For example compare set 1 a with set 1 d , set 1 c with set 1 e , set 2a with set 2d and set 2c with set 2e. The higher Cu/Fe selectivity of the 3E, 1 S stage configuration over the 2E, 2S stage configuration provides an added advantage for the 3E, 1 S staging configuration over the 2E, 2S configuration.
Example 2
[0032] In a manner similar to Example 1, Example 2 also compares a copper solvent extraction circuit having 2 extraction stages and 2 stripping stages (2E, 2S) with a copper solvent extraction circuit having 3 extraction stages and 1 strip stage (3E, 1 S). In this case the copper content of the leach solution was 61.37 g/l Cu at a pH of 1.8. This leach solution is representative of a concentrate leach solution. Two extraction isotherms were generated, one with 32 volume % LIX 84-I in a hydrocarbon diluent and one with 32 volume % LIX 984N reagent in a hydrocarbon diluent. LIX 84-I is a copper solvent extraction reagent available from Cognis Corporation of Gulph Mills, Pa., whose active copper extractant is 5-nonyl-2-hydroxyacetophenone oxime at a concentration of 1.54 molar. LIX 984N is a copper solvent extraction reagent available from Cognis Corporation whose active extractants are 5-nonyl-2-hydroxyacetophenone oxime (0.77 molar) and 5-nonylsalicylaldoxime (0.88 molar). The respective organic solutions were contacted vigorously with the copper leach solution at various organic to aqueous (O/A) ratios for sufficient time to obtain equilibrium. The resulting equilibrated organic phase and aqueous phases were analyzed by atomic absorption for copper. The results are set forth in Table 4 below.
TABLE 4 32 V/V % LIX 984N Approximate 32 V/V % LIX 84-I Organic O/A ratio Aqueous g/l Cu Organic g/l Cu Aqueous g/l Cu g/l Cu 20 13.16 2.46 3.56 3.00 10 18.64 4.38 7.41 5.67 5 25.08 7.31 14.91 9.56 3 31.66 9.85 24.21 12.64 2 36.33 11.61 31.49 14.65 1 45.97 14.40 43.41 16.80 2/3 51.62 16.15 50.88 17.77 1/2 54.37 16.54 53.87 18.12 1/3 56.52 16.76 56.08 18.27
[0033] In a manner similar to that described in Example 1, the isotherm data for each reagent in Table 4 was inserted into the Cognis Isocalc computer modeling program to predict with good accuracy the copper recovery expected in a continuous copper solvent extraction circuit when using the respective reagents at 32 volume % to treat the concentrate leach solution of this example. The following mixer efficiencies were used: 98% for extraction stage 2 and 95% for extraction stage 1 in the 2E, 2S circuits and 98% for extraction stage 3, 96% for extraction stage 2 and 95% for extraction stage one in the 3E, 1 S circuits. These mixer efficiencies are consistent with mixer efficiencies that are obtained in the 2E, 2S circuit and which can be obtained in a 3E, 1 S circuit of the invention in modern copper solvent extraction plants operating at temperatures of about 35° C. which is the temperature at which concentrate leach solutions will enter the copper solvent extraction plant. The stripped organic values that were used in the computer modeled circuit for LIX 84-I are consistent with stripped organic values that are obtained in operating copper solvent extraction plants when the barren strip solution has 30 g/l Cu and 168 g/l sulfuric acid and the pregnant strip solution has about 45 g/l Cu and 146 g/l sulfuric acid. The stripped organic values that were used for LIX 984N are consistent with the stripped organic values that are obtained in a plant when the barren strip solution has 35 g/l Cu and 180 g/l acid and the pregnant strip solution has 45 g/l Cu and 165 g/l sulfuric acid.
[0034] The results of the computer simulations are shown below in Table 5.
TABLE 5 Strip Advance Copper Net Transfer Organic O/A Re- g/l Cu/Vol Set Reagent Staging g/l Cu extraction covery % 1a LIX 84-I 2E, 2S 0.88 4.0 67.2% 0.321 1b LIX 84-I 3E, 1S 1.33 3.2 67.3% 0.404 2a LIX 984N 2E, 2S 3.61 4.63 80.0% 0.331 2b LIX 984N 3E, 1S 4.73 4.09 80.0% 0.375
[0035] In sets 1 a and 1 b the objective was to obtain about 67% copper recovery. It can be noted that the organic flow rate needed to obtain the desired copper recovery with the 2E, 2S staging (set 1 a ) is about 25% greater than the flow rate needed to obtain the same copper recovery with set 1 b (the 3E, 1 S staging) [(4.0-3.2)/3.2×100%]. This means that the mixer/settler tanks in a plant using the 2E, 2S staging would have to be 25% larger in size than the mixer/settler tanks in a plant using the 3E, 1staging. Thus a plant with 2E, 2S staging would have a higher capital cost by about 25% which is quite significant. For example, the cost to install a mixer/settler tank is about US $400 per square foot of settler area on a fully prepared site. Considering that large modern copper solvent extraction plants might have settlers that are 90 feet long and 90 feet wide, a single mixer settler unit of this size would cost about US $3.24 million without considering site preparation costs. If each mixer settler unit needed to be 25% larger the cost would be 4.05 million dollars per mixer settler unit giving a total increase in capital for the 2E, 2S stage configuration of US $3.24 million over the 3E, 1 S stage configuration.
[0036] If the site preparation costs are high, and they often are because of the location of copper plants, the savings for the smaller 3E, 1 S plant will be even greater.
[0037] In sets 2a and 2b, the objective was to recover 80% of the copper. It can be seen that the organic flow needed to obtain 80% copper recovery with the 2E, 2S staging is about 13.2% greater than the organic flow needed to obtain 80% copper recovery with the 3E, 1S staging [(4.63-4.09/4.09)×100%]. This means that the mixer/settler tanks in a plant with the 2E, 2S staging would need to be about 13.2% larger then the mixer/settler tanks needed for a plant with 3E, 1S staging. Again this would result in a significant capital savings for the 3E, 1S configuration.
[0038] In both set 1 and set 2 of this Example 2, the copper net transfer of the reagent is greater for the 3E, 1 S staging over the comparable 2E-2S staging. This shows that the reagent is used more effectively in a plant having 3E, 1 S staging when compared to a plant having 2E, 2S staging.
Example 3
[0039] In a manner similar to Examples 1 and 2, this Example 3 compares a copper solvent extraction circuit having 2 extraction stages and 2 stripping stages (2E, 2S) with a copper solvent extraction circuit having 3 extraction and 1 strip stage (3E, 1 S). In this example the copper content of the leach solution is 4.57 g/l Cu at a pH of 1.8. This leach solution is representative of heap leach solutions commonly found in copper heap leaching operations. An extraction isotherm was generated with a solution of 0.225 molar 5-nonyl-2-hydroxyacetophenone oxime in a hydrocarbon diluent. The respective organic solution was contacted vigorously with the copper leach solution at various organic to aqueous (O/A) ratios for sufficient time to obtain equilibrium.
[0040] The resulting equilibrated organic phases and aqueous phases were analyzed by atomic absorption for copper. The results are given in Table 6 below.
TABLE 6 Approximate O/A ratio Aqueous Phase g/l Cu Organic Phase g/l Cu 10 0.039 0.481 5 0.08 0.945 3 0.14 1.56 2 0.22 2.31 1.5 0.31 3.01 1 0.52 4.3 0.67 0.98 5.74 0.5 1.49 6.59 0.2 3.15 7.70
[0041] In a manner similar to that described in Examples 1 and 2 the isotherm data in Table 6 was inserted into the Cognis Isocalc computer modeling program to predict with good accuracy the copper recovery expected in a continuous copper solvent extraction circuit when using the organic solution of this example. The following mixer efficiencies were used: 94% for extraction stage 2 and 90% for extraction stage 1 in the 2E, 2S circuits and 95% for extraction stage 3, 91% for extraction stage 2 and 88% for extraction stage one in the 3E, 1S circuits. These mixer efficiencies are consistent with mixer efficiencies obtained for 2E, 2S circuits and which can be obtained in a 3A, 1S circuit in modern commercial copper solvent extraction plants using a reagent of this type operating at temperatures of about 22° C. which is a common temperature for heap leach solutions entering a copper solvent extraction plant. The stripped organic values that were used in the computer modeling program are consistent with stripped organic values that are obtained in operating copper solvent extractions plants when the barren strip solution has 35 g/l Cu and 180 g/l acid and the pregnant strip solution has 50 g/l Cu and 157 g/l sulfuric acid.
[0042] The results of the computer simulation are shown in Table 7 below.
TABLE 7 Strip Advance Copper Net Transfer Organic O/A Re- g/l Cu/Vol Set Reagent Staging g/l Cu extraction covery % 1a LIX 84-I 2E, 2S 0.31 0.645 90.1% 0.437 1b LIX 84-I 2E, 2S 0.31 0.85 95.0% 0.35 2a LIX 84-I 3E, 1S 0.56 0.573 90.1% 0.49 2b LIX 84-I 3E, 1S 0.56 0.64 95.1% 0.465
[0043] In sets 1 a and 2a the objective was to obtain about 90% copper recovery. It should be noted that the organic flow rate needed to obtain the desired copper recovery with the 2E, 2S staging (set 1 a ) is about 12.5% greater than the flow rate needed to obtain the same copper recovery with set 2a (the 3E, 1S staging) [(0.645-0.573)/0.573×100%]. This means that the reagent in the 3E, 1 S stage configuration is about 12.5% more efficient than that same reagent in 2E, 2S stage configuration. The increased net transfer of the reagent in the 3E, 1S staging also shows that the reagent is more efficient with 3E, 1 S staging when compared to the 2E, 2S staging.
[0044] In sets 1 b and 2b the objective was to obtain about 95% copper recovery. It should be noted that the organic flow rate needed to obtain the desired copper recovery with the 2E, 2S staging (set 1 a) is about 32.8% greater than the flow rate needed to obtain the same copper recovery with set 2a (the 3E, 1 S staging) [(0.85−0.64)/0.64×100%]. In this case the efficiency of the organic phase in the 3E, 1S stage configuration is about 32.8% greater than the efficiency of the same organic phase in a 2E, 2S stage configuration. The much higher net transfer of the reagent in set 2b compared to set 1 b confirms the higher efficiency of the 3E, 1S stage configuration.
[0045] In a plant with 2 extraction stages and 2 strip stages, a design that has been used commonly in the past, running under the conditions of set 1 a achieving 90.1% copper recovery which is a copper recovery that is often the basis for the design of copper solvent extraction plants, a simple change in the piping of the plant to a 3E, 1S configuration would allow the plant to achieve 95.1% copper recovery with all other conditions being the same (set 2b).
Example 4
[0046] In a manner similar to the previous examples, this example compares a copper solvent extraction circuit having 2 extraction stages and 2 stripping stages (2E, 2S) with a copper solvent extraction circuit having 3 extraction and 1 strip stage (3E, 1 S). In this Example 4 the leach solution has 5.97 g/l Cu, 2.7 g/l Fe at a pH of 2.0. The organic solution contained about 0.194 molar 5-nonyl-2-hydroxyacetophenone oxime, about 0.189 molar 5-nonylsalicylaldoxime and about 28.2 g/l of the equilibrium modifier dodecanone all in the hydrocarbon diluent SHELLSOL™ D70. The respective organic solution was contacted vigorously with the copper leach solution at various organic to aqueous (O/A) ratios for sufficient time to obtain equilibrium. The resulting equilibrated organic phases were analyzed for copper and iron while the aqueous phases were analyzed for copper. Analysis was by atomic absorption. The results are given in Table 8 below.
TABLE 8 Approximate Aqueous Phase Organic Phase O/A ratio g/l Cu g/l Cu ppm Fe 1.5 0.21 4.25 — 1 0.42 6.11 8.6 2/3 1.00 8.31 4.6 0.5 1.70 9.51 3.2 1/3 2.87 10.52 2.6 0.25 3.62 10.97 2.5 1/6 4.41 11.28 2.6 1/8 4.78 11.51 2.8 1/10 5.03 11.55 3.0
[0047] In a manner similar to that described in Examples 1-3 above, the isotherm data in Table 8 was inserted into the Cognis Isocalc computer modeling program to predict with good accuracy the copper recovery expected in a continuous copper solvent extraction circuit when using the organic solution of this Example 4. The following mixer efficiencies were used: 94% for extraction stage 2 and 90% for extraction stage 1 in the 2E, 2S circuits and 95% for extraction stage 3, 91% for extraction stage 2 and 88% for extraction stage one in the 3E, 1 S circuits. These mixer efficiencies are consistent with mixer efficiencies for 2E, 2S circuits and which can be obtained in a 3E, 1S circuit in modern copper solvent extraction plants using a reagent of this type operating at a temperature of about 22° C. The stripped organic values that were used in the computer modeled circuit are consistent with stripped organic values that are obtained in operating copper solvent extraction plants when the barren strip solution has 35 g/l Cu and 180 g/l acid and the pregnant strip solution has 50 g/l Cu and 157 g/l sulfuric acid. The results of the computer simulations are shown in Table 9.
TABLE 9 Strip Organic Advance O/A Copper Net Transfer Set Staging g/l Cu extraction Recovery g/l Cu/Vol % 1a 2E, 2S 1.95 1.0 96.2% 0.267 1b 3E, 1S 2.57 1.0 97.7% 0.271 2a 2E, 2S 1.95 0.68 91.0% 0.372 2b 3E, 1S 2.57 0.68 94.9% 0.387
[0048] In sets 1 a and 1 b the objective was to predict the copper recovery for the respective stage configuration when the advance organic/aqueous (O/A) flow across extraction is 1.0. It should be noted that the circuit having a 3E, 1S stage configuration achieves a higher copper recovery than the circuit having a 2E, 2S stage configuration.
[0049] In sets 2a and 2b the objective was to compare the 2E, 2S stage configuration with the 3E, 1 S stage configuration when the advance O/A is set to achieve about 95% copper recovery in the 3E, 1 S stage configuration. Note that under conditions where the 3E, 1 S configuration achieves about 95% copper recovery the 2E, 2S stage configuration only achieves about 91% copper recovery, all other conditions being the same.
[0050] Now as in Example 1, compare the Cu/Fe selectivity for the 2E, 2S sets in Table 9 with the Cu/Fe selectivity for similar 3E, 1S sets in Table 9. As in Example 1, the iron loading in the organic phase for each isotherm point is plotted against the copper loading for the same point. The resulting graph was then used to obtain an iron loading for any copper loading of the organic phase. For the sets in Table 9, the loaded organic was obtained from the computer simulated circuit run and then the iron loading for that copper loaded organic was obtained from the graph of iron loading verses copper loading. This Cu/Fe selectivity data for the sets in Table 9 is given in Table 10 below.
TABLE 10 Loaded Advance Copper Stripped Organic Cu/Fe O/A Re- Organic ppm Selec- Set Staging Extraction covery g/l Cu g/l Cu Fe tivity 1a 2E, 2S 1.0 96.2% 1.95 7.70 5.35 ˜1100 1b 3E, 1S 1.0 97.7% 2.57 8.40 4.35 ˜1300 2a 2E, 2S 0.68 91.0% 1.95 9.94 2.85 ˜2800 2b 3E, 1S 0.68 94.9% 2.57 10.90 2.50 ˜3300
[0051] As discussed in Example 1, Cu/Fe selectivity was calculated by dividing the copper transfer of the organic phase by the iron loading on the loaded organic phase [(Loaded Organic Cu—Stripped Organic Cu)/Loaded Organic Fe]. The data in Table 10 shows that for comparable conditions the 3E, 1 S stage configuration results in higher Cu/Fe selectivity than the 2E, 2S stage configuration. For example, compare set 1 a with set 1 b , and set 2a with set 2b. The higher Cu/Fe selectivity of the 3E, 1 S stage configuration over the 2E, 2S stage configuration provides an added advantage of the 3E, 1 S staging configuration over the 2E, 2S configuration. | A circuit configuration for a metal solvent extraction plant comprising:
A) an extraction section for extracting metal ions from an aqueous leach solution containing the metal ions with an organic solvent solution containing at least one metal extraction reagent, wherein the extraction section consists of three countercurrent extraction stages; and
B) a stripping section consisting of one stripping stage for stripping the metal ions from the metal extraction reagent. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a magneto-optical recording medium having a large magneto-optical effect when exposed to short-wavelength light and hence is suitable for high-density recording.
2. Description of the Prior Art
Magneto-optical recording has been put to practical use as an optical recording method that permits rewriting. Heretofore, single-layered rare earth-transition metal amorphous films having a strong magnetic anisotropy in a direction perpendicular to the film surface have been employed as magneto-optical recording films.
In particular, TbFeCo alloy amorphous films are being researched and developed for practical use. An increase in the recording density is a major aim in the field of magneto-optical recording. Shortening of the wavelength of writing/reading light is currently being studied as a method of achieving this. To increase the magneto-optical recording density in the future, it is indispensable to develop magneto-optical materials that have a high magneto-optical effect (the Kerr effect and Faraday effect) at short wavelengths. With such conventional TbFeCo alloy amorphous films, the magneto-optical effect tends to decrease monotonically as the wavelength of a laser beam becomes shorter, and sufficiently large Kerr rotation or Faraday rotation is not obtained at short wavelengths, which results in a drastic decrease in the output when it is read out by a laser beam.
On the other hand, there is a known amorphous film that is an alloy of a transition metal consisting mainly of Co and Fe and of rare earth elements consisting mainly of Nd and Pr (see, for instance, T. R. McGuire et al., "Magneto-optical Properties of Nd-Co and Nd-Fe Alloys," J. Appl. Phys. 61(8), Apr., 15, 1987, pp. 3352-3354). This film, although it has a large magneto-optical effect at short wavelengths, has in-plane magnetization but not perpendicular magnetization, and cannot realize high-density recording.
A double-layered film formed by laminating a Nd alloy rare earth-transition metal amorphous film and a TbFeCo amorphous film to utilize exchange coupling between them is proposed by Ito, et al. in "Magnetic and Magneto-optical properties of Nd alloy multilayers," Digest of the 13th annual conference on magnetics in Japan (1989), p. 325. However, the double-layered film disclosed therein has a Kerr rotation angle of 0.3 degrees at a wavelength of 400 nm, and does not fully realize intrinsic Kerr rotation of Nd alloys.
Among materials other than amorphous materials, crystalline Co and Fe are known to have large magneto-optical effects at short wavelengths. However, they are not available in the form of perpendicularly magnetized films and have received almost no attention heretofore as magneto-optical materials.
Here again, attempts have been made to obtain a perpendicular-magnetized film by laminating an in-plane magnetized film Co and a perpendicular-magnetized film TbFeCo to utilize exchange coupling between two films (see, H. Wakabayashi, et al., "Magnetic and magneto-optical properties of Co/TbFeCo exchange coupled films," Digest of the 13th annual conference on magnetics in Japan (1989), p. 326). However, in order to obtain a double-layered film that has good squareness according to the proposed approach, the thickness of Co must be 25 Å or less. Therefore, this film can have only a low Kerr rotation angle derived from the TbFeCo film alone at short wavelengths.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a magneto-optical recording medium that has a sufficiently large magneto-optical effect even at short wavelengths, reorients the magnetization in a direction perpendicular to the film surface, and permits high-density recording.
A magneto-optical medium according to the invention is composed of a first magnetic layer in the form of a rare earth-transition metal amorphous film including at least one rare earth element selected from a group consisting of Tb, Dy, and Gd and including at least one transition metal element selected from a group consisting of Fe and Co; a second magnetic layer in the form of either a rare earth-transition metal amorphous film including at least one rare earth element selected from a group consisting of Nd and Pr and including at least one transition metal element selected from a group consisting of Fe and Co, or a crystalline film including at least one element selected from a group consisting of Fe and Co; and a third magnetic layer in the form of a rare earth-transition metal amorphous film including at least one rare earth element selected from a group consisting of Tb, Dy, and Gd and including at least one transition metal element selected from a group consisting of Fe and Co, those layers being laminated successively, with the first layer being the first to be penetrated by light.
The thickness of the first layer is required to be not more than 20 nm, to allow a sufficient amount of light to be transmitted and make to the best use of the excellent magneto-optical effect of the second layer, and not less than 1 nm, to exert magnetic exchange coupling on the second layer and thus to reorient a sufficient strength of magnetization perpendicularly.
The thickness of the second layer is required to be not more than 20 nm, to allow magnetic exchange coupling to be received from the first layer and the third layer, and not less than 1 nm, to ensure an excellent magneto-optical effect at short wavelengths.
The thickness of the third layer is required to be not less than 2 nm, or preferably not less than 5 nm, to allow a sufficient strength of magnetic exchange coupling to be exerted. From the viewpoint of the cost, the upper limit is, preferably, 200 nm.
The preferable Curie temperatures of the first and third layers are required to be not more than 300° C., making them suitable for writing under heat by a laser beam. The more preferable temperature range is not less than 100° C. and not more than 200° C.
The preferable composition of the second magnetic layer is represented by the formula (A 1-a B a ) x (Fe 1-b Co b ) y T z , where A is at least one element selected from a group consisting of Nd and Pr, B is at least one element selected from a group consisting of Tb, Dy, and Gd, T is at least one element selected from a group of transition metals for improving anticorrosion, 0≦a≦0.9, 0≦b≦1, 0≦x≦40, 0≦z≦10, and x+y+z=100.
Examples of the first and third magnetic layers are TbFeCo, GdTbFeCo, DyTbFeCo, DyFeCo, and DyGdFeCo films.
The group T of transition metal elements consists of Ti, Zr, V, Nb, Ta, Cr, Mo, W, Pd, Pt, Au, and Al, which are known to improve anticorrosion. These elements may be included in the first or third layer. Since excessive addition of these elements would destroy the expected properties of the respective magnetic films, the additional amount, in either film, must be within 10 atomic percentage points.
For a fuller understanding of the nature and advantages of the present invention reference should be made to the following detailed description taken into conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of the general construction of a magneto-optical recording medium;
FIG. 2 is a graph showing the relationship between the thickness of the first layer and the Kerr rotation angle in a TbFeCo/NdCo/TbFeCo trilayer film;
FIG. 3 is a graph showing the Kerr hysteresis curve of an example of such a trilayer film;
FIG. 4 is a graph showing the relationship between the thickness of the second layer and the Kerr rotation angle in a TbFeCoCr/NdFeCo/TbFeCo trilayer film;
FIG. 5 is a graph showing the relationship between the thickness of the third layer and the Kerr rotation angle in a TbFeCoTa/PrFeCo/TbFeCoTa trilayer film;
FIG. 6 is a graph showing the relationship between the incident light wavelengths and the figures of merit in a TbFeCo/NdCo/TbFeCo trilayer film and a TbFeCo single layer film;
FIG. 7 is a graph showing the relationship between the thickness of the first layer and the Kerr rotation angle of a TbFeCo/Fe/TbFeCo trilayer film;
FIG. 8 is a graph showing the relationship between the thickness of the second layer and the Kerr rotation angle of a TbFeCo/Co/TbFeCo trilayer film; and
FIG. 9 is a schematic diagram of a magneto-optic disk drive system using the media of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the invention is explained below, with reference to the drawings.
FIG. 1 is a cross-sectional view of the general construction of a triple-layered structure consisting of a first layer 1, a second layer 2, and a third layer 3 made on a glass substrate 4. A laser beam L first penetrates the first layer of the trilayer film. All films in experimental examples referred to subsequently were made by a DC magnetron sputtering method.
Several samples were first made in which Tb 21 Fe 75 Co 4 (coercivity Hc=5 kOe, Curie temperature Tc=200° C.) amorphous films were used for the first and third layers and a Nd 20 Co 80 amorphous layer for the second layer, with a constant thickness of 10 nm for the second layer, a constant thickness of 100 nm for the third layer, and a variable thickness t 1 for the first layer. FIG. 2 shows the values of the remanent Kerr rotation angle measured by a laser beam of wavelength 400 nm incident from the glass substrate. This figure shows that the first layer is required to have a thickness of not less than 1 nm and not more than 20 nm in order to obtain a Kerr rotation angle of 0.3 or more degrees, which is suitable for practical use.
FIG. 3 shows a representative Kerr hysteresis loop measured by a laser beam of wavelength 400 nm incident from the glass substrate of a sample whose first layer is 5 nm thick. The figure shows that a perpendicular-magnetized film suitable for magneto-optical recording is obtained, showing an excellent squareness with a coercivity of 2 kOe.
Next, several kinds of samples were made in which a Tb 20 Fe 45 Co 29 Cr 6 (coercivity Hc=7 kOe, Curie temperature Tc=350° C.) amorphous film was used as the first layer, a Nd 20 (Fe 0 .65 Co 0 .35) 80 amorphous layer as the second layer, and a Tb 21 Fe 75 Co 4 amorphous film as the third layer, with a constant thickness of 5 nm for the first layer, a constant thickness of 100 nm for the third layer, and a variable thickness t 2 for the second layer. FIG. 4 shows the values of the remanent Kerr rotation angle measured by a laser beam of wavelength 400 nm incident from the glass substrate. The figure shows that a Kerr rotation angle of 0.3 or more degrees, suitable for practical use, is obtained when the range of thickness of the second layer is not less than 1 nm and not more than 20 nm.
Next, several kinds of samples were made in which Tb 24 Fe 65 Co 6 Ta 5 (coercivity Hc=8 kOe, Curie temperature Tc=150° C.) amorphous films were used for the first and third layers and a Pr 20 (Fe 0 .5 Co 0 .5) 80 amorphous layer for the second layer, with a constant thickness of 5 nm for the first layer, a constant thickness of 15 nm for the second layer, and a variable thickness t 3 for the third layer. FIG. 5 shows the values of the remanent Kerr rotation angle measured by a laser beam of wavelength 400 nm incident from the glass substrate. The figure shows that a Kerr rotation angle of 0.3 or more degrees, suitable for practical use, is obtained when the range of thickness of the third layer is not less than 2 nm.
For a triple-layered film with a first layer in the form of a 5-nm-thick Tb 19 Fe 67 Co 10 Nb 4 film, a second layer in the form of a 10-nm-thick Pr 20 Fe 24 Co 56 film, and a third layer in the form of 50-nm-thick Tb 19 Fe 67 Co 10 Nb 4 film, the Kerr rotation angle measured under the same conditions was 0.4 degrees, and the coercivity was 2 kOe. The Kerr hysteresis loop had excellent squareness.
FIG. 6 shows the figure of merit (the product of the square root of the reflection ratio and the Kerr rotation angle) of a triple-layered film of Tb 18 Fe 49 Co 33 (5 nm thick)/Nd 20 Co 80 (10 nm thick)/Tb 18 Fe 49 Co 33 (100 nm thick) as a function of the wavelength of incident light (1). The figure also shows the figure of merit of a conventional Tb 25 Fe 65 Co 10 film for comparison (2). It is evident from the figure that the triple-layered film according to the invention has a higher figure of merit than the conventional material throughout the entire wavelength range, and is an excellent magneto-optical recording material.
The following explanation concerns experimental examples using crystalline Co, Fe, or an alloy of them as the second layer.
Several kinds of samples were first made, in which Tb 18 Fe 49 Co 33 amorphous films were used for the first and third layers and an Fe crystalline film for the second layer, with a constant thickness of 7 nm for the second layer, a constant thickness of 100 nm for the third layer, and a variable thickness t 1 for the first layer. FIG. 7 shows the values of the remanent Kerr rotation angle measured by a laser beam of wavelength 400 nm incident from the glass substrate. This shows that the first layer is required to have a thickness of not less than 1 nm and not more than 20 nm in order to obtain a Kerr rotation angle of 0.3 or more degrees, suitable for practical use, as when the second layer is a rare earth-transition metal amorphous film.
Next, several kinds of samples were made in which Tb 18 Fe 49 Co 33 amorphous films were used for the first and third layers and a Co crystalline film for the second layer, with a constant thickness of 10 nm for the first layer, a constant thickness of 100 nm for the third layer, and a variable thickness t 2 for the second layer. FIG. 8 shows the values of the remanent Kerr rotation angle measured by a laser beam of wavelength 400 nm incident from the glass substrate. The figure shows that the second layer is required to have a thickness of not less than 1 nm and not more than 20 nm in order to obtain a Kerr rotation angle of 0.3 or more degrees, suitable for practical use, as when the second layer is a rare earth-transition metal amorphous film.
The other characteristics of Tb 21 Fe 75 Co 4 (t 1 =5 nm)/Co(t 2 =5 nm)/Tb 21 Fe 75 Co 4 (t 3 =100 nm) were as follows: coercivity=2 kOe, and Kerr rotation angle θ k =0.4 degrees (measured at 400 nm wavelength). The characteristics of Tb 21 Fe 73 Co 6 (t 1 =7 nm)/Fe(t 2 =7 nm)/Tb 21 Fe 73 Co 6 (t 3 =100 nm) were as follows: coercivity=3 kOe and Kerr rotation angle θ k =0.35 degrees (measured at 400 nm wavelength). The Kerr hysteresis loop in both triple-layered films had excellent squareness.
Experimental examples are shown in which the second layer is a crystalline alloy of Fe and Co. The characteristics of Tb 18 Fe 49 Co 33 (t 1 =10 nm)/Fe 70 Co 30 (t 2 =5 nm)/Tb 18 Fe 49 Co 33 (t 3 =100 nm) were as follows: coercivity=1.4 kOe, and Kerr rotation angle θ k =0.45 degrees (measured at 400 nm wavelength). The characteristics of Tb 18 Fe 49 Co 33 (t 1 =20 nm)/Fe 70 Co 30 (t 2 =5 nm)/Tb 18 Fe 49 Co 33 (t 3 =100 nm) were as follows: coercivity=1.9 kOe, and Kerr rotation angle θ k =0.30 degrees (measured at 400 nm wavelength). The characteristics of Tb 18 Fe 49 Co 33 (t 1 =10 nm)/Fe 50 Co 50 (t 2 =7 nm)/Tb 18 Fe 49 Co 33 (t 3 =100 nm) were as follows: coercivity=1.7 kOe, and Kerr rotation angle θ k =0.40 degrees (measured at 400 nm wavelength). All of the samples have high Kerr rotation at short wavelengths, and high coercivity, making them suitable for practical use. The Kerr hysteresis loop in both triple-layered films had excellent squareness.
Specific experimental examples have been given for various cases in which the first and third layers are TbFeCo alloy films and the second layer includes a rare earth element of a group consisting of Nd or Pr (hereafter called the Nd group).
A key objective of the present invention is to obtain a magneto-optical recording film with a high perpendicular magnetic anisotropy and a high Kerr rotation angle at short wavelengths, by sandwiching a magneto-optical recording film that has an in-plane magnetization but a high Kerr rotation angle at short wavelengths between magneto-optical recording films with a high perpendicular magnetic anisotropy (even with a low Kerr rotation angle at short wavelengths) and by optimizing their respective thickness. Therefore, any magneto-optical recording medium that has substantially the same characteristics as those of TbFeCo alloys may be used for the first and third layers. For instance, a GdTbFeCo film may be used for the first or third layer, since GdTbFeCo is not inferior to TbFeCo in Kerr rotation angle and perpendicular magnetic anisotropy, as shown by D. K. Hairston, et al. in FIG. 2 of "The TM dependence of the magneto-optic signal in GbTb-TM thin films," J. Appl. Phys. 63(8), Apr. 15, 1988, pp. 3621-3623. Further, evaluation of a DyTbFeCo disk and a TbFeCo disk in FIG. 4 of "Compositional dependence of recording noise in amorphous rare-earth-transition metal magneto-optical disks," J. Appl. Phys. 63(8), Apr. 15, 1988, pp. 3856-3858, shows that both are substantially equal in performance. In view of this, the TbFeCo film may also be replaced by a DyTbFeCo film. Moreover, as shown by Endo et al. in "Magnetic and magneto-optic properties of amorphous Dy-Fe-Co and Tb-Fe-Co films," Journal of the Magnetics Society of Japan, Vol. 8, No. 2, 1984, pp. 101-104, a DyFeCo film has magnetic and magneto-optical properties similar to those of a TbFeCo film. Therefore, a DyFeCo film may be used for the first or third layer instead of the TbFeCo film. As shown by Sumi et al. in "Read/write characteristics of GdDyFeCo magneto-optical disk," Digest of the 11th annual conference on magnetics in Japan (1987), P. 273, a GdDyFeCo film is a magneto-optical recording material that has substantially the same properties as those of a TbFeCo film. Therefore, the TbFeCo film may be replaced by a GdDyFeCo film.
At least one rare earth element selected from a group consisting of Tb, Dy, and Gd (hereafter called the Tb group) may be added to the second layer. This is because addition of an element of the Tb group to the second layer enhances the perpendicular magnetic anisotropy of the second layer itself and hence increases the perpendicular magnetic anisotropy of the entire trilayer film. However, if the additional amount of the Tb group element is excessive, the amount of the Nd group element becomes insufficient, and the second layer and hence the entire trilayer film cannot have a high Kerr rotation angle at short wavelengths. Therefore, the additional amount of the Tb group element should be not more than 90 atomic percent of all the rare earth elements. One example of a rare earth-transition metal amorphous film with an additional element of the Tb group that can be used for the second layer is an NdGdFeCo film. As shown by Ito et al. in FIG. 3 of "Magnetic and Magneto-optical properties of Nd alloy multilayers," Digest of the 13th annual conference on magnetics in Japan (1989),p. 325, a single-layered film of Nd 5 Gd 22 (Fe 68 Co 32 ) 73 actually has a Kerr rotation angle of 0.336 degrees at 400 nm. This is larger than the value of TbFeCo at 400 nm (approximately 0.2 degrees), and the shape of its spectrum demonstrates that the decrease in the Kerr rotation angle at short wavelengths is small. Therefore, it is expected that the use of this film as the second layer of the trilayer film according to the invention will also result in a sufficiently large Kerr rotation angle at a short wavelength range.
Another example of a rare earth-transition metal amorphous film with an additional element of the Tb group that can be used for the second layer is a NdTbFeCo film. As shown by Ota in FIG. 7 of "High density recording of optical memory," Journal of the Magnetics Society of Japan, Vol. 14, No. 4, 1990, pp. 617-623, and Nd 12 Tb 16 Fe 36 Co 36 film has substantially the same properties as the NdGdFeCo film, and its use as the second layer is expected to result in a sufficiently large Kerr rotation angle at short wavelengths. A NdDyFeCo film may also be used for the second layer, because its magneto-optical properties do not vary much, even when Tb is replaced by Dy in the rare earth-transition metal amorphous layer, as described in the foregoing article by Endo et al.
FIG. 9 is a schematic diagram of an optical data storage system of the present invention and is designated by the general reference number 100. System 100 uses an optical media disk 110 which is similar to the media as shown in FIG. 1. An optical head 120 is positioned below medium 110. Head 120 is moved in a radial direction relative to disk 110 by a linear motor 122. A bias magnet 130 is located above medium 110 and is connected to a magnet control 132.
A laser 150 produces a polarized light beam 152. Laser 150 is preferably a laser diode. Light beam 152 is collimated by a lens 154 and circularized by a circularizer 156. Circularizer 156 is preferably a prism.
Beam 152 passes to a beamsplitter 158. A portion of beam 152 is reflected toward a lens 160. Lens 160 focuses the light to a power monitor optical detector 162. Detector 162 is connected to a laser control 164. Detector 162 provides control 164 with a power monitor signal representative of the power level of beam 152 which is used to adjust the power of laser 150 as appropriate.
The remaining portion of beam 152 passes through beamsplitter 158 to a mirror 170. Mirror 170 reflects the light towards a focussing lens 172. Lens 172 focuses beam 152 onto the disk 110. Lens 172 is mounted in a lens holder 174. Holder 174 may be moved relative to disk 110 by an actuator motor 176. Mirror 170, lens 172, holder 174, and motor 176 are preferably located in the optical head 120.
A light beam 180 is reflected from the disk 110, passes through lens 172 and is reflected by mirror 170. A portion of the light beam 180 is then reflected by beamsplitter 158 to a beamsplitter 190. Beamsplitter 190 divides the beam 180 into a data beam 194 and a servo beam 196.
Data beam 194 passes through a quarter waveplate 200 to a polarizing beamsplitter 202. Beamsplitter 202 divides beam 194 into two orthogonal polarization components. A first polarization component beam 204 is focused by a lens 206 to a data detector 208. A second polarization component 210 is focussed to a lens 212 to a data optical detector 214. A data circuit 216 is connected to detectors 208 and 214 and generates a data signal representative of the data recorded on medium 110.
A servo beam 196 is focussed by a lens 220 onto a segmented optical detector 222, such as a spot size measuring detector as is known in the art. A focus servo 228, as is known in the art, is connected to detector 222 and motor 176. Servo 228 controls motor 176 to adjust the position of lens 172 as appropriate in order to maintain proper focus. A track and seek servo 230, as is known in the art, is connected to detector 222 and motor 122. Servo 230 causes motor 122 to adjust the position of head 120 as appropriate. A disk drive controller 240 as is known in the art, provides overall control for servo 228 and 230, as well as laser control 164 and magnet control 132.
The operation of system 100 may now be understood. During a write operation, controller 240 causes laser control 164 to energize laser 150 to provide a high powered polarized beam 152. Beam 152 is powerful enough to heat the medium 110 to above its Curie temperature. At the same time, controller 240 causes magnet control 132 to energize magnet 130. The laser 150 is pulsed responsive to the data to be recorded on the disk and the data is recorded on the disk as the changes in magnetic domain orientations.
During a read operation, controller 240 causes laser control 164 to energize laser 150 to generate a low power polarized beam 152. Beam 152 is focussed to medium 110. The low power beam does not heat medium 110 to above its Curie temperature. The reflected light 180 has its plane of polarization rotated one way or the other depending upon the magnetic domain orientations of the spots recorded on the medium 110. This is a result of the Kerr effect. These differences in polarization are detected by detectors 208 and 214, and data circuit 216 outputs a digitized data signal representative of the recorded data. Data circuit 216 is known in the art.
While the preferred embodiments of the present invention have been illustrated in detail, it should be apparent that modifications and adaptations to those embodiments may occur to one skilled in the art without departing from the scope of the present invention as set forth in the following claims. | A magneto-optical medium is comprised of three layers. The first layer is made of a rare earth-transition metal amorphous film from one to twenty nanometers thick. The second layer is comprised of a rear earth-transition metal amorphous film or crystalline film and is one to twenty nanometers thick. The third layer is comprised of a rare earth-transition metal amorphous film and is not less than two nanometers thick. The resulting medium has a sufficiently large magneto-optical effect even at short wave lengths and is perpendicular magnetized film. A data storage system including the magneto-optical medium therein. | 6 |
RELATED APPLICATIONS
This application claims the benefit of priority under 35 U.S.C. §119(e) from U.S. Provisional Patent Application 61/163,697, entitled “System and Method For Longitudinal and Radial Drilling”, which was filed Mar. 26, 2009, the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
A system and method for enabling longitudinal and radial drilling in a wellbore is described. The system and method enable an operator to perforate the casing of a wellbore with an under-reamer at the end of a drill string and, without removing the drill string from the wellbore, initiate and complete radial drilling of the wellbore into the surrounding formation. The system utilizes a perforation tool having a ball seat, which upon seating a drop ball in the ball seat enables the perforation tool to move from a closed position to an open position thereby allowing access to the formation using a jetting tool. Prior to seating the drop ball, an under-reaming operation may be performed using a hydraulic pressure activated under-reaming tool.
BACKGROUND OF THE INVENTION
Oil and gas wells are drilled vertically down into the earth strata with the use of rotary drilling equipment. A tube known as casing is placed down into the well after it is drilled in order to provide stability to the drill hole for and during the subsequent recovery of hydrocarbons from the well. The casing defines the cross-sectional area of the well for transportation of oil and gas upwardly from the well. The casing is usually made of steel and is generally 4.5-8 inches in external diameter and 4-7.5 inches in internal diameter. The casing may hang freely in portions of the well and will often be cemented in place with grout and/or cement. As is well known, after casing a well, the cased well must be perforated through the casing to permit formation fluids to enter the casing from any zones of interest adjacent to the casing.
In addition to simply perforating a well and allowing formation fluids to flow into the well, well production can be improved by subjecting the well and producing formations to fracturing operations in which fractures are induced in the formation using high pressure pumping equipment. Further still, other drilling methods such as horizontal or directional drilling may be employed to enhance hydrocarbon recovery.
However, each of these technologies can be extremely costly such that the cost presents a significant barrier to enhanced production in some applications. Moreover, such techniques may not be able to exploit thin production horizons. Generally, the limitations of these production enhancement technologies results in what the industry refers to as by-passed production.
As a result, there has been a need for systems and methods to effectively enhance production of reservoirs beyond that which may be achieved through simply perforating a well or by the very expensive fracturing or horizontal or directional drilling techniques. In particular, there has been a need for systems and methods that can effectively enhance production and at a cost significantly below that of many past techniques.
More specifically, there has been a need for improved radial or longitudinal drilling in which the well casing can be effectively penetrated in a radial direction to the longitudinal axis of the well to gain access to the surrounding earth strata. Radial access to the formation has been achieved by various techniques including fluid jetting. While fluid jetting is a known technique, there continues to be a need for systems that improve the overall efficiency of such techniques and, in particular, the ability to enable radial jetting by minimizing the number of steps in the overall process of perforating a well and subsequently performing a radial fluid jetting operation.
A review of the prior art reveals that a number of technologies have been utilized in the past. For example, U.S. Pat. No. 6,971,457 describes a method for drilling holes in casing using a multiple U-Joint method. This method allows the jetting tool to be located down well in a different slot than the casing perforator, wherein it can then be used once the perforation is made.
U.S. Pat. No. 6,920,945 also describes a method for drilling holes in casing using a multiple U-Joint method. In this case, once the perforation is drilled, the perforation device is removed and a flexible tube is inserted to penetrate the perforation and jet drill the formation.
Other patents include U.S. Pat. No. 6,550,553 which describes a method for drilling holes in casing using a multiple U-Joint method; U.S. Pat. No. 6,523,624 which describes a method for drilling holes in casing using a flexible spline drive and a cutter to cut holes in casing; U.S. Pat. No. 6,378,629 which describes a method for drilling holes in casing using a multiple U-Joint method; U.S. Pat. No. 6,189,629 which describes a jet cutting tool rotatable in the downhole position allowing for multiple radial drills in which the jet drilling tool erosion drills the casing using a fluid and an abrasive; U.S. Pat. No. 5,853,056 that describes a ball cutter to drill the casing; U.S. Pat. No. 7,441,595 describing an alignment tool to ensure that multiple passage ways can be accessed; and U.S. Pat. No. 7,195,082 describing a directional control system to work with a jet drilling system.
In addition, U.S. Pat. Nos. 6,964,303; 6,889,781; 6,578,636 describe drilling systems for porting a casing and using a jet drilling system for formation drilling.
Further still, U.S. Pat. No. 6,668,948 describes a jet drilling nozzle with a swirling motion applied to the fluid; U.S. Pat. No. 6,530,439 describes a jet drilling hose and nozzle assembly with thruster jets incorporated in the hose to advance the drilling hose during the drilling process; U.S. Pat. No. 6,412,578 describes a multiple U-Joint casing boring technology; U.S. Pat. No. 6,263,984 describes a rotating and non-rotating jet drilling nozzle system; U.S. Pat. Nos. 6,125,949 and 5,413,184 describe a ball cutter for drilling a window in the casing and using a jet drilling assembly for drilling the formation; and, U.S. Pat. No. 4,708,214 describes a jet drilling nozzle assembly.
While the prior art may provide a partial solution, each are limited in various ways as briefly discussed below.
In particular, past systems may be limited by the practical effectiveness of the system downhole or by inherent problems in the design of the systems. Such problems may include the strength, durability and accuracy of a flexible shaft and/or the effectiveness of a ball cutter. Other problems include the number of steps required, the complexity of the systems and, hence the maintenance costs associated with such systems.
Abrasive jet techniques and rotary techniques may be further limited in narrow casing ID's deployments and problems of ports that introduce potential tear/binding points.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided a lateral jetting system for providing access for a jetting tool to a downhole formation comprising: a body adapted for attachment to a drill string, the body having a jetting orifice; a sliding sleeve slidingly retained within the body, the sliding sleeve having a fluid channel for enabling fluids to flow from an uphole side of the sliding sleeve to a downhole side of the sliding sleeve; a plug seat within the fluid channel for receiving a plug to seal the fluid channel; a jetting trough uphole of the plug seat for enabling a jetting hose to be radially deflected from the sliding sleeve wherein the sliding sleeve is operable between a closed position where the jetting trough is not aligned with the jetting orifice and an open position where the jetting trough is aligned with the jetting orifice; and, a shear pin for retaining the sliding sleeve in the closed position; wherein hydraulic pressure applied to the sliding sleeve will cause the shear pin to shear such that the sliding sleeve will move from the closed position to the open position when a plug is seated against the plug seat.
In further embodiments, the fluid channel is sequentially defined by the jetting trough, a circumferential groove on the exterior of the sliding sleeve, a side port and a central throughbore in fluid communication with one another. Preferably, the circumferential groove is adjacent a lower end of the jetting trough and/or the plug is a drop ball.
In another embodiment, the body includes a corresponding circumferential groove to the circumferential groove which together collectively define a generally circular circumferential groove size to permit the passage of the drop ball therethrough.
In yet another embodiment, the system includes at least two dogs diametrically positioned on the body for biasing the body to a central position in a wellbore.
In another embodiment, the system further comprises at least one o-ring operatively connected to the sliding sleeve and body for sealing between the sliding sleeve and body.
In another aspect of the invention, a method for radial jetting a well bore in a system having an under-reamer and lateral jetting system as above is provided, the method comprising the steps of: a) applying a hydraulic pressure to an upper surface of the under-reamer tool to effect under-reaming and access to a formation; b) introducing a drop ball to the drill string and pumping the drop ball to effect seating of the drop ball within the ball seat and block the passage of fluid to the under-reamer; c) increasing hydraulic pressure within the drill string to shear the shear pin and cause the sliding sleeve to move from the closed position to the open position; d) advancing a jet hose in the drill string such that the jet hose seats within the jetting trough and is radially deflected along the jetting trough to the jetting orifice; and e) conducting lateral jetting with the jet hose.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is described with reference to the accompanying figures in which:
FIG. 1 is a plan view of an assembled downhole tool in accordance with one embodiment of the invention;
FIG. 2 is a cross-sectional view of an assembled downhole tool in accordance with one embodiment of the invention;
FIG. 3 is an exploded view of a lateral jetting system in accordance with one embodiment of the invention;
FIGS. 4A and 4B are a cross-sectional views of a lateral jetting system of the downhole tool showing the system in closed and open positions respectively in accordance with one embodiment of the invention;
FIG. 4C is a side view of a lateral jetting system in accordance with one embodiment of the invention; and,
FIGS. 5A-5E are plan, side, perspective, top, and bottom and perspective views respectively of a sliding sleeve of a lateral jetting system in accordance with one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
With reference to the figures a downhole tool system enabling lateral jetting from within well casing is described.
As shown in FIGS. 1 and 2 , a lateral jetting system 10 includes a lateral jetting section (LJS) 18 , an under-reamer section 14 , a bullnose 16 and a crossover sub 12 .
Overview
In an operation to under-ream and laterally jet a cased well, the system 10 is attached to a drill/coiled tubing string (not shown) using the crossover over sub 12 . The LJS 18 is attached to the cross-over sub and the LJS is attached to the under-reamer 14 which in turn is attached to the bullnose 16 .
The system 10 is pushed into the well to a desired depth and drilling fluid is circulated down through the coiled tubing, through the cross-over sub, LJS, under-reamer and out through the bullnose as shown in FIG. 2 .
At the commencement of the under-reaming operation, the operator increases the flow rate of drilling fluid through the system such that hydraulic pressure acting on piston surface 14 a overcomes spring 14 b and causes milling arms 14 c to pivot outwardly and engage with the well casing. The combined hydraulic pressure and rotation of the drill string will cause the milling arms to mill the casing so as to create a milled passage to the formation through the casing.
After completing the under-reaming operation, hydraulic pressure is released and the milling arms will retract into the under-reamer under the action of spring 14 b.
The system is then lowered further into the well such that the LJS is substantially aligned with the milled passage.
At surface, a drop ball is then introduced into the coiled tubing where it is allowed to fall by gravity and hydraulic fluid pressure such that the drop ball moves to the LJS where the drop ball then becomes lodged or seated within the LJS and blocks the passage of fluid through the LJS to the under-reamer.
Hydraulic fluid pressure is then increased to a level that then causes a shear pin within the LJS to shear, thereby causing a sliding sleeve within the LJS to displace downhole such that an LJS jetting port is opened.
Once the LJS jetting port is opened, a jetting hose and tool is lowered down the drill string through the jetting port wherein radial jetting using the jetting tool can be performed.
The various sub-components of the system and their operation are described in greater detail below and with reference to the Figures.
Crossover Sub 12
The crossover sub 12 includes an upper body 12 a having an appropriate connection system 12 b for attachment to a drill string. The crossover sub has a throughbore 12 c to allow a jet hose (not shown) and cutting/milling fluid to pass through the tool to the LJS.
Lateral Jetting System 18
As shown in FIGS. 3 and 4A , 4 B and 4 C, the LJS 18 includes a sliding top sleeve 18 a that is joined to the top of a sliding sleeve 18 b by a dowel pin 18 c . The top end of the sliding top sleeve 18 a is a guide to funnel a jetting hose and drop ball (not shown) into the sliding sleeve. The sliding top sleeve 18 a is telescopically seated within lower body 18 f.
The bottom end of the sliding top sleeve includes a curved surface that forms a top side of a jetting trough 18 d . The jetting trough guides the jetting hose as it transitions (extends) from the well bore into the formation through a side port 19 a . The sliding top sleeve and sliding sleeve are separate pieces to enable manufacturing of the curved surface.
As noted a dowel pin 18 c is used to connect the sliding top sleeve to the sliding sleeve. Once assembled these three components form the jetting trough that preferably is a rounded quarter circular groove. The sliding sleeve also includes a side port groove 18 e that is a semi-circular groove that wraps approximately 90 degrees around the exterior body of the sliding sleeve from the bottom end of the jetting trough to a side port 18 h . A corresponding generally semi-circular groove 18 g is located on the inside of the lower body 18 f wherein the two semi-circular grooves define a fluid path from the lower end of the jetting trough to the side port 18 h . By virtue of their semi-circular shape, these grooves also form the pathway for the drop ball. Thus, the normal fluid path through the tool is circuitous as fluid initially is deflected outwardly along the jetting trough, circumferentially around the sliding sleeve and back towards the middle of the sliding sleeve where it continues longitudinally through bore hole 18 o in the center of the sliding sleeve 18 . The purpose of the circuitous path is to eliminate any lipped surfaces that might otherwise impede a jetting hose along the curved surface of the jetting trough.
The lower body 18 f includes lower body port 21 that provides a passageway for a jetting hose from the sliding top sleeve through the lower body to the formation.
In operation, when the drop ball is dropped into the downhole assembly, the drop ball follows the path of the fluid and eventually reaches the LJS where it passes along the curved surface 18 d , around grooves 18 e , 18 g into ball well 18 h and seats in ball portal or seat 18 i ( FIG. 5 ).
Once the drop ball is seated, fluid flow is blocked to the under-reamer tool and with continued pumping of drilling fluid there is a build up of pressure above the sliding sleeve 18 b . This pressure buildup causes shear pin 18 j to shear allowing the sliding sleeve to shift downward from a closed position ( FIG. 4A ) into an open position ( FIG. 4B ) that enables lateral jetting.
That is, as shown in FIGS. 4A and 4B , in FIG. 4A , the sliding sleeve 18 b is uphole with the shear pin 18 j intact and the jetting trough 18 d not aligned with lower port groove 18 h (closed position). FIG. 4B shows the sliding sleeve 18 b in the downhole position wherein shear pin 18 j has been sheared such that the jetting trough 18 d is aligned with the lower port groove 18 h (open position).
In the mid section of the sliding sleeve are two O-ring grooves 18 k for containing corresponding O-rings (not shown) that seal the topside of the downhole assembly from the bottom side during this transition period. Below the O-ring grooves is an alignment pin groove 18 l . The alignment pin groove mates with an alignment pin 18 m which together keep the sliding sleeve in the proper orientation after the shear pin has been sheared.
Near the bottom of the sliding sleeve is a mating shear pin hole 18 n that acts as a seat and knife edge for the shear pin. Inside the sliding sleeve there is also a bore hole 18 o that allows the milling fluid to flow through this component before the drop ball is dropped as described above.
The drop ball is a precision ground sphere that seats into the ball portal 18 i to commence the chain of events that cause the sliding sleeve to transition from the milling mode (closed position) into the lateral jetting mode (open position).
The lower body 18 f also has upper threads 18 p that connect with upper body 18 y and lower threads 18 q that connect into a lower body cap 18 x which in turn connect to the under-reamer or another tool. Internally the lower body 18 f has a bore 18 r for accommodating the sliding sleeve components.
In addition, the LJS includes a slip cage retainer 18 s that is slid over the outside of the lower body. The slip cage retainer secures at least two dogs, preferably four dogs 18 t , dog springs 18 u and slip cage 18 v . The dogs serve as well bore centralizers and the dog springs 18 u apply outward pressure to the dogs. The dogs may also provide positive feedback to the operator when engaged with milled casing to verify the correct position of the LJS with respect to the milled casing.
A spacer sleeve 18 w and slip cage retainer 18 s align and secure the slip cage 18 v against lower body cap 18 x . The slip cage retainer 18 s also secures the top edge of the four dogs and the slip cage. The slip cage has four rectangular windows to incorporate the dogs. These windows secure the dogs so that they are 90° apart.
The slip cage also has four wide ribs 19 that help centralize the downhole assembly while still allowing fluid to flow past the assembly. The slip cage also has a round portal 19 a which aligns with the portal in the lower body and the jetting trough in the sliding sleeve.
In line with the portal is a keyway on the outside barrel of the lower body. This keyway and mating key 18 z ensure that the slip cage is installed in the correct orientation.
The shear pins are made from a material with the appropriate shear strength to allow the sliding sleeve to slide at the desired fluid pressure after the drop ball has been dropped.
As noted above, the lower body cap 18 x is a crossover between the LJS 12 and the under-reamer tool. The top of the lower body cap has an appropriate thread and the bottom of the lower body cap has an appropriate thread such as a 2⅜″ API box thread. The top end of the under-reamer 14 has a corresponding 2⅜″ API Pin thread.
Under-Reamer
As described above, the under-reamer 14 is used to mill out the well casing at the specified depth. The under-reamer upper body 14 e consists of a mandrel having appropriate threads (eg. a 2⅜″ API pin thread on the top). This API thread threads into the bottom of the LJS 12 . The mandrel threads into an under-reamer lower body 14 d . As known to those skilled in the art, the under-reamer will preferably include a set of backwards facing wash jets to divert some of the drilling fluid to the outside of the under-reamer. This fluid is used to wash milled chips into the sump of the well. The piston 14 a applies pressure to deploy the milling arms under hydraulic fluid pressure such that a differential is created between the piston and the under-reamer lower body. The piston sits on compression spring 14 b that is used to return the piston to its retracted state after milling is completed.
The milling arms 14 c are knife arms with carbide inserts on both the top and bottom sides of the milling arms. The milling arms are pinned to the under-reamer lower body and can pivot about this pin.
Typical Thread Dimensions
The top of the LJS has appropriate connector threads such as a 2.75 Stub ACME box thread that threads into the bottom of the crossover sub 12 at the top of the tool string. The bottom of the LJS has a 2⅜″ API thread that threads into the top of the under-reamer tool 14 .
The bullnose 16 has a 2⅜″ API Pin thread on the top that threads into the bottom of the under-reamer.
Although the present invention has been described and illustrated with respect to preferred embodiments and preferred uses thereof, it is not to be so limited since modifications and changes can be made therein which are within the full, intended scope of the invention as understood by those skilled in the art. | A system and method for enabling longitudinal and radial drilling in a wellbore is described. The system and method enable an operator to perforate the casing of a wellbore with an under-reamer at the end of a drill string and, without removing the drill string from the wellbore, initiate and complete lateral jetting of the wellbore into the surrounding formation. The system utilizes a perforation tool having a ball seat, which upon seating a drop ball in the ball seat enables the perforation tool to move from a closed position to an open position thereby allowing access to the formation using a jetting tool. Prior to seating the drop ball, an under-reaming operation may be performed using a hydraulic pressure activated under-reaming tool. | 4 |
SUMMARY OF THE INVENTION
The present invention relates to an improved open-end spinning machine utilizing a quick yarn traverse winding system, called a QT system, and to a method of stopping the same.
In practical mill operations the open-end spinning machines are usually stopped during non-operating hours of the mill, in addition, in some cases, an open-end spinning machine is stopped when a yarn breakage is detected so as to repair the broken yarn. In such cases, it is required that the open-end spinning machine be easily restarted.
To facilitate easy restarting of an open-end spinning machine, many stopping methods have been proposed. For example, a usual method for stopping a conventional open-end spinning machine is to first stop the supply of fibers to the spinning rotor, which collects the fibers into a yarn. Then, after a predetermined time has passed, the rotation of the draw off rollers, which withdraw the yarn from the spinning rotor, and the winding drum which frictionally rotates the bobbin, and the traverse motion of the traverse guide, which traverses the yarn along the bobbin, are stopped. When the machine is started again, the draw off rollers and the winding drum are first rotated in the direction opposite to the normal rotating direction thereof. This allows the yarn wound around the bobbin to be unwound and the end of the yarn situated in a delivery tube connected to the spinning rotor to be sent back into the spinning rotor.
At the same time fibers are supplied into the spinning rotor by a combing roller so as to facilitate the piecing up of the yarn. After a predetermined time has passed, the draw off rollers and the winding drum are rotated in the normal direction, and the traverse of the traverse guide is simultaneously started, so that the winding of the yarn is commenced.
However, in the above described method, because the yarn is exposed to an excessive yarn tension, yarn breakage may occur frequently between the winding drum and the yarn traverse guide while the draw off rollers and the winding drums are rotated in the direction opposite to the normal rotating direction thereof. The reason for this is as follows. In a so called quick traverse winding system, a traverse guide is moved by a grooved cam, and a pin which slides in the groove of the grooved cam. If the traverse guide is moved in the direction opposite to its normal direction, due to the rotation of the grooved cam in a direction opposite to its normal rotating direction, excessive forces may be generated on the grooved cam or the pin. Therefore, it is not desirable to move the traverse guide utilized in the quick traverse winding system in the direction opposite to its normal direction. To avoid the excessive forces generated on the grooved cam or pin, in many conventional machines the yarn traverse guide is kept at a standstill while the draw off rollers and the winding drum are rotated in the direction opposite to their normal direction. However, this method results in yarn breakages for the following reason. When the traverse guide is stopped while the draw off rollers and the winding drum are rotated in a direction opposite to their normal direction, the position where the yarn is unwound from the cheese to the yarn guide can move away from the yarn guide. This results in the yarn between the yarn traverse guide and the discharging position of the cheese being exposed to an excessively increased tension and breakage of the yarn can occur. Of course, in a case where the discharging position of the cheese moves toward the yarn traverse guide, the yarn tension between the discharging position and the yarn traverse guide will not increase and no yarn breakage will occur.
To eliminate the above-mentioned yarn breakage, some conventional machines are provided with a device for disengaging a yarn from the yarn traverse guide while the draw off rollers and the winding drum are rotated in the direction opposite to their normal direction. However, the machine having such a complicated mechanism may not only be expensive, but also troublesome from the maintenance point of view and, therefore, such a machine is not usually utilized in practical mill operations.
An object of the present invention is to provide an open-end spinning machine and a method of stopping the same, by which the above-mentioned defects can be eliminated.
Another object of the present invention is to provide an open-end spinning machine and a method of stopping the same, by which the increase of tension on the yarn between the yarn traverse guide and the yarn discharging position of the cheese can be maintained within a predetermined range while the draw off rollers and the winding drum are rotated in a direction opposite to their normal rotating direction.
A further object of the present invention is to provide an open-end spinning machine and a method of stopping the same by which the yarn is wound around a certain portion of the cheese when the machine is turned off and comes to a stop.
The above-mentioned and further objects, as well as novel features, of the present invention will more fully apparent from the detailed description of the same, set forth below, with reference to the accompanying drawings. It is to be understood, however, that the drawings are for purposes of illustration only and are not intended as a definition of the limits of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic elevational view of an open-end spinning machine for carrying out the method of the present invention;
FIG. 2 is a wiring diagram utilized in the machine shown in FIG. 1;
FIG. 3 is an operational diagram of the machine shown in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
An open-end spinning machine, according to the present invention is explained hereinafter with reference to the accompanying drawings. Although the open-end spinning machine is usually provided with a plurality of spinning units, an open-end spinning machine which is provided with only one spinning unit, is shown in FIG. 1. Referring to FIG. 1, a spinning unit 1 comprises a spinning rotor 2 rotatably mounted on a frame 5, feed rollers 3 and a delivery tube 4. The feed rollers 3 are utilized for supplying fibers 6 to a combing roller (not shown). The combing roller is rotatably mounted within the spinning unit 1, so as to be rotated with the spinning rotor 2, and is utilized for combing the supplied fibers 6 and for supplying said combed fibers 6 to the spinning rotor 2. The spinning rotor 2 collects the supplied fibers 6 into a yarn 7 and twists the yarn 7. A draw off roller 8, having a press roller 9 swingably mounted thereon, for withdrawing the yarn 6 from the spinning rotor 2 via the delivery tube 4, is provided at a position downstream of said delivery tube 4. A guide bar 10, for guiding the yarn 7, is disposed at a position between the draw off roller 8 and a traverse guide 11 disposed on a traverse rod 12. An end of the traverse rod 12 is provided with a pin 13 which slidably penetrates into a groove 14a formed on a surface of a groove roller 14. Consequently the traverse guide 11 is traversed to and fro when the groove roller 14 is rotated. A winding drum 15 is disposed at a position downstream of the traverse guide 11 and is utilized for frictionally rotating a bobbin 16, rotatably mounted on a pair of cradle arms 17, so that the yarn 7 is wound around the bobbin 16 and forms a cheese 18.
Both a shaft 21 of the draw off roller 8 and a shaft 22 of the winding drum 15 are rotated in the same direction by way of the gear trains 24, 25 and 26. Each of the shafts 21 and 22 is rotatably supported by a bearing (not shown) which is fixed to the frame 5. The two shafts 21 and 22 are driven by an electric motor 33. Each shaft 21, 22 is driven in a normal rotating direction by the motor 33 by way of an electromagnetic clutch 51, which is mounted on the shaft 21. Each shaft 21, 22 is driven by the motor 33 in the reverse rotating direction by way of an electromagnetic clutch 52 which is mounted on a shaft 39. Gear trains 27, 28, 29, 30, 31, 32 and 34 are provided as driving gear trains, but the gear trains 27, 28 and 29 are used only in case it is required to drive the shaft 21 in the reverse rotating direction. A shaft 20 of the feed roller 3 is driven by the gear 34 by way of a gear 35 and an electromagnetic clutch 53. The shaft 20 of the feed roller 3 and the shaft 22 of the winding drum 15 are provided with a magnetic brake 62 and a magnetic brake 61, respectively. The magnetic brakes 61 and 62, and electromagnetic clutches 51, 52 and 53, are controlled by an electric control circuit 70. An electric motor 36 drives the spinning rotor 2 by means of an endless belt 42 which is slidably bridged between a wheel 37, connected to the electric motor 36, and a wheel 38. It should be noted that the endless belt 42 also drives other spinning rotors which belong to respective open-end spinning units; however, other open-end spinning units are not shown in FIG. 1. A shaft 23 of the grooved roller 14, which extends behind the gears 24, 25, 26, 27, 28 and 29, is driven by the motor 33 by way of gear trains 31, 32, 40 and 41, and an electromagnetic clutch 54 mounted on the shaft 23. The shaft 23 of the grooved roller 14 is provided with a magnetic brake 63. The electromagnetic clutch 54 and the magnetic brake 63 are controlled by the electric control circuit 70. The electromagnetic clutches 51, 52, 53 and 54 and the magnetic brakes 61, 62 and 63 include exciting coils 51C, 52C, 53C, 54C, 61B, 62B and 63B (FIG. 2), respectively, for the driving thereof and these exciting coils are wired as shown in FIG. 2.
The electric circuit 70 for controlling the open-end spinning machine is hereinafter explained with reference to the accompanying FIG. 2. In FIG. 2, PB1 designates a push-button switch for starting the operation of the open-end spinning machine of the present invention. PB2 designates a push-button switch for stopping the operation of the open-end spinning machine. MS and ms-1 through ms-3 designate a solenoid coil of a relay and the contacts of the relay, respectively, for starting the main motor 33 (FIG. 1) mechanically connected to feed rollers 3, draw roller 8, groove roller 14 and winding drum 15 via suitable power transmitting means such as gear trains, as shown in FIG. 1, and for starting the motor 36 connected to the spinning rotor 2. T1 through T7 and t1 through t7 designate time switches and the contacts thereof, respectively. CR1 through CR6 and cr1-1 through cr6-3 designate solenoid coils of relays and the contacts of the relays, respectively. OL designates a relay switch which operates when an overload current flows.
The operation of the open-end spinning machine according to the present invention is hereinafter explained with reference to FIGS. 2 and 3.
A. Starting Operation of the Open-end Spinning Machine
(1) When the push-button switch PB1 is pushed, the solenoid coil of the relay MS is excited and the circuits (not shown) of the main motor 33 and motor 36 (FIG. 1) are closed, whereby the main motor 33 and the motor 36 are started. As a result, the spinning rotor 2 and the combing roller (not shown), connected to the motor 36, are rotated up to a normal high speed after a start-up time T a . Since the normal speed of the spinning rotor 2 is significantly higher than that of the other means, the long start-up delay time T a is generated by the inertia of the spinning rotors 2, while the spinning rotors 2 are sped up. Since the main motor 33 is disconnected from the feed roller 3, the draw off roller 8 and the winding drum 15 at the starting up thereof, the main motor 33 reaches its normal rotating speed in a very short time after the push-button switch PB1 is pushed. At the same time, the circuit comprising the push-button switch PB2, for stopping the open-end spinning machine, the contact ms-1 of the relay MS and either the time switch T1 or T2 is closed. Then, the break contact t2 of the time switch T2 having a predetermined time delay T 2 is closed immediately. For a predetermined delay time T 1 , which is adjusted to be slightly longer than the start-up time T a , the time switch T1 is energized and is closed.
(2) When the contact t1 of the time switch T1 is closed, the solenoid coil of the relay CR1 is energized. Then, the contact cr1-1 of the relay CR1 is closed and cr1-2 of the relay CR1 is opened and the time switch T3 is energized. Since the contact cr1-1 of the relay CR1 is closed, the circuit comprising the contact cr1-1, the break contact cr3-2 of the relay CR3 and the solenoid coil 52C, of the electromagnetic clutch 52 mounted on the shaft 39, is closed. Because the electromagnetic clutch 52 is connected to the winding drum 15 and the draw off roller 8 via gear trains 24, 25 and 26, for reversely rotating the winding drum 15 and the draw off roller 8, when the above-mentioned circuit including the solenoid coil 52 is closed, the winding drum 15 and the draw off roller 8 are rotated in a direction opposite to their normal rotating direction. As mentioned in item (1) above, when the push-button switch PB1 is pushed, the spinning rotor 2 is rotated. This causes the air pressure within the spinning rotor 2 to be decreased and the yarn 7 becomes slack due to the above-mentioned reverse rotation of the draw off roller 8. Therefore, an end of the yarn (not shown) situated in the delivery tube 4 is caused to move back into the spinning rotor 2 by the above-mentioned decreased air pressure.
(3) After the time switch T3 is energized for a predetermined delay time T 3 , the make contact t3 of the time switch T3 is closed and the solenoid coil of the relay CR2 is energized. When the solenoid coil of the relay CR2 is energized, the circuit comprising the contact cr2-2 of the relay CR2, the break contact cr5-1 of the relay CR5 and the exciting coil 53C, for driving the clutch 53 connected to the feed roller 3, is closed. Then the feed roller 3 starts to rotate and fibers 6 begin to be supplied into the spinning rotor 2. As a result, the end of yarn and the supplied fibers are pieced up within the spinning rotor 2.
(4) When a predetermined delay time T 4 has passed after the close of the make contact t3 of the time switch T3 and after the time switch T4 is energized, the time switch T4 is closed and both the solenoid coil of the relay CR3 and time switch T5 are energized. When the solenoid coil of the relay CR3 is energized, the break contact cr3-2 opens and the exciting coils 52C become open. In addition, the circuit comprising the contact cr3-3 of the relay CR3, the break contact cr6-2 of the relay CR6 and the exciting coil 51C for driving the electromagnetic clutch 51, is closed. Then the winding drum 15 and the draw off roller 8 are rotated in their normal rotating direction.
The predetermined delay times T 3 and T 4 of the time switches T3 and T4 are suitably determined so that the above-mentioned piecing up operation can be carried out and the newly supplied fibers 6 collected in the spinning rotor 2 can be withdrawn from the spinning rotor 2 to the draw off roller 8 and press roller 9.
(5) For a predetermined time T 5 , the time switch T5 is energized and, then, the time switch T5 is closed for exciting the solenoid coil of the relay CR4. Thereafter, the circuit comprising the contact cr4-2 of the relay CR4, the break contact cr5-2 of the relay CR5 and the exciting coil 54C for driving the clutch 54 is closed. As a result, the groove roller 14, connected to the clutch 54, starts to rotate in its normal rotating direction. Consequently, the traverse guide 11 is traversed to and fro via the groove roller 14.
The traverse of the traverse guide 11 may be started at any time by adjusting the delay time T 5 of the time switch T5. This means the traverse of the traverse guide 11 may even be started just when the draw off roller 8 and the winding drum 15 are started by setting the delay time T 5 at zero.
The open-end spinning machine according to the present invention is started and enters into a normal operation as described above.
B. Stopping Operation of the Open-end Spinning Machine
(1) When the push-button switch PB2 is pushed, the operation of the solenoid coil of the relay MS for operating the main motor 33 and the motor 36 (FIG. 1) is stopped. Then the main motor 33 is turned off. However, the main motor 33 is at this time connected to the feed roller 3, draw off roller 8 and the winding drum 15, and has a large inertia, and, consequently, the main motor 33 continues its rotation for a while. In addition, when the relay MS is stopped, the motor 36 is turned off and is brought to a standstill after a certain delay time T b . The delay time T b is generated by the inertia of the spinning rotors 2. The fiber supply, however, is stopped, when the feed roller 3 is stopped, before the spinning rotor 2 is stopped. At the same time, the time switch T2 is energized.
(2) When the solenoid coil of the relay MS is open, the circuit comprising the break contact ms-2, break contact t7 of the time switch T7, having a predetermined delay time T 7 , and either the solenoid coil of the relay CR5 or the time switch T6 is closed. Then the solenoid coil of the relay CR5 is energized and the time switch T6 is energized.
(3) When the solenoid coil of the relay CR5 is energized, both the circuit comprising the contact cr2-2 of the relay CR2, the break contact cr5-1 of the relay CR5 and the exciting coil 53C for driving the clutch 53, and the circuit comprising the contact cr4-2 of the relay CR4, the break contact cr5-2 of the relay CR5 and the exciting coil 54C for driving the clutch 54 are opened. Then, the driving of the electromagnetic clutch 53 connected to the feed roller 3 and the electromagnetic clutch 54 connected to the groove roller 14, with which the traverse guide 11 is engaged, is stopped. At the same time, the circuit comprising the contact cr5-3 and either the exciting coil 62B, for driving the brake 62 connected to the feed roller 3, or the exciting coil 63B, for driving the brake 63 connected to the groove roller 14 with which the traverse guide 11 is engaged, is closed. Then the feed roller 3 and the traverse guide 11 are braked and brought to a standstill.
(4) When the predetermined time T 6 has passed after the time switch T6 is energized, the time switch T6 is closed and the circuit comprising the contact ms-2 of the relay MS, the contact t6 of the time switch T6 and the solenoid coil of the relay CR6, is closed. Then, the solenoid coil of the relay CR6 is energized and the contact cr6-1 is closed so that the time switch T7 is energized.
(5) When the solenoid coil of the relay CR6 is energized, the circuit comprising contact cr3-3 of the relay CR3, the break contact cr6-2 of the relay CR6 and the exciting coil 51C for driving the electromagnetic clutch 51 is opened. Therefore, the electromagnetic clutch 51 connected to the winding drum and the draw off roller 7 becomes open. At the same time, the circuit comprising contact cr6-3 and the exciting coil 61B, for driving the magnetic brake 61, is closed. Then, the magnetic brake 61 connected to the winding drum 15 and draw off roller 8 becomes engaged and both the winding drum 15 and the draw off roller 8 are brought to a standstill, while the main motor 33 continues its rotation due to its inertia.
In this case, it is necessary that the delay time T 6 of the time switch T6 be adjusted so that it is suitable for the maintaining of the end of the yarn within the delivery tube 4.
(6) When the time switch T7 is energized for the predetermined time T 7 , the time switch T7 is closed and the solenoid coils of the relays CR5 and CR6, wired to the break contact t7, become open. Then the exciting coils 62B, 63B and 61B for driving the magnetic brakes 61, 62 and 63, respectively, become open. The delay time T 7 of the time switch T7 is adjusted so that the time switch can be closed after the winding drum 15 and the draw off roller 8 are brought to a complete standstill.
(7) When the predetermined time T 2 is passed after the push-button switch PB2 is pushed, the time switch T2 is closed. Then the break contact t2 of the time switch T2 is opened and, at that time, all of the holding circuits are open.
The stopping operation of the open-end spinning machine according to the present invention is completed as described above. During the stopping operation of the machine the yarn 7 is wound around the cheese 18 at a certain portion of the cheese 18. This is because, the traverse guide 11 is brought to a standstill before the winding drum 15 and the draw off roller 8 are brought to a standstill, and the yarn 7 fed via the draw off roller 8, the winding drum 15 and the traverse guide 11 is wound around the cheese at the above-mentioned certain portion. Consequently, at the time of restarting the operation of the open-end spinning machine, it is possible to rewind the yarn 7 wound around the above-mentioned certain portion of the cheese 18, so that the yarn tension between the discharging point of the cheese 18 and the traverse guide 11 does not vary and a smooth starting operation can be carried out. | Disclosed is an open-end spinning machine and a method of stopping the same. The machine comprises: feed rollers, for supplying fibers to a combing roller, connected to a main power source via a clutch; a spinning rotor, for collecting the fibers combed by the combing roller into a yarn and for twisting the yarn, connected to another power source via a clutch; a draw off roller and a press roller urged toward the draw off roller, for withdrawing the yarn from the spinning rotor, connected to the main power source via an endless driving belt and to a brake; a traverse guide, for traversing the withdrawn yarn along a bobbin supported by a pair of cradle arms, connected to the main power source via a clutch and to a brake; a winding drum, for frictionally driving the bobbin to wind the yarn around the bobbin and form a cheese, connected to the main power source and; a controlling device, for controlling the brakes and clutches according to a predetermined program, by which the traverse guide is stopped when both the feed rollers and the spinning rotor are turned off, but before both the draw off rollers and the winding drum are stopped. By utilizing this machine and method, the number of yarn breakages occurring during the starting operation is decreased. | 3 |
TECHNICAL FIELD
[0001] A seat belt system of a four-point arrangement is provided. Particularly, a four-point seat belt system is provided having a shoulder belt arrangement with adjustable retractors and guide loops to provide both security and comfort to the wearer-occupant.
BACKGROUND OF THE INVENTION
[0002] Automotive vehicles incorporate a variety of restraint systems to provide for the safety of vehicle occupants. For example, it is known in the vehicle art to provide various types of seat belts or restraint systems for restraining an occupant in his or her seat and providing controlled deceleration of portions of the body to limit the forces applied to the occupant's body during rapid deceleration of a vehicle from a cause such as a collision. Various types of seat belts and restraint systems have been used in automobiles, trucks, and other vehicles and are commonly known today.
[0003] Known seat belt systems typically used in commercially available production vehicles are three-point restraint systems with a lap belt and a shoulder belt extending over one shoulder of the occupant and connecting with the lap belt. The lap belts are anchored at one end, to the seat or to the vehicle adjacent the seat. The shoulder belts are connected at one end to the vehicle or to the seat and at the other end to the lap belt or lap belt buckle mechanism.
[0004] Four, five, and six-point restraint systems are among some of the seat belt and restraint systems that are particularly utilized in off-road type vehicles and other sport-type vehicles in order to provide additional restraint for occupants over two and three-point restraint systems. These seat belt systems tend to have multiple adjustable cinching mechanisms and are awkward and difficult to operate and properly position on an occupant. They also may be less comfortable and more complex due to the multiple mechanisms and therefore not amenable to quick donning and doffing on multiple occasions as may be required in a passenger vehicle.
[0005] Of particular interest to the automotive industry today is the four-point seat belt restraint system. Some of the four-point seat belt systems currently envisioned are essentially parallel shoulder belts. While providing a certain degree of protection, the systems currently envisioned may cause the seat occupant discomfort as a consequence of the shoulder belts contacting the neck during belt use. In addition, this discomfort may well be exacerbated if the lateral spacing of the shoulder belt is small. For example, if the lateral spacing of the shoulder belt is 130 mm along an occupant's clavicles, discomfort may result, since the belts may contact the occupant's neck area. As a consequence use of the four-point seat belts might be less than that of three-point belts negating the expected improvement in performance in society as a whole.
[0006] A further difficulty created by four-point seat belt restraint systems that use parallel shoulder belts is that the belts will fit differently on different sized occupants. For example, the belts may be too wide for smaller occupants and may be too narrow for larger occupants depending on the centerline-to-centerline spacing. This could affect the ability to maintain the position of the seat belts on the shoulders of the occupants during normal vehicle operation as well as during an impact event.
[0007] Other difficulties with known four-point seat belt restraint systems relate to the buckling systems. Specifically, the buckle-tongue arrangement of some four-point seat belt systems, in which the left hand shoulder belt and lap belt are connected to the buckle (or to the tongue) and the right hand shoulder belt and lap belt are connected to the tongue (or to the buckle), may have the tendency to “ride up” or move in an upward direction, that is, away from the occupant's lap during normal vehicle operation. The effect of this “ride up” could result in pre-submarining of the occupant, thus possibly leading to submarining of the occupant in an impact event.
[0008] Accordingly, a need exists today for an improved four-point seat belt system for use in vehicles that provides proper and constant belt alignment during normal vehicle operation as well as during an impact event. Such a system must be comfortable to the wearer. In addition, a need also exists for a four-point seat belt restraint system that prevents pre-submarining by restricting the movement of the lap-belt portion of the belt system from the pelvis to the abdomen during an impact event.
SUMMARY OF THE INVENTION
[0009] The disclosed embodiments of the invention provide a four-point seat belt restraint system mounted on a vehicle seat which maintains proper belt alignment and routing for the four-point system during normal use and during impact events as well as properly reducing and distributing forces applied to the body of the occupant during rapid deceleration conditions. In the preferred embodiment the four-point seat belt restraint system includes a pair of shoulder belts which wrap around the upper portion of the vehicle seat. Each of the pair of shoulder belts converges at a seat belt buckle assembly thereby defining a V-shape. The shoulder belts are anchored to the seat, for example, by a single retractor having a dual spool or by a pair of retractors which may be relocated to adjust for both occupant size and occupant comfort. The shoulder belts are anchored on the seat so that they cross one another. As an alternative to anchoring the shoulder belts to the seat the shoulder belts could be mounted to the vehicle. Both arrangements assist in maintaining the V-shape configuration of the shoulder belts.
[0010] A vertically-movable headrest having a pair of spaced-apart horizontally-movable seat belt loops is optionally provided. Vertical movement of the headrest and horizontal movement of the seat belt loops enhance the ability of the described four-point seat belt restraint system to allow and improved and more comfortable fit for a great variety of occupants having different builds.
[0011] A pair of lap belts is provided. Each of the lap belts is anchored to the underside of the seat by a retractor. A lap belt loop may be provided for each of the lap belts which may be manually or automatically adjusted vertically. Vertical adjustment of the lap belt loops also enhances the suitability of the four-point seat belt restraint system for a variety of different occupants. Both shoulder belt and lap belt tension may be adjusted as desired.
[0012] Other features of the invention will become apparent when viewed in light of the detailed description of the preferred embodiment when taken in conjunction with the attached drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] For a more complete understanding of this invention, reference should now be made to the embodiment illustrated in greater detail in the accompanying drawings and described below by way of examples of the invention wherein:
[0014] FIG. 1 illustrates a front view of a four-point seat belt restraint system in a non-use position according to a first embodiment of the invention;
[0015] FIG. 2 illustrates a perspective view of a vehicle seat incorporating the four-point seat belt restraint system in a non-use position according to a second embodiment of the invention;
[0016] FIG. 3 illustrates a front view of the second embodiment of the four-point seat belt restraint system shown in FIG. 2 illustrating the headrest in its raised position and the headrest seat belt loops in their retracted positions;
[0017] FIG. 4 illustrates the same view as FIG. 3 but shows the headrest in its lowered position and the headrest seat belt loops in their extended positions;
[0018] FIG. 5 illustrates a front view of an alternate embodiment of the present invention; and
[0019] FIG. 6 illustrates a front view of another alternate embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] In the following figures, the same reference numerals will be used to refer to the same components. In the following description, various operating parameters and components are described for one constructed embodiment. These specific parameters and components are included as examples and are not meant to be limiting.
[0021] Referring to the drawings and in particular to FIG. 1 , one embodiment of a four-point seat belt restraint system, generally illustrated as 10 , is shown. A seat 12 , typically for use in an automotive vehicle (not shown), includes a generally upright seat back 14 extending between a top portion 16 and a bottom portion 18 for supporting the back of a seated occupant. The seat 12 further includes a generally horizontal seat cushion 20 projecting forwardly from the bottom portion 18 of the seat back 14 and extending between an inboard or right side 22 and an outboard or left side 24 for supporting the bottom of the seated occupant. The inboard side 22 is further defined by the side of the seat 12 adjacent the inboard or middle of the vehicle and the outboard side 24 is further defined by the side of the seat 12 adjacent the outboard or outside of the vehicle as is commonly known in the art.
[0022] The four-point seat belt restraint system 10 includes a first, or inboard shoulder belt webbing 26 extending from the top portion 16 to the bottom portion 18 of the seat back 14 adjacent the inboard side 22 of the seat cushion 20 . The four-point seat restraint system 10 further includes a second, or outboard, shoulder belt webbing 28 extending from the top portion 16 to the bottom portion 18 of the seat back 14 adjacent the outboard side 24 of the seat cushion 20 . The four-point seat belt restraint system 10 further includes a first, or inboard, lap belt webbing 30 extending from the inboard side 22 of the seat cushion 20 to a buckle (tongue) component 32 and a second, or outboard, lap belt webbing 34 extending from the outboard side 24 of the seat cushion 20 to a tongue (buckle) component 36 . It is to be understood that the component 32 can be either a buckle or a tongue and the component 36 can be either a tongue or a buckle. References made to these elements are made with this interchangeability in mind.
[0023] It is preferred that a downward force be applied to the first shoulder belt webbing 26 and to the second shoulder belt webbing 28 . Such a force helps to maintain the buckle/tongue as low on the occupant as possible to minimize submarining. Belt webbing tension is in part a function of the weight of the components 32 and 36 (in addition to the retractor force exerted by the shoulder belt retractors 44 and 42 and by the lap belt retractors 38 and 40 ). The lower the buckle rides on the occupant, the greater the tension applied to the shoulder belt 26 and the shoulder belt 28 . Accordingly, a lower position of the components 32 and 36 may be achieved by the optional addition of weights. Specifically, a weight 33 may be added to the buckle (tongue) component 32 and a weight 37 may be added to the tongue (buckle) component 36 . The weights 33 and 37 may be composed of any of a variety of materials including, for example, a metal such as lead or a high density polymer. The weights 33 and 36 may be disposed internally with respect to the components 32 and 36 or may be fitted externally. Furthermore, the weights 33 and 36 may be interchangeable with greater or lesser weights depending on the requirements of the occupant.
[0024] The first lap belt webbing 30 is anchored to the seat 12 by a retractor 38 . The retractor 38 is anchored to the seat by fasteners including bolts, welds and the like. The second lap belt webbing 34 is anchored to the seat 12 by a retractor 40 , also attached to the seat 12 by the mentioned fasteners. The retractors 38 and 40 are fixed to the seat 12 . Fixation may be achieved in a variety of ways. One method of fixation is illustrated whereby the retractors 38 and 40 are positioned substantially under the seat 12 . The location of the lap belt retractors 38 and 40 under the seat makes packaging of the retractors easier and more economical, particularly in vehicles where seat-to-tunnel or seat-to-door spacing is restricted. As an alternative the retractors 38 and 40 may be attached to the sides of the seat (not shown).
[0025] While two retractors 38 and 40 are illustrated it is to be understood that a single retractor may be used in lieu of the shown and discussed pair. Conversely, the retractors 38 and 40 may be substituted for by a rigid, fixed anchor as is known in the art. The retractors 38 and 40 may be of a variety of types, including mechanical, mechanical with electric lock-up, electromagnetic, and others. An electric retractor is valuable in that it offers a selected tension (either constant or varying) to be imposed on the lap belts 30 and 34 to aid in maintaining the components 32 and 36 as low on the occupant's lap as possible. In addition, a high lap belt tension also resists lateral motion of the lap belts 30 and 34 , thereby assisting in maintaining the buckle-tongue interface of the components 32 and 36 as close to the centerline of the occupant as is possible. This arrangement offers an improvement over known restraint systems using conventional mechanical retractors. The retractors 38 and 40 are also equipped with dynamic pretensioners (of the pyrotechnic type or of another design). The retractors 38 and 40 also may be equipped with static pretensioning.
[0026] The first shoulder belt webbing 26 may be fixed or may be releasably attachable to the buckle (tongue) component 32 and the second shoulder belt webbing 28 is releasably attachable to the tongue (buckle) component 36 . The buckle (tongue) component 32 may be fixed or may be releasably attachable to the tongue (buckle) component 36 . (By allowing for the possibility of releasable attachment of the belt webbing to the buckle component ease of both assembly and service is enhanced.) This arrangement results in the illustrated V-shape defined by the substantial convergence of the first shoulder belt webbing 26 and the second shoulder belt webbing 28 at the components 32 and 36 . The first shoulder belt webbing 26 and the second shoulder belt webbing 28 have a large lateral spacing as illustrated from the occupant's neck (not shown) while still providing effective support by the convergence along the centerline of the occupant at the area of the components 32 and 36 . This increased lateral spacing at the upper part of the seat 12 increases occupant comfort for occupants of different sizes, including smaller occupants having smaller necks, narrower shoulders and shorter upper torso eights. This geometry also aids in keeping seat belts on the occupant's shoulders at all times, while lowering the risk of soft tissue neck injury and enhancing comfort for wide range of occupant builds.
[0027] It is to be understood that the buckle arrangement illustrated in FIG. 1 may be altered so that, for example, the buckle component is provided on the shoulder webbing. The configuration shown is intended as being illustrative and not limiting.
[0028] The first shoulder belt webbing 26 is anchored to the seat 12 by a retractor 42 that is fixedly secured to the seat 12 by fasteners including bolts, welds and the like. The second shoulder belt webbing 28 is anchored to the seat 12 by a retractor 44 which is also fixedly secured to the seat 12 by the noted fasteners. The retractors 42 and 44 are preferably but not necessarily equipped with load-limiting features which may be of the single or multiple level and discrete or continuous type as is known in the art. Load limiting offers the advantages of enhancing control of the occupant's upper torso kinematics, and limiting the tension load applied by the shoulder belt to the lapbelt, approximately limiting the load transferred by the restraint system to the upper torso, thus helping to minimize submarining in an impact event. The dynamic and static load pretensioners described above with respect to the retractors 38 and 40 combines with this load limiting feature to assist in minimizing submarining. Pre-impact tensioning is useful in reducing slack prior to an impact which in turn may improve occupant coupling to the seat and to the restraint system.
[0029] As illustrated in FIG. 1 , the retractor 42 is positioned on the seat back at a location that is on the side opposite that of the first shoulder belt webbing 26 . The retractor 44 is also positioned on the seat back at a location that is on the side opposite that of the second shoulder belt webbing 28 . This arrangement defines a crossed pattern that allows for the desired belt orientation and belt angles relative to the occupant's shoulder and was determined from testing with human volunteers to improve comfort. The first shoulder belt webbing 26 and the second shoulder belt webbing 28 follow over the top of the seat 12 and provide a change of direction without twisting or folding at the top of the seat back. This arrangement also provides for enhanced occupant comfort and performance in that the first shoulder belt webbing 26 and the second shoulder belt webbing 28 are able to lie more naturally on the curve of the occupant's shoulder.
[0030] An alternate embodiment of the four-point seat belt restraint system of the present invention is illustrated in FIGS. 2 through 4 and is generally illustrated as 50 . A seat 52 is shown and includes a generally upright seat back 54 extending between a top portion 56 and a bottom portion 58 for supporting the occupant's back. The seat 52 further includes a generally horizontal seat cushion 60 projecting forward from the bottom portion 58 of the seat back 54 . The seat cushion 60 extends between an inboard or right side 62 and an outboard or left side 64 for supporting the seated occupant. The inboard side 62 is further defined by the side of the seat 52 adjacent the inboard or middle of the vehicle and the outboard side 64 is further defined by the side of the seat 52 adjacent the outboard or outside of the vehicle.
[0031] A movable headrest 66 is attached to the area of the top portion 56 of the upper seat back 54 in a known manner. The headrest 66 is movable between a raised position illustrated in FIG. 3 and a lowered position illustrated in FIGS. 2 and 4 . The headrest 66 includes a pair of lateral seat belt loops 68 and 68 ′. Each of the loops 68 and 68 ′ is movable between an outboard position and an inboard position. The inboard position is illustrated in FIG. 3 while the outboard position is illustrated in FIGS. 2 and 4 . It should be noted that while the configuration of the seat belt loops 68 and 68 ′ are shown as being loops that surround the shoulder belts 70 and 72 , other configurations of belt retainers may be used such as substantially horizontal flanges.
[0032] The loops 68 and 68 ′ retain the shoulder belts 70 and 72 in a spaced apart configuration with respect to the body of the seat occupant. By achieving a certain separation between shoulder belts 70 and 72 the comfort of the occupant is optimized. Ideally the shoulder belts 70 and 72 are spaced such that they are positioned over the clavicles of the adult occupant (not shown). This spacing may vary, but ideally is between about 180 mm and about 208 mm from the centerline of the shoulder belt 70 to the centerline of the shoulder belt 72 at about the height of the front edge of the clavicle of a mid-sized male occupant. The spacing of the shoulder belts 70 and 72 is symmetrical about the centerline of the occupant.
[0033] As set forth above in FIG. 1 and as described in conjunction therewith in relation to the four-point seat belt restraint system 10 , the four-point seat belt restraint system 50 shown in FIGS. 2 through 4 includes a first, or inboard shoulder belt webbing 70 extending from the top portion 56 of the seat back 54 to the bottom portion 58 . A second, or outboard shoulder belt webbing 72 is also provided and similarly extends from the top portion 56 of the seat back 54 to the bottom portion 58 of the seat back 54 .
[0034] The four-point seat belt restraint system 50 further includes a first, or inboard, lap belt webbing 74 extending from the inboard side 62 to a buckle (tongue) component 76 . The system 50 further includes a second, or inboard, lap belt webbing 78 extending from the outboard side 64 of the seat cushion 60 to a tongue (buckle) component 80 . The first lap belt webbing 74 is anchored to the seat 52 by a retractor 82 . The retractor 82 is anchored to the seat 52 by fasteners as previously described. The second lap belt webbing 78 is similarly anchored to the seat 52 . The retractors 82 and 84 are similar in form and function to the retractors 38 and 40 mentioned above and described with respect to FIG. 1 , including all of the listed possible variations useful in adjusting belt tension.
[0035] The retractors 82 and 84 are disposed beneath the seat cushion 60 . This positioning provides the lap belt webbings 74 and 78 with an anchoring position that is substantially forward of the seat back 52 . Positioned in this manner the lap belt webbings 74 and 78 also provide a more comfortable arrangement for the occupant/wearer.
[0036] The buckle (tongue) component 76 is releasably attachable to the tongue (buckle) component 80 . The first shoulder belt webbing 70 may be releasably attached to the components 76 and 80 and the second shoulder belt webbing 72 may be releasably attached to the components 76 and 80 . A “V” configuration defined by the first shoulder belt webbing 70 and the second shoulder belt webbing 72 is formed by convergence of the webbings 70 and 72 at the components 76 and 80 . The lateral spacing provided by this configuration and all of the benefits achieved thereby are the same as that discussed above with the four-point seat belt restraint system 10 discussed above.
[0037] The headrest 66 may be raised to a position illustrated in FIG. 3 or may be lowered to a position illustrated in FIG. 4 . In addition, the lateral seat belt loops 68 and 68 ′ may be adjusted horizontally between the inboard position illustrated in FIG. 3 and the outboard position illustrated in FIGS. 2 and 4 . Vertical adjustment of the headrest 66 (or, as an alternative, load-bearing posts mounted on the seat back [not shown]) allows for vertical adjustment of the lateral seat belt loops 68 and 68 ′. The adjustment of both the headrest 66 and its associated lateral seat belt loops 68 and 68 ′ may be automatically made (as by mechanical, magnetic or electrical movement) or may be made manually, as an alternative or in combination with the automatic adjustment feature. By horizontal movement of the lateral seat belt loops 68 and 68 ′ with respect to the headrest and upon vertical movement of the headrest 66 , the preferred lateral spacing of the shoulder belts 70 and 72 can be achieved for occupants having different sizes, particularly for occupants having differently-sized torsos. The occupant is thus provided with added comfort and has the added benefit of benefiting from improved seat belt system performance in both normal driving conditions and during an impact event.
[0038] The first shoulder belt webbing 70 is anchored to the seat by a retractor 86 that is movably secured to the seat 52 by fasteners described above. The second shoulder belt webbing 72 is fixedly secured to the seat 52 by a retractor 88 that is movably secured to the vehicle seat 52 by fasteners. The retractors 86 and 88 are shown in their first, lower position in FIG. 3 and have been relocated to their second, higher position in FIG. 4 . While two positions are illustrated it is to be understood that a range of positions may be possible utilizing the appropriate connectors. Movement of the retractors 86 and 88 between positions provides the occupant with different shoulder belt arrangements as dictated by the occupant's size and shape. This arrangement also helps to prevent twisting or folding of the belts.
[0039] The seat restraint system 10 is designed to control occupant motion and reduce force levels on the occupant's chest. During a crash event the system 10 allows the occupant's torso to reach the vertical position or forward of vertical at the time of peak belt forces. The pretensioning of the retractors 38 and 40 by pyrotechnical, electrical, mechanical, or other means ensures contact of the lap belts 30 and 34 with the pelvis during the crash loading. As shown in FIG. 2 , a seat ramp 89 , also included in the seat restraint system 10 , further minimizes the horizontal travel and vertical drop of the occupant's pelvis. The seat ramp 89 may be of various type, style, material, and shape as known in the art. The seat ramp 89 is commonly made from sheet metal and may be deformable during a collision. The seat-ramp 89 is most commonly located beneath seat cushion padding as illustrated in FIG. 2 , under the occupant's pelvis and thigh region. The seat ramp 89 is angled with the front portion higher vertically than the rear portion, so as to prevent the forward horizontal travel of an occupant during a forward collision. In order for an occupant to travel in a forward direction the occupant would need to slide up the seat ramp 89 against the force of gravity, rather than for example a flat seat, which would have less resistance. Also, for a similar reason the seat ramp 89 in having an inclined shape, during a forward collision, when an occupant tends to move forward in the direction of the collision, the shape and material of the seat ramp 89 resists the ability for the occupant's pelvis to drop vertically. The combination of the above-described system components, when properly coupled, prevents the possibility of the shoulder belts 26 and 28 from pulling the lap belts 30 and 34 off of the pelvis during a crash, resulting in one form of “submarining” whereby the occupant's pelvis slides under the lap belt.
[0040] To increase the adaptability of the four-point seat belt restraint system 50 to a variety of differently-sized occupants, a vertically adjustable lap belt loop 90 is provided to restrict side-to-side movement of the first lap belt webbing 74 . For the same reason a vertically adjustable lap belt loop 92 is provided to restrict side-to-side movement of the second lap belt webbing 78 . As illustrated in FIGS. 3 and 4 , the vertically adjustable lap belt loop 90 and the vertically adjustable lap belt loop 92 can be moved from raised positions to lowered positions, the latter positions being illustrated by vertically adjustable lap belt loop 90 ′ and vertically adjustable lap belt loop 92 ′ with the lap belt webbing being shown in broken lines. This vertical adjustment functions to allow a change in the angle of the lap belt webbings 74 and 78 and hence alter the vertical component of the static lap belt force to due the lap belt retractors 82 and 84 , respectively. As noted above, static belt tension assists in keeping the lap belt webbings 74 and 78 on the occupant's lap. Movement of the adjustable lap belt loops 90 and 92 to their lowered positions illustrated in broken lines translates to a larger vertical component of the static belt force, resulting in increased resistance to the ride up of the components 76 and 80 . Conversely, movement of the adjustable lap belt loops 90 and 92 to their upper positions translates to a smaller vertical component, thus enhancing occupant comfort. Vertical adjustment of the adjustable lap belt loops 90 and 92 may be made either manually or automatically.
[0041] The angle of the lap belt webbings 74 and 78 is preferably substantially between about 0° and 32° from vertical and is more preferably about 16° from vertical in a side view such as that shown in FIG. 2 . Selection of the angle depends on the balance of the downward force on the components 76 and 80 with the necessary restraining force. Also considered is the balance between the downward force of the lap belts 74 and 78 against the upward force on the shoulder belts 70 and 72 .
[0042] The seat belt and retractor configurations discussed above relate to one preferred embodiment of the present invention in which the seat belt retractors are fitted to the seat itself. An alternate arrangement is shown in FIG. 5 in which the seat belt retractors are mounted instead to an area of the vehicle interior adjacent to the seat.
[0043] Particularly, a vehicle seat assembly, generally illustrated as 100 , is shown in which a vehicle seat includes a vehicle seat back 102 and a vehicle seat base 104 . The vehicle seat base 104 is fixed (or is movably attached) to a vehicle floor pan 106 in a conventional manner.
[0044] A pair of shoulder belts 108 and 110 is provided. The shoulder belt 108 extends through an aperture 112 formed in the vehicle seat back 102 . The shoulder belt 110 extends through an aperture 114 also formed in the vehicle seat back 102 . The apertures 112 and 114 maintain the shoulder belts 108 and 110 in the preferred configuration set forth above with respect to the embodiment shown in FIGS. 2 through 4 .
[0045] One end of the shoulder belt 108 is attached to a buckle (tongue) component 116 . The other end of the shoulder belt 108 is attached to a shoulder belt retractor 118 . One end of the shoulder belt 110 is attached to a tongue (buckle) component 117 . The other end of the shoulder belt 110 is attached to a shoulder belt retractor 120 . It is to be understood that the component 116 can be either a buckle or a tongue and the component 117 can be either a tongue or a buckle. References made to these elements are made with this interchangeability in mind. The shoulder belt retractors 118 and 120 are fixedly attached to the vehicle interior such as on vehicle interior cross-member 122 .
[0046] A pair of lap belt webbings 124 and 126 is provided in relation to the vehicle seat base 104 . One end of the lap belt webbing 124 is attached to the buckle (tongue) component 116 . The other end of the lap belt webbing 124 is attached to a lap belt webbing retractor 128 . Similarly, one end of the lap belt webbing 126 is attached to the tongue (buckle) component 117 . The other end of the lap belt webbing 126 is attached to a lap belt webbing retractor 130 . The lap belt webbing retractors 128 and 130 are fixedly attached to the vehicle interior such as on vehicle interior cross-member 132 . To maintain the lap belt webbing 124 in its proper position relative to the vehicle seat base 104 a guide loop 134 is provided and is preferably attached to the vehicle seat base 104 . In addition, to maintain the lap belt webbing 126 in its proper position relative to the vehicle seat base 104 a guide loop 136 is provided and is preferably attached to the vehicle seat base 104 . Both of the guide loops 134 and 136 may be adjustable (for example, vertically) as set forth above with respect to the embodiment illustrated in FIG. 3 .
[0047] An alternative arrangement for attachment of the seat belt retractors to an area of the vehicle other than the seat shown in FIG. 5 is illustrated in FIG. 6 . With reference to FIG. 6 , a vehicle seat assembly, generally illustrated as 200 , is shown in which a vehicle seat includes a vehicle seat back 202 and a vehicle seat base 204 . The vehicle seat base 204 is fixed (or is movably attached) to a vehicle floor pan 206 .
[0048] A first shoulder belt 208 and a second shoulder belt 210 are provided. The first shoulder belt 208 extends through an aperture 212 formed in the vehicle seat back 202 . The second shoulder belt 210 extends through an aperture 214 also formed in the vehicle seat back 202 . Like the apertures 112 and 114 shown in FIG. 5 and discussed in relation thereto, the apertures 212 and 214 maintain the shoulder belts 208 and 210 in the preferred configuration v-shape discussed above.
[0049] One end of the first shoulder belt 208 is attached to a buckle (tongue) component 216 . The other end of the first shoulder belt 208 is attached to a first shoulder belt retractor 218 . One end of the second shoulder belt 210 is attached to a tongue (buckle) component 217 . The other end of the second shoulder belt 210 is attached to a second shoulder belt retractor 220 . The component 216 can be either a buckle or a tongue and the component 217 can be either a tongue or a buckle.
[0050] The first shoulder belt retractor 218 and the second shoulder belt retractor 220 are fixedly attached to the vehicle interior such as on vehicle interior cross-member 232 . As illustrated, the first shoulder belt retractor 218 is fitted to the interior cross-member 232 at a point opposite the aperture 212 and the second shoulder belt retractor 220 is fitted to the interior cross-member 232 at a point opposite the aperture 214 . Thus positioned a criss-cross arrangement of the first shoulder belt 208 and the second shoulder belt 210 is defined on the back side of the vehicle seat back 202 .
[0051] A pair of lap belt webbings 224 and 226 is provided. One end of the lap belt webbing 224 is attached to the buckle (tongue) component 216 . The other end of the lap belt webbing 224 is attached to a lap belt webbing retractor 228 . One end of the lap belt webbing 226 is attached to the tongue (buckle) component 217 . The other end of the lap belt webbing 226 is attached to a lap belt webbing retractor 230 . The lap belt webbing retractors 228 and 230 are fixedly attached to the vehicle interior cross-member 232 . A guide loop 234 is provided and is preferably (but not exclusively) attached to the vehicle seat base 204 to maintain the lap belt webbing 224 in its preferred position. Similarly, a guide loop 236 is also attached to the vehicle seat base 204 to maintain the lap belt webbing 226 in its preferred position. Both of the guide loops 234 and 236 may be adjustable in for example, the vertical direction.
[0052] While the invention has been described in connection with one or more embodiments, it is to be understood that the specific mechanisms and techniques which have been described are merely illustrative of the principles of the invention, numerous modifications may be made to the methods and apparatus described without departing from the spirit and scope of the invention as defined by the appended claims. | A four-point seat belt system for restraining a vehicle occupant in a vehicle seat is disclosed. Two shoulder belts are provided which are buckled together with a pair of lap belts. The convergence of the shoulder belts created at the buckles defines a V-shaped configuration which aids in occupant safety and comfort. Movably-adjustable retractors are provided to anchor the upper end of each shoulder belt to the vehicle seat. A movable headrest having a pair of laterally-adjustable belt loops is provided to further enhance occupant security and comfort. | 1 |
FIELD OF THE INVENTION
This invention relates to gas and air filtration systems. In particular, it relates to the removal of fine particulates like dust from gaseous flows.
BACKGROUND OF THE INVENTION
In the previous art, various combinations of ionizing and dust collecting elements have been used to produce high efficiency electronic air filters. One classic example is the standard precipitator type electronic air filter in which ionizing fine wires of about 0.005 inches diameter, charged at about 7 kilovolts are placed between grounded plates to generate a corona and charge the dust particles passing therethrough. Further down the air flow path, alternating charged and grounded plates collect the charged particles of dust.
Precipitating filters, while highly efficient, produce large number of ions and generate ozone. They also consume distinct quantities of current at high voltage, thereby requiring substantial power supplies.
Another type of electronic air filter is the non-ionizing, polarized dielectric media type. This is not as efficient as the precipitator type but it is cheaper and easier to maintain. This filter uses filament pads of non-conducting, dielectric material sandwiched between charged and grounded screens which produce electrostatic fields to polarize these pads. Any particulates passing through the filter also get polarized and they are attracted and collected by the packed filaments within the pads. This type of system produces very few ions, if any at all, no ozone and consumes virtually no current. The power supply required is thus of a low power type.
Prior art patents based on the polarization principle by the present inventor are U.S. No. 4,549,887 and No. 4,828,586. The first patent describes a pair of outer hinged screens for enclosing a pair of glass fibre pads with a central grid therebetween. The central grid, made of coarse wire mesh that is on the order of 0.020 inches in diameter, is charged to around 7000 volts and the outer screens are grounded. This combination does not generate ions significantly. The spacing between the charged screens is between one and two inches, producing a steep electric field gradient. This field gradient polarizes the non-conducting glass fibres rendering them active in trapping dust particles, and more effective than non-polarized pads.
An advantage of this type of filter is that the accumulated dust is readily removed by exchanging the glass fibre pads for fresh pads.
Both of the above designs have disadvantages. The precipitator type, although it is very efficient when clean, because of the limited surface of the collecting plates, its efficiency drops as the filter loads up with dust. The filter's loading capacity, especially for the larger particles, is very low. Maintenance of the precipitator type filters is very tedious especially in industrial and commercial applications. Also they are expensive both in original investment and operating costs since they have very elaborate construction and have large high voltage power supplies that consume anywhere from 80 to 150 watts.
The polarizing filters do not have the disadvantages of the precipitator filters but they lack efficiency.
In view of the foregoing, it is the object of my present invention to provide an electronic filter which is highly efficient, easy to maintain and inexpensive.
The invention in its general form will first be described, and then its implementation in terms of specific embodiments will be detailed with reference to the drawings following hereafter. These embodiments are intended to demonstrate the principle of the invention, and the manner of its implementation. The invention in its broadest and more specific forms will then be further described, and defined, in each of the individual claims which conclude this Specification.
SUMMARY OF THE INVENTION
The invention herein is based on combining features of polarization and ionization in one simple design. Generally, the embodiment of my present invention consists of fibrous pads of dielectric material placed between a charged active grid and a grounded screen similar to as described in my previous patents. The charged grid is, however, made in such a way that it provides a degree of ionization within the air flow passing through the filter. This may be achieved either by providing fine wires which produce ions because of the high potential gradient that such wires form; or by providing an array of fine, sharp points carried by conductive filaments which do the same thing. Besides producing ions, the ionizing grid produces an electrostatic field between the grid itself and the grounded screen which polarizes the fibrous pad which is located therebetween. In this way, the filter operates both in the polarizing mode and the ionizing mode at the same time.
The foregoing summarizes the principal features of the invention and some of its optional aspects. The invention may be further understood by the description of the preferred embodiments, in conjunction with the drawings, which now follow.
Several embodiments of the present invention will hereinafter be described by way of example only and with reference to the following drawings herein.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows an exploded perspective view of the compounds of a basic filter with fine wires as the ionizing grid.
FIG. 2 shows the construction of the assembled filter of FIG. 1 in cross-sectional view.
FIG. 3 shows a central grid composed of fine, ionizing wires.
FIGS. 4, 5 and 6 show alternate arrangements for the ionizing grid.
FIG. 7 shows an exploded perspective view of a pad where the ionizing grid is attached to one of the fibrous pads.
FIG. 8 shows a perspective view of a hinged filter arrangement where the two outside screens are hinged together and the central ionizing grid is hinged with insulating hinges. Power to the central grid is supplied by a high voltage power supply attached to one of the outside screen frames.
FIG. 9 is a similar figure to FIG. 8 except that the central ionizing grid is attached to one of the fibrous pads. High voltage to the grid is supplied via a conducting strip connected to a high voltage power supply.
FIG. 10 is a graph showing the removal of particles over time from a room using respectively a prior art polarized filter, a prior art precipitating ionizing filter and a filter according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A convenient way of providing an ionizing grid is to render a cord of composite filaments of short fibres, such as cotton, conductive. Each of the short fibres may be of a small enough diameter to effect ionization. Alternately, or additionally, each fibre may provide an end that has around it a higher field gradient than the fibre itself thereby creating ions.
This grid of broken fibre lengths joined in a conductive string may be prepared by applying a conductive material, such as a high carbon ink, to the fibre. A conductive path may similarly be deposited onto a fabric woven with similar filaments.
In this manner, a source of ionization is provided that is substantially less expensive than a system based on use of a grid of fine wires. Nevertheless, such wires may be employed as the ionizing source for the invention.
Referring to the drawings, FIG. 1 shows the assembly of components for a cartridge filter according to the invention. Two outside perforated retainers form the outside case of the filter. Two outside conducting polarizing screens 2 are mounted within the frames 1. Two fibrous pads 3, preferably made of glass fibres, are placed centrally between the polarizing screens 2. Located centrally between the pads 3 is the ionizing grid 4. Ionizing grid 4 comprises fine wires 5 which ionize the surrounding air when high voltage is applied to them by virtue of a high potential gradient which is present around the wires. The diameter of wires 5 is preferably between 0.001 and 0.007 inches causing ionization at a potential of 7000 volts. Their spacing is between 0.5 inches and 2 inches. The spacing between the grid 4 and screens 3 is between one half and one inches to produce the polarizing field gradient.
FIG. 2 shows a cross-sectional view of the cartridge filter shown in FIG. 1 when assembled. A high voltage power supply 6 connects to ionizing grid 4 via probe 7. Power supply 6 and probe 7 are preferably detachable. (See U.S. Pat. No. 4,828,586).
FIG. 3 shows a detail of construction of central grid 4 which comprises fine ionizing wires 5.
Operation of the filter is as follows: High voltage (about 5 to 10 KV) is applied to central grid 4 which, by virtue of its fine wires, ionizes the air and dust particles in the space between grid 4 and outside screens 2. At the same time, because of the high voltage applied to grid 4, an electrostatic field is also created between grid 4 and screens 2 and thus polarizes the non-conducting, dielectric fibrous pads 3. Dust particles or any particulate matter entering the filter become charged due to ionization and are attracted and collected by the polarized fibrous pads 3. This double action of ionization and polarization makes for a filter of improved efficiency.
FIG. 4 shows an alternate construction of the central grid 4. A length of fibrous string 8, such as one made of cotton having broken fibre ends is treated with a conducting solution, such as colloidal graphite, to render it conducting. String 8 is attached to a conducting frame 9. Fibrous string 8, because of its composition of fine fibres with multiple ends and, because it is rendered conducting, functions the same way as fine wires in ionizing dust particles.
FIG. 5 shows another alternate construction where an ionizing grid 10 is formed by depositing conducting paint or colloidal graphite on a sheet of gauze 11. Gauze 11, because of its composition of fine fibres and because it is rendered conducting, functions the same way as fine wires 5 in effecting ionization.
FIG. 6 shows another alternate construction for the central grid. In this case, a grid 12 is painted with conducting paint or colloidal graphite on coarse, fibrous paper 13. This paper 13 is perforated with perforations 14 to allow air to pass through. This arrangement also functions the same way as grid 4 in effecting ionization of dust particles because the coarse fibrous paper also has fine fibers which act in the same manner as the fibers in string 8 of FIG. 4.
FIG. 7 shows an alternate construction which is similar to the filter shown in FIGS. 1 and 2. In this case, the ionizing grid element consists of a fibrous conductive string 5a composed of fine filaments attached to one of the fibrous filter trapping pads 3. Fibrous string is again made conductive by coating it with conductive material like colloidal graphite. Conductive string 5a is connected to a high voltage power supply in a similar manner as shown in FIG. 2. Operation of this filter is as described above.
FIG. 8 shows a filter arrangement where two screens with frames 15 are hinged together to form the outside of a filter. (See also U.S. Pat. No. 4,549,883). Fibrous pads 16 are positioned on either side of central grid 4. Grid 4 is attached to its own one of frames 15 by insulating hinges 17. A high voltage power supply 18 connects to grid 4 via electrode 19 when the filter is closed. A cord 20 is connected to a low voltage power supply for supplying power to high voltage power supply 18. Operation of this filter is the same as described above for the cartridge filter shown in FIGS. 1 and 2.
FIG. 9 shows a similar arrangement as that of FIG. 8 except that in this case a conducting grid 21 is formed on one side of fibrous pad 10. Grid 21 is made by painting conducting elements directly on the fibrous pad.
Grid 21 is connected to power supply 18 via conducting strip 22 and wire 23. Strip 22 is attached to one of frames 15 by insulating hinges 24. Grid 21 functions the same way as grid 4 in the arrangement of FIGS. 1 and 2.
It is possible to construct any of the above mentioned arrangements using any of the different ionizing grid constructions described herein.
FIG. 10 shows the results of comparative tests made on a 20"×20"×2" cartridge type polarizing filter and the same filter with conductive fibrous strings. The high voltage used was 10 KV on the cartridge filters.
The tests were made by generating smoke in a sealed 570 cubic feet room. A ventilator was used to circulate air through the filters and the level of contamination was measured using a CLIMET INNOVATION 500 particle counter. The particle counter is capable of counting different particle sizes in the air as is drawn through the tube into the instrument. The counts used were for particles down to a 0.3 micron size, which is the most difficult particle size to capture, and the most numerous. The instrument was set to count the particles in 0.2 cubic feet of air every minute. All tests were made with 1000 cubic feet per minute (CFM) of air circulating through the filters as measured by an EBTRON air velocity meter.
The results show that by using ionization as well as polarization, (middle curve) the efficiency of filter improves as compared to using only polarization. Precipitators may be more efficient but it uses much more energy to operate. They have much less loading capacity and are far more expensive to operate. Precipitator require between 80 to 100 watts of power to operate while both the polarized media and the new polarized media/ionization type filters use only about 1.5 watts to operate. In both of the latter cases, the trapping pads, once coated with dust may be readily removed and exchanged for fresh, clean pads.
While two fibrous pads have been shown throughout as embracing the high voltage grid, only one is required. Two pads are preferred to cover the high voltage grid and prevent inadvertent contact.
Conclusion
The foregoing has constituted a description of specific embodiments showing how the invention may be applied and put into use. These embodiments are only exemplary. The invention in its broadest, and more specific aspects, is further described and defined in the claims which now follow.
These claims, and the language used therein, are to be understood in terms of the variants of the invention which have been described. They are not to be restricted to such variants, but are to be read as covering the full scope of the invention as is implicit within the invention and the disclosure that has been provided herein. | A high efficiency electronic air filter is disclosed in which pads of dielectric fibres are sandwiched between electrically charged, ionizing elements and grounded screens. The ionizing elements charge the dust particles passing through the filter and at the same time polarize the fibrous pads. In this way, the charged particles are attracted and collected on the fibrous pads with improved efficiency. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates generally to the documentation and evaluation of real estate investments, and more particularly, to automated real estate loan origination and underwriting processes from initial customer contact to commitment.
Methods for documentation and evaluation of real estate loan applications are well known in the investment industry, however, the specific sequence of steps directed toward preparation of the substantial necessary documentation and chosen method of analysis of the financial parameters are a matter of choice. For commercial and industrial real estate investment, the volume of supporting documentation and analysis is substantial, as are the dollar amounts and investment risk. Furthermore, consistency of such procedures and expeditious processing is important. To this end, proprietary computer applications have been developed by individual business entities, which automate individual aspects of the loan preparation, evaluation and authorization process.
In some cases, investment deals are compiled by business entity personnel who may be geographically distant from the central office, and possibly philosophically distant from the entity's investment policy and standards. Equally important, is early scrutiny of certain deal parameters against threshold parameters which serve to exclude potential real estate deals that fall outside the interests of the business entity. Consequently, the cost of compiling pertinent data and executing an appropriate and effective analysis of the data is an important factor. This is especially true for a business entity that conducts such transactions on a routine basis.
Computer applications directed toward compiling information about real estate property are known. For example, U.S. Pat. No. 5,794,216 describes an application program executed by a computer that includes a database containing multimedia information for each property, including images of the property, and database-stored parameters corresponding to portions of the image. The multimedia information includes market data and images of the property and neighboring circumstances.
Computer applications directed toward evaluating real estate are also known. For example, U.S. Pat. No. 5,680,305 describes a computer application that provides a method for evaluating real estate for use by a business entity. The application provides for storage of property description data, usage data, such as rental financial history, and other factors. A numerical “utilization indicator” is determined from these parameters, and after further processing, a “score” is developed, which represents a quantitative evaluation of the real estate property.
U.S. Pat. No. 5,966,699 describes a method for conducting electronic auctions of loan applications. In this method, a computer system connected to the Internet or other network electronically communicates “electronic” loan application forms from a prospective borrower to a loan authorizer, who maintains viable applications in a database, for subsequent electronic communication to one or more loan institutions for quotations.
Therefore, a data acquisition computer program is required for compiling loan origination information including financial and physical information relating to a specific property and multimedia real estate market information associated with the property, together with a credit request and loan application. The architecture of the computer program needs to be configured so as to provide consistency of processing among a variety of potential users through use of embedded choices, rules and financial models. The application should require only one-time entry of data in a non-linear sequence of data input screens, and should auto-populate documents with input data and generated values wherever appropriate. The system should be capable of electronically communicating loan documents to business entity personnel at any point during the document preparation process.
BRIEF SUMMARY OF THE INVENTION
The system and method according to the present invention employs a tool in the form of a personal computer application that automates the real estate loan origination and underwriting process for use by a business entity. The method of the present invention includes steps to be followed by one or more members of the business entity, as well as automated processes within the computer application. Some of the method steps are optional, and advantageously, all of the steps can be followed in any sequence.
While any of the steps of the method could be taken first, logically, and for purposes of description, the first described step of the method of the present invention is the step of storing in the computer application the basics of the real estate loan application, or “deal”, including property location, property metrics, estimated risks, loan terms and other loan and borrower details, by input of such values on one or more input screens. The next series of steps include data entry into a number of subsequent screens, in any order. Some of the subsequent screens test data inputs against pre-stored rules and based on the results of the tests, display information and commentary. The pre-stored rules are defined according to underwriting and pricing guidelines acceptable to the business entity. Other screens auto-populate certain fields with calculated results obtained by analysis of debt and equity data, using known financial models.
The system makes available to the user a set of computer screens presented in a generally non-linear sequence. The particular sequence of presentation is arranged to be under user control while at the same time, the sequence is also responsive on a real-time basis to the input data. In this way, the sequence of screens displayed for any given deal dynamically vary, depending on data entry.
Advantageously, in another step of the method, the system makes available to the user word processing-based documents, such as a loan application and credit request, which have been pre-formatted and auto-populated by the system with both input data and calculated data. In the preferred embodiment, the user initiates a one-way link (accomplished automatically by system utilization of known Windows-based, dynamic links) between the application and the word processing application present on the same computer as the system of the present invention.
For example, in the preferred embodiment, a “Key Metrics” portion arranged to appear within either a credit request or preliminary loan application is generated, in which selected financial data, such as profitability values such as investor rate of return (IRR), return on investment (ROI), net operating income (NOI), loan structure values, and performance calculations, are arranged in a standard format. These documents are available for editing by one or more members of the business entity, for example, by including paragraphs of text commentary and description. These documents become part of the overall loan origination package made available for subsequent evaluation internal to the business entity and quotation by financial institutions.
The system takes advantage of intranet and Internet connectivity to enable collaborative data input and evaluation among potentially geographically disparate users. Accordingly, in another optional step of the method, a user can instruct the system to initiate a network communication with other members of the business entity regarding a particular loan application. Optionally, the system can be instructed to copy selected data screens to a server storage location and automatically populate an email message with either attached data screens or hyperlinks to the storage location of the data screens.
Other steps of the method of the present invention include accessing the remaining data input screens of the system. It is expected that an implementation of the present invention includes screens tailored to the needs of the business entity, and therefore specific screens and screen contents will vary, depending on the needs and preferences of the business entity. As a non-limiting example, additional screens include a “Loan” screen for input of loan-related data, a “Cash Flow/Evaluation” screen, which includes various income/expense-related sub-screens, a “Deal Recap” screen, which summarizes the deal, based on all subsisting data, a “Market” screen which provide for input of the results of an analysis of the market associated with the property to be financed, and an “Asset” screen, which provides for input of the physical features of the property. In some cases, the system provides commentary dynamically responsive to the input.
Also included in the preferred embodiment is an “Execution” screen, which provides for input of subjective information characterizing the borrower in terms such as, for example, property experience, market experience, financial wherewithal, and forecasted reaction to adverse conditions, including specified types of litigation and criminal activity.
A “Deal Analysis” screen is included, which dynamically adjusts to the input data and calculated values, thereby providing a summary listing of attributes. Advantageously, this screen displays in a single location, the rules/guidelines which have been activated as a result of data input. Also included are “Loan Application” and “Credit Request” screens, in which pertinent data is input and organized into final form for processing. An “Execution” screen is included, which provides input of subjective information characterizing the borrower in terms such as, for example, property experience, market experience, financial wherewithal, and forecasted reaction to adverse conditions, including specified types of litigation and criminal activity.
A work pad screen taking the form of a spreadsheet, is provided for general use. An “Image” screen is provided, in which images captured by known Microsoft Windows-based methods, or the equivalent, can be added, deleted, arranged and reviewed. Typically, imaged maps and photographs of the site are included as input to the Image screen.
The result of operation of the steps of the system and method of the present invention is the compilation of information that is input, screened and edited by one or more team members having expertise pertinent to individual data types. This compilation includes calculated values obtained by execution of algorithms, i.e., financial models, that analyze debt and equity investments. Also included are multimedia files, such as imaged maps and photographs of the property and surrounding geographic area. This compilation is automatically arranged in any desirable output format, including a loan origination package made available for subsequent evaluation internal to the business entity and, as desired, quotation by financial institutions. Other automated outputs are possible, such as, for example, a loan request.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified block diagram of an overall computing environment including a computer system 10 of the present invention;
FIG. 2 illustrates an example of a “Screen Deal” input screen for entering basic data, according to the present invention;
FIG. 3 illustrates an example “Property Cash Flow” input screen, according to the present invention;
FIG. 4 illustrates an example “Loan” input screen, according to the present invention;
FIG. 5 illustrates an example “Cash Flow/Valuation” input screen, according to the present invention;
FIG. 6 illustrates an example “Deal Recap” input screen, according to the present invention;
FIG. 7 illustrates an example “Asset” input screen, according to the present invention;
FIG. 8 illustrates an example “Market” input screen, according to the present invention;
FIG. 9 illustrates an example “Execution” input screen, according to the present invention;
FIG. 10 illustrates and example “Environmental Issues”, input screen according to the present invention;
FIG. 11 illustrates an example “Deal Analysis” input screen, according to the present invention;
FIG. 12 illustrates an example “Loan Application” input screen, according to the present invention;
FIG. 13 illustrates an example “Images” input screen, according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention include a data acquisition computer program for compiling loan origination information including financial and physical information relating to a specific property and the real estate market associated with the property, together with a credit request and loan application, other outputs as desired, and steps of a method for using the program. The architecture of the computer program, or application, is configured to provide the benefit of consistency of processing among a variety of potential users, in some cases through ample use of embedded menus, from which the user makes an informed selection among fixed choices for a given data field. Rules imbedded within the application and associated with one or more data input fields automatically operate to assist the user in compiling a data conforming to standards and policies of the business entity. Similarly, use of known fixed financial models, although optionally, a choice among models can be provided, further contributes to consistency of loan origination and underwriting. The application is configured so that specific data entries are made only once by the user, leaving to the application the task of populating copies of that input data into other fields, as necessary.
Importantly, as a result of the non-linear flow of the data input screens, input can be made at the convenience of each user, and is not system-driven. Moreover, emphasis on network-connectivity among users and interested parties, enables conveyance of early (partially complete) versions of a particular compilation of data describing pertinent real estate market demographics, the physical, financial, and usage data relating to a specific real estate property, together with loan and credit applications, collectively referred to as a “deal”, to business entity personnel who, in other loan originating arrangements, might be the last, or nearly the last to review the deal. Such early scrutiny has been shown to be very effective in forestalling deals which fall outside the standards or interests of the business entity. It has been recognized that input from such individuals helps to formulate the initial version of the deal and avoid unnecessary delay resulting from re-writes.
FIG. 1 is a simplified block diagram of an overall computing environment including a computer system 10 of the present invention, including at least one computer 12 , which preferably is a personal computer, and a plurality of computer applications arranged to operate in computer 12 . Computer system 10 is arranged to cooperatively connect to external data sources 13 over a network. External sources 13 include data sources arranged to make data available upon demand over an intranet ( 14 ), or the Internet ( 15 ), as applicable. Computer 12 is arranged to operate both independently of, and connected to, network 14 , 15 , which optionally, can be an intranet or the Internet. Computer 12 is also arranged to operate a plurality of applications, including at least one desktop application 16 directed to loan origination and underwriting, written in a suitable programming language, such as, for example, the Delphi (trademark of InPrise Corporation) programming language, a spreadsheet application 18 , such as, for example, Excel (trademark of Microsoft Corporation), a word processing application 20 , such as, for example, Word (trademark of Microsoft Corporation), an optional database application 22 , such as, for example, Access (trademark of Microsoft Corporation), an internet browser application 24 , such as, for example Internet Explorer (trademark of Microsoft Corporation), and other applications, as appropriate.
In an alternative embodiment, a database application running on a central sever is arranged to capture and archive summary information or file copies for general use within the business entity, or to facilitate collaboration. Personal computers 11 suitably network-connected to computer 12 enable other members of the business entity to communicate with the user of computer 12 . In the preferred embodiment, computers 11 and 12 are configured to be interconnected upon demand, via intranet 14 and also by corporate LAN/WAN networks (not shown). Such communication includes electronic mail. Optionally, at least one of personal computers 11 is a server configured and arranged to perform known server functions, including storage of data files, and operation of web-related applications for communicating stored data to users via intranet and internet connections.
The desktop application 16 is configured and arranged to include local user input 27 , i.e., data entered by a user at the personal computer on which application 16 is running. Local user input 27 is verified against a set of pre-determined input rules 21 resident in application 16 . Input rules 21 are automatically activated by application 16 upon data entry by the user, and are configured to screen input for typographical errors and logical errors. Remote user input 28 , i.e., data communicated over a suitable network from other business entity personnel is communicated to the local user generally in the form of email and optionally, via documents attached to email. The local user transfers this information, as appropriate, as data input 27 to the application. Similarly, the local user accesses commercial sources 29 external to the business entity, and initiates data transfer to application 16 .
A desirable operating system 26 is Windows (trademark of Microsoft Corporation), OS/2 (trademark of IBM Corporation), or any such other operating system that supports the use of an extended memory, a DLL loading function, and a virtual storage, multi-window GUI environment.
FIG. 2 illustrates, but not by way of limitation, an example arrangement of a computer input screen 50 for entering basic data pertaining to a request for a loan in connection with a specific real estate property. The example input screen 50 titled “Screen Deal”, is one of a series of input and informational screens comprising the system 10 of present invention. The data input from all of these screens is stored in the database application 22 linked to desktop application 16 . System 10 includes a computational program that is configured to perform arithmetic calculations and comparisons of the input data. The computed results are also stored in the database application 22 . In the preferred embodiment the database application and computational program is a commercially available spreadsheet application 18 .
System 10 , in the preferred embodiment, is configured and arranged to automatically populate one or more associated spreadsheets by way of a data input and display application including data input screens such as screen 50 and other screens to be described. Also, informational screens are provided, which generally reflect calculated results of data entered into the associated spreadsheet, and may pose summaries, questions or warnings to the user, based on subsisting input data. Return On Investment (ROI), Internal Rate of Return (IRR) and Net Income are displayed at the top of every screen, and represent the deal's (either debt or equity) profitability. These values are constantly updated as the user provides information into the system. In a separate embodiment, system 10 also populates selected input and calculated values into a database associated with a commercially available database application that is dynamically linked with the input and display application, and is a part of, system 10 .
Screen Deal input screen 50 includes several features that advantageously appear on all screens of the present invention. Generally, included is a display of any set of icons, which, upon user selection using known Windows techniques, direct system 10 to display a corresponding, respective screen. For example, in the preferred embodiment, button icon channels 52 , called “channels” for convenience, are displayed on the left side of screen 50 , which direct system 10 to display screens corresponding to each major screen or suite of screens, described below. As a result, the user can conveniently navigate randomly from any particular screen to any other screen by known Windows navigation techniques.
Additional features in common with all screens of system 10 include functional pull-down menus 54 , which also are a known feature of Windows applications. These pull-down menus are screen-specific and offer functionality tailored to the currently displayed screen. For example, in the preferred embodiment, the pull-down menus labeled “File”, “Edit”, “Online”, “Activities”, and “Help”, appear at the top of screen 50 .
Other features in common with all screens of system 10 include guideline warnings representing rule violations, which are displayed throughout the application, as well as being summarized in a “Deal Analysis” channel. Guideline warnings are displayed as appropriate, based on system logic, which responds to both input data as well as calculated values.
The screens of system 10 optionally are suites of screens corresponding to the channels 52 . For a given channel, a corresponding suite of screens are identified by tab icons 56 near the top of the input area of each screen. These tabs enable the user to switch among members of the suite. Any set of input or informational screens sufficient to display pertinent fields can be included. For example, in the preferred embodiment, Screen Deal suite of screens 50 includes “General Information”, “Programs” and “Property Cash Flow” tabs and corresponding screens, described below. Inclusion of such screens in the design of the system 10 is based both on the need for input data, as well as providing direction to the system, based on the data input. For example, in the preferred embodiment, the “Programs” tab provides a screen that offers a selection of programs to the user, each program being arranged to employ a respective financial model to be used for debt and equity analysis. Moreover, the content and availability of other screens is dynamically determined according to specific data entered on any given screen, as described further, below. This process comprises automatic application of a set of pre-determined rules 23 , stored within application 16 , as data fields are entered.
FIG. 2 also shows an example “General Information” screen 51 , indicated by a tab 58 of the same name. This screen includes data input fields labeled according to the data type intended for input. Each field is connected to an associated spreadsheet and the input data is made available for subsequent computation, as described below. Specific computations are effected by application of pre-determined computation rules 25 , which are part of application 16 . Although screen 50 can include any number of appropriate input fields describing the property, risk, and loan terms, as understood in the loan origination industry, the preferred embodiment includes general information fields 59 describing the Property Location, Property Type, metrics such as Size and Year Built. For example, one selection of industry-standard input fields relating to risk 60 includes Estimated Risk Values, including Asset Risk, Market Risk, and Execution Risk. Still other input fields relating to loan terms 61 , including requested loan amount, requested term, interest rate type, loan purpose, and purchase price, input fields relating to borrower cash and capital needs. Screen 50 is arranged to display a Calculated Overall Risk Value 63 based on the estimated risk values 61 . Any field, such as “Loan Purpose” 57 , can have an associated pull-down menu of choices, the selection of which results in auto-population of the corresponding input field. Advantageously, restriction to a selection from a fixed menu of choices achieves consistency among users.
FIG. 3 illustrates an example “Property Cash Flow” arrangement 62 , obtained when the user selects tab 64 labeled “Property Cash Flow” from tabs 56 located near the top of Screen Deal 50 . In the preferred embodiment, inputs made to screen arrangement 62 are incorporated into calculations made by an attached spreadsheet. Icon buttons 70 revealing pop-up worksheets such as, for example, “Average Economic Occupancy Growth”, “Rental Growth” and “Other Growth” are located adjacent pertinent input fields on screen 62 , so that tabular input of growth data corresponding to, for example, six years of experience, can be entered by the user onto respective worksheets, calculated and returned as a calculated result, which is available for manual or optionally, automatic input into the appropriate field in screen 62 . In addition, other economics data input fields 71 include a “Effective Gross Income” value, a “Net Operating Income” value and a “Cash Flow After Reserves” value. In addition, detailed operating expense input fields 72 and tenant improvement costs and leasing commission values are input in screen 62 . Advantageously, a tenant improvement and leasing commission calculator is provided in the form of a pop-up window for the convenience of the user. This calculator provides a window formatted to receive this data, and calculates sums of the data input. Provision is made for input of multiple years of expense values, which are made available for subsequent computation and display, as necessary.
FIG. 3 also includes a “Programs” tab 73 , the selection of which instructs system 10 to display a screen (not shown) including selectable program options. In instances in which the business entity uses more than one “program” of threshold values for selected parameters, thus screen offers a selection button associated with each program option. Preferably, the choice of options that are displayed is dynamically dependent on subsisting data entered into the application. The user selection of a program results in a respective arrangement of automatically populated values into all pertinent data fields. Each program of thresholds and associated preferences are determined by the business entity.
FIG. 4 illustrates an example suite of loan screens which are obtained through user selection of icon button channel 74 , labeled “Loans”, from channels 52 , which are visible on every screen presented by system 10 . In the preferred embodiment, selection of “Loan” button 74 instructs system 10 to display the first of the suite of screens, each titled “Loans”, wherein each screen is further identified by a tab including a descriptive sub-title. User selection of the “General Terms” tab 75 instructs system 10 to display the corresponding screen. Optionally, other tabs, which can be selected in any order, indicating additional screens related to “loans”, are displayed near the top of the screen.
Advantageously, if the deal is an equity deal, as determined by selection of “Equity Deal Type” on the General Information screen of the Screen Deal suite of screens, then the suite of loan screens is replaced with a Deal Structure suite of screens (not shown). Deal Structure screens include data input fields characteristic of equity deal types, and are comparable to the suite of loan screens. In addition, the Loan Application and Credit Request suites of screens are also changed to be reflective of the information/structure needs of an equity transaction.
In the preferred embodiment, with the general terms screen 75 displayed, the user can select from pull-down menus options for “Lien Position” 76 , which includes, for example, selectable fields labeled “First” or “Second Mortgage” or “Equity/Joint Venture”. Advantageously, this fixed Flow”, % of Residual”, and “Minimum Residual Participation”. “Origination and Prepayment Fees and “Rate” input fields 79 and “Prepayment Options” fields 80 , including parameters known in the loan origination industry.
In one embodiment, the suite of “Loans” screens represented by the General Terms screen 75 , optionally includes other screens (not shown), each accessed by a tab. For example, in FIG. 4 , a “Sources” screen is displayed in which system 10 populates the screen with summary information relating to funding “sources” and corresponding “uses”, in balance-sheet format. Other screens can provide input fields for borrower cash equity, additional collateral, and earnout, as well as input fields relating to senior debt and annual debt service.
FIG. 5 illustrates an example Cash Flow/Valuation suite of screens, with the “Valuation” screen 81 displayed. “Valuation” screen 81 provides input fields for “Direct Capitalization” values 82 , “Discounted Cash Flow” 83 , and “Sales Comparables” 84 . The default calculations for these values consist of a mixture of user inputs and values driven by the system logic of system 10 . The user has the discretion of overriding both the input and the calculated values, should specific circumstances of the deal so dictate. In the preferred embodiment, in general, data fields associated with capital funding are auto-populated from other inputs to other screens. A “Percent Direct Capital” input field 85 is provided. A pull-down menu of calculation method selections 86 including “Average/Current Proforma NOI”, “Current NOI”, and “Proforma NOI”. In addition, text fields 86 are available for entry of user comments.
FIG. 5 also shows other tabs representing additional screens included in the suite of Cash Flow/Valuation suite of screens 81 , including tabs 87 labeled “Income By Year”, “Expense By Year”, and “Capital Expenditures By Year”. These screens include data input fields known in the loan origination industry, for example, “Income By Year” includes, for example, net rental income, expense recoveries and other income fields. The remaining screens of the suite include similar known inputs for expense and capital expenditures. Advantageously, in the preferred embodiment, pop-up worksheet screens are available to tally a number of years-average economic opportunity, and various types of income growth, as necessary. The number of years presented dynamically changes based on the loan term. In addition, system 10 trends forward the data input on the Screen Deal—Property Cash Flow screen, based on the growth rates previously assigned by the user.
FIG. 6 illustrates an example Deal Recap suite of screens, with the deal recap screen 90 displayed. Screen 90 provides an informational display of a “Deal Overview” 91 of the deal in terms of selected values of interest to the business entity. Any selected values can be displayed according to preferences of the business entity. For example, in addition to size and commitment amount, specific calculated underwriting values are displayed. Pricing values are displayed along with return values, including, for example, ROI, net income and IIR. Optionally, the details of these return values and other associated values, as identified by the business entity, are displayed in one or more additional informational screens.
FIG. 7 illustrates an example suite of “Asset” screens which are obtained through user selection of icon channel 95 , labeled “Asset”, from icon button channels 52 . In the preferred embodiment, selection of “Asset” channel 95 instructs system 10 to display the “Characteristics” screen 96 , indicated by an icon tab of the same name, displayed near the top of the screen. Assets screen 96 includes asset “Description” fields 97 , which include pertinent data fields known in the loan origination industry. Optionally, other input screens providing input fields for additional asset-related fields can be provided as necessary, and identified by selectable icon tabs.
FIG. 8 illustrates an example suite of “Market” screens which are obtained through user selection of channel 100 , labeled “Markets”, from icon button channels 52 . In the preferred embodiment, selection of “Market” channel 100 instructs system 10 to display a market demand screen 101 labeled “MSA Demand”, which is one of several metropolitan statistical area analysis screens. These screens can be configured to display any number of data input fields pertinent to characterizing market demand. In the preferred embodiment, screen 101 , as shown in FIG. 9 , is arranged in a grid format, in which at the left side is a list of market descriptors 102 , and across the top of the grid are column titles 103 indicating degrees of risk, including, for example, “less risky-1”, “2”, “3”, “4”, “5-more risky”, and “not selected”. The user optionally selects, for each listed market descriptor, an icon button from the appropriate column of degrees of risk button icons. A check-mark icon appears as overlaying each selected button. Advantageously, for each position of the Windows pointing device over a button icon, an information window 104 dynamically changes to display both definitions and experience-based information for that particular combination of risk and market descriptor.
In the preferred embodiment, the market demand screen 101 includes market descriptors such as, for example, number of jobs, employment growth, employment volatility, job diversity, population growth, demographic diversity, business environment, cost of services, defense employment exposure, single employer risk, single industry risk, infrastructure, size of skilled workforce, quality of life.
Also in the preferred embodiment, the market demand screen 101 includes “User Selected Market Risk” field 105 , which is auto-populated by system 10 with a value developed from previously entered numeric risk data, and a “Calculated Market Risk Rating” field, which is auto-populated by a calculated sum representing the above-described, subjective data indicated by checked grid buttons. Optionally, guideline warnings characterizing the disparity between these two risk rating values are auto-populated in a word processing document. A user, who edits such a document, would thereby have the opportunity to further expand on the reasons surrounding the difference in risk assessment.
Another metropolitan statistical area (MSA) analysis screen titled, for example, “MSA Supply”, (not shown) includes market descriptors such as, for example, metropolitan statistical area total inventory, metropolitan statistical area total inventory trend, metropolitan statistical area total inventory condition, metropolitan statistical area occupancy, metropolitan statistical area absorption per year, and metropolitan statistical area growth constraints.
Still another metropolitan statistical area titled, for example “Sub market Demand & Supply”, (not shown) includes market descriptors such as, for example, overall metropolitan statistical area demand, overall metropolitan statistical area supply, overall submarket demand, overall submarket supply.
FIG. 9 illustrates an example suite of “Execution” screens 200 which are obtained through user selection of channel 201 , labeled “Execution”, from icon button channels 52 . User selection of icon tab 202 , labeled “Borrower” instructs system 10 to display a “Borrower” screen 201 , which includes data input fields 203 which answer the question, “Does the Borrower have the experience to execute the business plan?”. These fields include borrower name, general real estate experience in years, property type experience in years, local market experience in years and number of similar properties owned. Input field grouping 204 includes input fields are intended to answer the question, “Does the Borrower have the financial wherewithal to perform?”, including net worth, liquid assets and empire risks, which includes user-selectable options, including operating shortfalls, highly leveraged, contingent liabilities, and difficulty with lenders.
A third borrower grouping of input fields 205 are intended to answer the question “How do we expect the Borrower to behave in bad times on their history?” These fields include check-mark icon entries for criminal activity, various civil litigation-related actions, and history with the business entity. Similar questions in connection with the tenant(s) can be provided.
FIG. 10 illustrates another input screen 66 titled “Environmental Issues” of the Execution suite of screens 200 . Screen 66 lists pre-determined environmental issues 67 arranged as the vertical component of a grid pattern. Across the top of the grid pattern are displayed five column headings 68 , for example, “Not Present”, “Green”, “Yellow”, “Red”, and “Not Selected”, although any suitable set of headings will suffice. Arranged within the grid, beneath the column headings, are icon buttons 69 , which the user selects according to a judgement of the degree of presence of a respective environmental item. Each selection results in the display of an icon checkmark, and mere location of the Windows cursor results in the appearance of explanatory commentary in an information window 55 . Included also, is a text-input window, made available for the user to add comments.
FIG. 11 illustrates an example of a deal analysis screen 210 , which is obtained through user selection of channel 201 , labeled “Deal Analysis”, from icon button channels 52 . Deal Analysis screen 201 is an informational screen displaying a list 202 of all guideline/rule warnings responsive to data input to-date. This list is a dynamic list drawn from a library of text descriptors each of which characterizes a specific aspect of the deal. For any given deal, the list automatically reflects an analysis of the numeric input data, the system-calculated values, and the non-numeric characterization inputs, e.g. the risk analysis described in connection with other input screens. Advantageously, a display of explanatory text appears in a window 203 , when the user selects each listed characterization. Where appropriate, the text includes context-sensitive data (pertinent to the current deal) embedded within the explanatory text. A questions window 204 is provided, also corresponding to each listed characterization, in which system 10 displays key questions dynamically based on data provided in other input screens.
FIG. 12 illustrates an example suite of loan application screens 208 which are obtained through user selection of channel 209 , labeled “Loan Application”, from icon button channels 52 . The Loan Application channel 52 instructs system 10 to display the “Borrower Information” screen 210 . Screen 210 includes data fields 211 identifying the borrower, including name, address, entity type, state of organization, along with fields identifying controlling principal(s), and indemnitors. Most, and potentially all of these fields are auto-populated by system 10 , using previously input data. This will depend, of course, on the sequence of input screen selection, and completeness of data entry, as of the selection of the Loan Application channel 209 . Other screens (not shown) optionally included in the Loan Application suite 208 display all information known in the loan origination industry as necessary for comprising, a complete loan application. Specific requirements may vary and are typically defined by the business entity. For example, Loan Application screen 210 shows exemplary tabs respectively titled “Property Information” 212 , “Basic Loan Terms” 213 , “Source and Uses” 214 and “Other Terms” 215 , as indicative of such information screens. The data fields of Loan Application screen suite 208 are used by system 10 to automatically generate a loan application suitable for printing or electronic transmission to a loan underwriting entity.
As indicated in connection with FIG. 4 , which illustrates a suite of loan screens, if the deal type is a debt deal, then the suite of loan application screens shown in FIG. 12 are displayed. If the deal type is an equity deal, as determined by selection of “Equity Deal Type” on the General Information screen of the Screen Deal suite of screens, then the suite of loan application screens 208 is replaced by a suite Credit Request screens which reflect the information/structural requirements of an equity transaction.
FIG. 12 shows channel 220 , labeled “Credit Request” among icon button channels 52 , the selection of which instructs system 10 to display a suite of “Credit Request” screens (not shown). The Credit Request screens include the same information display fields as described in connection with “Loan Application” screen suite 208 . Potentially all of these fields are auto-populated by system 10 , using previously input data, depending on prior completeness of data input. The data fields of Credit Request screens associated with the Credit Request channel 220 are used by system 10 to automatically generate a credit request suitable for printing or electronic transmission to a credit approval entity.
FIG. 12 also shows, selection of a channel labeled “Work Pad” 222 provides to the user a screen having basic spreadsheet capability, for use as a convenient calculator for incidental calculation.
FIG. 13 illustrates a channel 224 labeled “Images”, which upon user selection, enables the user to add, insert, and delete images, by selection of buttons 225 , 226 and 227 , respectively. After images are input and arranged in desired sequence, the user can instruct system 10 to sequentially display the images by selecting navigation keys 232 . These images are also moved by system 10 to either the Preliminary or Credit Request word processing documents along with the other deal-related information.
Referring to any of FIGS. 2-13 , a set of menu choices are displayed at the top of each screen, including standard Windows choices such as “File”, “Edit” and “Help”. In the preferred embodiment, other functionality is also included in the form of menu choices. For example, a menu choice is configured to provide a view of deals grouped by category, such as geographic region, state, or product type (apartment, commercial, etc.). Optionally, system 10 calculates a comparison of any of a group of data fields of interest to the business entity (currently these are “canned reports).
Advantageously, a copy of the deal recap screen 90 , illustrated in FIG. 6 , is made available on one or more networks, according to the needs of the business entity. Preferably, the copy of screen 90 is made available on the business entity intranet. The copy of screen 90 is created automatically when a user saves for the first time and is then automatically updated on each subsequent save. This functionality requires that the user be connected to the network, for example, an intranet, at the time that the save occurs, and does not require that the user select or otherwise identify or copy the screens. As an automatic function, system 10 copies one or more deal files, for example, the financial model file, the Loan Application file, and the Credit Request file, from the user's hard drive, stores them in a server database in a packaged form suitable for transmission and display over an intranet or optionally, the Internet. The user, through menu selection, instructs the system 10 to automatically populate an email message including a hyperlink to the selected screens, and to automatically send the message to one or more addressees indicated by the user.
Another optional menu choice is a tracking function, which enables the user to view all posted documents. All data which has been changed over the initial input is graphically highlighted, so that a viewer is able to view the change history by clicking on the data. This information becomes visible in a pop-up window because the data is tagged with at least the revised data author's name, date and time, and old and new value.
Still other optional menu choices include direct links to web pages providing commercially available market research data and financial reporting data, such as Dunn & Bradstreet (registered trademark). If the user has already provided the postal ZIP Code to system 10 , as part of the property description, such links will automatically route system 10 to data pertinent to the deal. Similarly, links to commercial map sources, including orbital images as well as area street maps and aerial photographs are accessed the same way. Copies of such information are obtained by known Windows editing methods. | A system and method for use by a business entity for loan origination and underwriting in connection with real estate investment using a computer implemented application having a plurality of data input and dialog screens requiring one-time entry of data. The method includes steps to be followed in any sequence by one or more users of the business entity for using the system. The method includes inputting and storing loan origination information via data input screens, the information including financial and physical information relating to a specific real estate investment. The input loan origination information is dynamically compared with pre-determined rules and a dialog screen is displayed on a near real-time basis if any of said rules are violated. The input data is dynamically compared with other rules for determining the ongoing sequence of data input and dialog screens. Comparison with other rules results in the calculation of calculated values and automatically generated dialog text, some of which is automatically populated in word processing documents, an automated loan request and a credit application. The system includes both manual and automatic input of market data quantitatively describing the real estate market associated with the property, as well as multimedia data describing the property and the region surrounding the property. A report representing all of the stored input and calculated values are automatically produced in both paper and electronic form suitable for loan origination and underwriting. | 6 |
FIELD OF THE INVENTION
[0001] In general, the present invention relates to a new method for recovering nickel from a laterite or partially oxidised lateritic ore. In a preferred embodiment, the present invention provides a new process for treating partially oxidised ore which contains a substantial proportion of its iron component in ferrous form, and which involves heap leaching, atmospheric leaching or pressure leaching of the ore, or any combination of these leaching methods, followed by nickel and cobalt recovery and impurity removal by an ion exchange process and the production of mixed nickel and cobalt hydroxide. Cobalt may also be recovered separately following a further ion exchange, solvent extraction or other known processes by precipitation as cobalt hydroxide or cobalt sulfide.
BACKGROUND OF THE INVENTION
[0002] Laterite nickel and cobalt ore deposits generally contain oxidic type ores, limonites, and silicate type ores, saprolites, as two layers in the same deposits, separated by a transition zone.
[0003] The higher nickel content saprolites tend to be treated by a pyrometallurgical process involving roasting and electrical smelting techniques to produce ferro-nickel. This treatment normally involves a drying step, followed by a reduction roast step to partially convert the nickel oxides to nickel, and smelting in an electrical furnace. This is a highly energy intensive process and requires a high grade saprolite source to make it economic. It also has the disadvantage that financial value of any cobalt in the ore, which is recovered into the ferro-nickel, is not realised.
[0004] The high nickel and cobalt content limonite is normally commercially treated hydrometallurgically by the High Pressure Acid Leach (HPAL) process using sulphuric acid in which iron is precipitated as hematite as ferric oxide, or by a combination of pyrometallurgical and hydrometallurgical processes, such as the Caron reduction roast-ammonium carbonate leach process.
[0005] Other acid leach processes for extracting nickel and cobalt from laterites are described in the literature. These include atmospheric pressure acid leaching, separately leaching the limonite and saprolite fractions by combinations of high pressure and atmospheric leaching, and heap leaching. In these acid leach processes sulfuric acid is usually the acid of choice, but the use of hydrochloric acid, or organic acids has also been described. As the iron in the ores treated is in the ferric state, the leached iron is precipitated as jarosite, goethite, ferrihydrite, hematite or iron hydroxide, depending on the technology used. The relevant recovery methods for nickel and cobalt described are also limited to the treatment of liquor containing ferric as the unique iron component.
[0006] A common feature in atmospheric pressure acid leaching is that a substantial portion of the high iron content of the laterite leaches along with the nickel and cobalt, and reports as ferric ions in the product leach solution (PLS), and current processes for treatment of the (PLS) focus on the recovery of target metals such as nickel, cobalt and occasionally copper from the leachate containing ferric as the dominant iron component.
[0007] Heap leaching is a conventional method of economically extracting metals from ores and has been successfully used to recover materials such as copper, gold, uranium and silver. Generally it involves piling raw ore directly from ore deposits into heaps that vary in height. The leaching solution is introduced onto the top of the heap to percolate down through the heap. The effluent liquor is drained from the base of the heap and passes to a processing plant where the metal values are recovered.
[0008] Heap leaching of laterites is taught in U.S. Pat. No. 5,571,308 (BHP Minerals International, Inc), which describes a process for heap leaching of high magnesium containing laterite ore such as saprolite.
[0009] U.S. Pat. No. 6,312,500 (BHP Minerals International, Inc) also describes a process for heap leaching of laterites to recover nickel, which is particularly effective for ores that have a significant clay component such as nickel-containing smectite and nontronite (greater than 10% by weight).
[0010] A major problem with the heap leach process is that the leachate produced contains, in addition to the nickel and cobalt values targeted, large quantities of ferric iron ions and a variety of other impurities. The purification of similar nickel solutions from commercial laterite acid leach processes involves neutralisation of the acid content, precipitation of ferric iron ions, followed by production of a nickel/cobalt intermediate, a re-dissolution step, and complex solvent extraction stages to produce saleable nickel and cobalt. The purification steps generally aim for complete removal of iron and the other impurities.
[0011] Ion Exchange (IX) processes have been disclosed for the extraction of both the nickel and cobalt from the nickel leachate, leaving the major impurities in the raffinate.
[0012] US Patent 95/16118 (BHP Minerals International Inc.) describes an ion exchange process for separating nickel from the leachate from treatment of laterite by the pressure acid leach process. Nickel is extracted by the resin at pH less than 2, and stripped with sulfuric acid for subsequent electrowinning. Cobalt remains in the raffinate along with other impurities, and after solution neutralisation, is precipitated as a sulfide.
[0013] Patent WO 00/053820 (BHP Minerals International Inc.) describes the ion exchange extraction of nickel and cobalt from acid sulfate leach solution onto the resin, and the subsequent acid stripping of the metals from the resin, and their separation by solvent extraction.
[0014] U.S. Pat. No. 6,350,420 B1 (BHP Minerals International Inc.) also teaches the use of ion exchange resin in a resin in pulp process to extract nickel and cobalt onto the resin from an acid leach slurry.
[0015] The preferred resin used in these patents is Dow M4195 which has the functional group bis-picolylamine and the adsorption constants indicating selectivity of the resin at pH 2 are in the order of Cu 2+ >Ni 2+ >Fe 3+ >Co 2 +>Fe 2+ >Mn 2+ >Mg 2+ >Al 3+ . The above patents all aim to produce relatively pure nickel solution, or nickel and cobalt strip solutions from the ion exchange resins.
[0016] An improvement to the ferro nickel process described earlier is taught in International Patent application (PCT/AU.2005/001360) (BHPBilliton SSM Development Pty Ltd) which teaches a method of producing a nickel/iron hydroxides to feed the smelting step. This involves heap leaching of the laterite, an ion exchange stage with Dow M4195 to separate nickel and some of the iron from the ferric ion containing product liquor. As ferric ion concentration in the PLS produced is ten times the concentration of the nickel ions, the effective resin capacity for nickel adsorption is decreased due to the loading of the ferric ions.
[0017] It has been surprisingly found following detailed experimental work and pilot plant operation, that contrary to what is taught in prior art, some partially oxidised laterite ores which are less weathered, or have a younger geological history, contain a substantial proportion of their iron content in ferrous form, and when acid leached in a heap leach process to recover nickel, generate a product leach solution in which most of the iron is in ferrous form. This discovery has required a changed philosophy for iron treatment in hydrometallurgical processes in the laterite industry, and has led to the process of the present invention which overcomes or at least alleviates one or more of the difficulties associated with the prior art.
[0018] The above discussion of documents, articles and the like is included in the specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention before the priority date.
SUMMARY OF THE INVENTION
[0019] In general, the present invention relates to a new method for recovering nickel from partially oxidised laterite ore which contains a substantial proportion of its iron content in the ferrous state. In a preferred embodiment, the present invention provides a new process for treating laterite ore which contains a substantial proportion of its iron component in ferrous state, and which involves heap leaching, atmospheric pressure leaching, high pressure leaching, or any combination of these leaching processes of the ore, followed by nickel and cobalt recovery, impurity removal by an ion exchange process, solvent extraction or other known methods and mixed nickel and cobalt hydroxide production by neutralisation.
[0020] Accordingly, the present invention resides in a process for the recovery of nickel and/or cobalt from laterite or partially oxidised laterite ores having a high ferrous iron content, said process including the steps of:
a) providing a laterite or partially oxidised laterite ore wherein a substantial proportion of the iron present in the ore is in its ferrous state; b) acid leaching the ore to provide a product leach solution containing at least ferrous iron, nickel and/or cobalt together with acid soluble impurities; and c) recovering the nickel and/or cobalt from the product leach solution with a selective ion exchange resin in an ion exchange process leaving the ferrous iron and other acid soluble impurities in the raffinate.
[0024] The term “substantial proportion” as used in relation to describing the content of ferrous iron in the laterite ore, is indicative that the laterite ore contains a relatively higher proportion of ferrous to ferric iron than found in many laterite ore deposits. Typically, what is meant by a “substantial proportion” is that the content of ferrous iron represents about 30% or greater of the total iron content in the laterite ore.
[0025] The process of the present invention is particularly suitable for the recovery of cobalt together with the nickel. The selective ion exchange resin in one embodiment, is selective for the adsorption of nickel, but preferably is selective for the adsorption of both nickel and cobalt in a nickel and cobalt recovery process.
[0026] In general, the present invention provides a process for producing a nickel hydroxide or mixed nickel/cobalt hydroxide intermediate from laterite ore. It is applicable to laterite ore bodies, such as partially oxidised laterites, where a substantial proportion of the iron is in ferrous form, and reports to the leachate as ferrous ions. The invention is particularly applicable to a process where the laterite ore has been subjected to a heap leach process, wherein the nickel and cobalt is leached with sulfuric acid to form a product leach solution (PLS) containing nickel, cobalt, iron in ferrous and ferric form and acid soluble impurities, the process preferably includes the steps of:
1. Partially neutralising the PLS to precipitate and separate any ferric iron from solution. The PLS is then in a ferrous sulfate media form. 2. Contacting the product leach solution containing the nickel, cobalt, ferrous iron and acid soluble impurities with preliminary ion exchange (IX) resin, wherein the resin selectively adsorbs any copper from the solution leaving the nickel, cobalt, ferrous iron and the acid soluble impurities in the raffinate; 3. Contacting the raffinate with a selective ion exchange resin wherein the resin selectively adsorbs nickel and cobalt, leaving the ferrous iron and other impurities in the raffinate. 4. Stripping the nickel and cobalt from the selective ion exchange resin with a sulfuric acid solution to produce an eluate containing nickel and cobalt; and 5. Neutralising the eluate to precipitate a mixed nickel cobalt hydroxide product; or separating the cobalt before precipitation by known processes such as sulfidation, solvent extraction, or ion exchange.
[0032] In general, the process forms part of an overall process for the recovery of nickel and/or cobalt. Preferably, the product leach solution is produced by a heap leach process wherein at least one heap of ore is established and leached with a sulfuric acid supplemented liquor stream, which will percolate through the heap to produce a product leach solution containing at least nickel, cobalt, ferrous and ferric iron and acid soluble impurities. More preferably, the heap leach process is established in a counter current system whereby:
a) a primary and a secondary heap are established; b) the secondary heap is treated with a liquor stream comprising recycled raffinate from the ion exchange process supplemented by sulfuric acid and the recycled acidic PLS from the primary heap, to produce an intermediate PLS; and c) treating the primary heap with the intermediate PLS to produce the PLS containing at least nickel, cobalt, iron and acid soluble impurities.
[0036] Whereas it is envisaged that the product leach solution will be produced by a heap leach process, preferably a counter current heap leach process, the process may also be applied to a product leach solution containing at least nickel, cobalt and ferrous iron produced from partially oxidised lateritic ore by leaching with sulfuric acid by other means, such as leachate from a pressure acid leach process, an atmospheric leach process, or any combination of pressure, atmospheric and heap leaching.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 illustrates a flow sheet of the invention illustrating each aspect of the invention for recovery of nickel and cobalt from laterite ore containing a substantial proportion of iron in the ferrous state, including the leach process, ferric iron precipitation, copper removal, and production of nickel/cobalt sulphate solution.
DETAILED DESCRIPTION OF THE INVENTION
[0038] In a preferred embodiment, where the product leach solution results from an acid heap leach process, high ferrous iron content laterite ore is crushed to a size, preferably less than 25 mm size, and agglomerated if required for heap porosity using water, sulfuric acid, or other binding materials, to improve heap permeability
[0039] The agglomerated ore may be arranged into a single heap but preferably at least two heaps, a primary and a secondary heap, to be operated as a counter current heap leach system. The counter current heap leach process has the advantage of lower acid consumption, lower ferric ion concentration and a cleaner product leach solution than the single heap system.
[0040] In a preferred method, which is illustrated in FIG. 1 , the liquor stream (1) is sourced from the acidic nickel depleted recycled raffinate from the nickel and cobalt ion exchange step, supplemented with sulfuric acid (2), and added to the secondary heap leach (3) of Run of Mine ore (4), producing an intermediate product leach solution (5). The leach stage (3) may alternatively be an atmospheric, pressure or combination of heap, atmospheric or pressure leach processes. In one embodiment (not illustrated) the intermediate product leach solution is then added to a primary heap leach in a counter current process. This produces a nickel and cobalt rich product leach solution (PLS) with low acidity and low ferric ion concentration, which also contains ferrous iron and a number of other impurities. When the secondary heap is depleted of nickel, it is discarded, the primary heap becomes the secondary heap, and a new ore heap becomes the primary heap.
[0041] In the embodiment in FIG. 1 , the product leach solution is neutralised by the addition of a suitable neutralising agent, preferably limestone, to a pH of 2-3 (6), and a preferred temperature around 80° C., but at any temperature between ambient and 90° C., in order to precipitate any ferric iron present as goethite or ferric hydroxide. Removal of ferric iron increases the effective resin capacity to extract nickel and cobalt as the ion exchange resins used to recover nickel downstream will also adsorb ferric iron. Ferrous iron, which is not adsorbed by the nickel IX resins, remains in the product leach solution.
[0042] If the nickel and cobalt are to be recovered by ion exchange, any copper present in the product liquor is preferably removed first, as the resins suitable for nickel recovery also adsorb copper and it would become an impurity in the final product. After solid/liquid separation to remove the precipitates (7), any copper in the product leach solution is removed by a preliminary ion exchange stage (8). The preferred preliminary ion exchange resins for copper IX are Amberlite IRC 748 or Bayer TP 207, but other suitable resins with selectivity for copper may be used. The copper (9) is stripped from the resin by sulphuric acid, and rejected if in small quantities.
[0043] If there is sufficient copper in the product leach solution to economically justify recovery, the copper removal step may be a solvent extraction step, using reagent such as Lix 84 or Lix 984, followed by electrowinning or cementation to recover the copper.
[0044] Accordingly, in one embodiment of the invention, prior to the recovery of nickel in the ion exchange process, any copper present in the product leach solution may be removed by contacting the product leach solution with a preliminary ion exchange resin as part of the ion exchange process, to selectively adsorb any copper present from the solution leaving the nickel, cobalt, ferrous iron and the acid soluble impurities in a preliminary raffinate.
[0045] In a further embodiment of the invention, prior to the recovery of nickel in the ion exchange process, any copper present in the product leach solution may be removed by treating the product leach solution with an organic reagent in a solvent extraction process to selectively extract any copper present leaving the nickel, cobalt, ferrous iron and the acid soluble impurities in the raffinate.
[0046] The raffinate from the copper IX is then subjected to a nickel selective ion exchange step, preferably a nickel and cobalt selective ion exchange step (10), to recover the nickel and cobalt, which are adsorbed on the resin. The selective ion exchange resin for example, preferably is a resin with a bis-picolylamine functional group. Most preferably it is Dowex M4195. At pH 2 the adsorption constants indicating selectivity of the resin are in the order is Cu 2+ >Ni 2+ >Fe 3+ >Co 2 +>Fe 2+ >Mn 2+ >Mg 2+ >Al 3+ . Therefore the resin can recover nickel and cobalt selectively (as ferric iron has already been removed), and ferrous iron and other acid soluble impurities remain in the raffinate. The raffinate is then partially neutralised with lime or other suitable neutralising agents (11) at pH 10-11 to precipitate out and remove ferrous hydroxide and other impurities such as Mg for disposal (12), before recycling the liquor to the leach stage if required (13).
[0047] The retained nickel and iron are stripped from the resin using a mineral acid, preferably a sulfuric acid solution (14), to produce an eluate containing nickel and cobalt sulfates (15). Other resins with selectivity for nickel and cobalt, such as Amberlite IRC 748, or Bayer TP207 may also be used as the ions (ferric and copper), for which these resins have a higher selectivity than nickel and cobalt ions have been removed.
[0048] A mixed nickel/cobalt hydroxide precipitate (MHP) may then be produced from the eluate by neutralisation with magnesium oxide to pH 8-9.
[0049] The liquor stream treated by this process may also be supplemented by leachate containing at least nickel, cobalt and ferrous iron from a pressure acid leach process, an atmospheric leach process, or any combination of pressure and atmospheric leaching of laterite ores. In other alternative embodiments, the product leach solution for the ion exchange process can be sourced directly from the leachate of such leach processes, without a heap leach process.
[0050] In other alternative embodiments, the nickel and cobalt may be recovered from the IX eluate, either together by other known precipitation processes such as sulfidation, or separately by known separation methods such as solvent extraction, ion exchange or selective precipitation, followed by electrowinning or hydrogen reduction.
[0051] Accordingly, in another embodiment of the invention, the nickel and cobalt are recovered from the eluate by either:
i) neutralising the eluate to a pH of about 8-9 to precipitate the nickel and cobalt as a mixed nickel/cobalt hydroxide product; or ii) separating the cobalt from the eluate by precipitation, solvent extraction or other known methods, and then subsequently neutralising the eluate to a pH of about 8-9 to precipitate the nickel as a nickel hydroxide product.
[0054] Each of the embodiments described illustrates various alternatives in the process and various combinations of the alternatives should be considered as forming part of the invention described herein.
[0055] There are several advantages of the process described where laterite contains a substantial proportion of ferrous iron rather than ferric iron as described in prior art.
[0056] Stoichiometric calculations indicate that the acid consumption to dissolve one unit of ferrous ion is two thirds of the acid consumption to dissolve ferric iron. Similarly, the limestone consumption to precipitate ferrous irons in effluent treatment is only two thirds of the limestone consumption to precipitate ferric irons. Consequently, processing a ferrous iron containing laterite in the process of the invention uses significantly less acid for leaching, and less limestone for neutralisation of the acid used. This is economically better for processing ferrous containing laterite ores, when compared to processing ferric containing laterite ores.
[0057] In some prior art processes, sulfur dioxide is used to control ORP to the range of 600-700 mV (vs AgCl/Pt probe) to break down and leach the cobalt-containing mineral asbolane (Mn, Co)O 2 . In addition, the ORP control of <900 mV (vs AgCl/Pt probe) was essential to protect the Dow 4195 resin used in the IX recovery of nickel from oxidants such as Cr 2 O 7 2+ Cr(VI), and Mn 4+ in the PLS.
[0058] A further advantage of this process is that with ferrous ions Fe 2+ leached from ferrous containing laterite ore, the ORP of PLS is naturally within the range to liberate cobalt from asbolane and to protect Dow M4195 resin from oxidants without introducing any sulphur dioxide or other reductants.
[0059] The process of the invention also offers advantages in the selection and economy of use of the IX resins.
[0060] IX with Dow M4195 resin is taught in patent WO 00/053820(BHP Minerals international Inc.) as a preferred route to recover nickel and cobalt from heap leaching PLS, because it has a unique higher affinity (selectivity) to Ni 2+ than Fe 3+ compared to other commercial resins such as Amberlite IRC748, Bayer TP207 and Purolite S930. Although Dow M4195 has this unique selectivity, its price is significantly higher than the other resins and an economic hurdle for application.
[0061] The existence of a substantial proportion of ferrous in ferrous containing laterite processed in this invention may allow the choice of a cheaper resin in the acid leach/IX processing route for nickel recovery, thus improving the economics. The high ferrous iron content of product liquor, and the low ferric content offer the following other advantages for the IX processing route.
[0062] If Dow M4195 resin is used for the nickel extraction IX stage, the effective nickel capacity of the resin is increased, as all ferric iron has been removed in the first neutralisation step, and the ferrous iron is not preferentially adsorbed by the resin. The capital investment of the IX route is therefore reduced due to the higher effective nickel capacity per unit of resin, when it is dominated by only ferrous ions.
[0063] A further advantage is that with no ferric ions loaded on the resin, cobalt can also be loaded easily, improving the efficiency of cobalt recovery by the IX process.
[0064] Without the interference of ferric ions, the inexpensive resins such as Amberlite IRC748, Purolite S930 and Bayer TP207 could replace Dow M4195 for the copper removal IX stage. The loaded copper on these resins can be stripped out with mild acidic solution instead the ammoniacal solution used for Dow M4195.
[0065] The above description is intended to be illustrative of the preferred embodiment of the present invention. It should be understood by those skilled in the art, that many variations or alterations may be made without departing from the spirit of the invention.
EXAMPLES
Example 1
The Composition of Partially Oxidised Laterite Ores and the PLS (Pregnant Leachate Solution) of Heap Leach and Atmospheric Agitation Leach
[0066] Table 1 compares the chemical compositions of the fully oxidised and partially oxidised laterite ore, marked with the content of ferrous ions (Fe 2+ ). Mineralogical investigation identified magnetite (Fe 3 O 4 ) and the lower saprolite zone (which is distinguished from the upper saprolite zone by less oxidation) were the major mineral phases containing ferrous ions (Fe 2+ ).
[0067] Table 2 and Table 3 show the compositions of heap leach PLS and atmospheric agitation leach PLS respectively. Ferrous ions in the PLS verified substantial ferrous ions (Fe 2+ ) contained the tested laterite ore.
[0000]
TABLE 1
Chemical Compositions (%) of Fully and
Partially Oxidized Laterite Ores
Tot.
Laterite ore
Fe
Fe 2+
Mg
Ni
Co
Indonesian limonite
40.8
nd*
1.3
1.53
0.10
Indonesian saprolite
8.5
nd*
14.6
3.37
0.03
New Caledonian limonite
47.1
nd*
0.4
1.33
0.16
New Caledonian saprolite
7.7
nd*
23.3
1.00
0.02
Western Australian low-Mg ore
25.4
nd*
4.9
2.50
0.07
Western Australian high-Mg ore
10.0
nd*
16.6
1.38
0.02
South American partially oxidized
30.60
8.36
3.98
1.38
0.10
limonite
South American partially oxidized
14.38
4.93
15.53
0.96
0.04
saprolite
South American partially oxidized
22.6
6.6
6.9
1.30
0.10
laterite composite of limonite and
saprolite
nd*: Not detected
[0000]
TABLE 2
Heap Leach PLS Compositions of South American Partially
Oxidised Laterite Composition of Limonite and Saprolite
with Weight Ratio of 1:1 and Various Leaching Conditions
Sample
ORP*
Fe 3+
Fe 2+
Mg
Ni
Co
No.
mV
pH
g/L
g/L
g/L
g/L
g/L
1
432
2.31
0.7
4.7
12.01
2.00
0.23
2
383
2.99
0.0
4.0
13.17
2.14
0.30
3
415
2.21
3.25
15.98
6.34
1.52
0.11
4
476
1.47
28.52
2.93
6.69
1.04
0.08
ORP*: versus Pt/AgCl probe
[0000]
TABLE 3
Atmospheric Agitation Leach PLS Compositions of South American
Partially Oxidized Limonite and Saprolite (80° C., constant 100 g/L
H 2 SO 4 , liquid/solid ratio: 10 mL:1 gram)
Ni Ext.
Fe 3+
Fe 2+
Mg
Ni
Co
Ore
%
g/L
g/L
g/L
g/L
g/L
Limonite
93.5
16.0
7.3
3.79
1.09
0.076
Saprolite
91.0
8.5
5.6
10.2
0.74
0.043
Example 2
Atmospheric Leaching of Ferrous Bearing Nickel Laterite Ore
[0068] One litre of 25% w/w limonite slurry was added to an agitated three litre reactor and heated to 60° C. 98% sulphuric acid was added to the slurry with the acid/limonite weight ratio of 650 kg acid per dry tonne of ore, increasing the leach temperature to approximately 100° C. The limonite slurry was leached for three hours, after which time approximately 90% of the solid was dissolved.
[0069] Approximately one litre of 25% w/w saprolite slurry was added to the limonite leached slurry. The presence of saprolite consumes remnant free acidity. This in turn causes ferric iron present in solution to precipitate, either as a jarosite or as goethite. The precipitation of iron generates free acidity in solution which further leaches the saprolite slurry. This process continues to equilibrium over eleven hours, with a leach temperature of 100° C. maintained throughout.
[0070] After saprolite leaching a slurry of limestone is added to the reactor. The limestone neutralises any remaining acid in solution and precipitates any remaining ferric ions.
[0071] FIG. 2 shows the relationship between ferrous and ferric iron and nickel in solution with time during the atmospheric leach process. The graph shows that with time ferric iron ions are precipitated from the liquid phase, showing the separation of ferric ions from nickel and ferrous ions in solution. The concentration of nickel increases with time as the saprolite slurry is leached and remains unaffected by the precipitation of ferric ions. The obtained PLS is an intermediate product for the manufacture of nickel/cobalt mixed hydroxide or sulfide, ferronickel, metallic nickel powders or nickel cathode.
Example 3
Nickel Recovery with Ferric Ions Precipitation Followed by IX Separation/Purification
[0072] In a pilot plant operation, the heap leach PLS was heated at 80° C. and neutralised to pH 2.5-3.5 with limestone slurry to precipitate ferric ions as goethite or para-goethite or ferrihydrite or hydroxide. Ferrous ions Fe 2+ were not precipitated under such conditions. After solid/liquid separation with a frame filter, the filtrate containing Ni 2+ and Fe 2+ was first passed through a Copper-IX fixed-bed column to scavenge Cu 2+ . The solution was then passed through an IX device named ISEP ° in which 30 IX columns charged with ion exchange resin Dow M4195 are fixed on a carousel. An acidified, synthetic spent electrolyte solution, manufactured to correspond to a nickel electrowining solution was used as a stripping solution. Almost all impurities such as ferrous, aluminum, chromium and magnesium ions were rejected into the raffinate, with nickel recovered in the eluate. Table 4 illustrate the compositions for the feed in/out solution to ferric ions precipitation, ISEP® feed solution, raffinate and eluate. Variations in the composition of various liquid streams indicated that nickel was separated from impurities and purified with the consecutive operation of ferric ions precipitation and ion exchange. The obtained elution solution is an intermediate product for manufacture of nickel/cobalt mixed hydroxide or sulfide, ferronickel, metallic nickel powders or nickel cathode.
[0000]
TABLE 4
Average Compositions of Liquid Streams of the Process of Heap Leach-
Ferric Ions precipitation-Nickel Recovery with IX (Ion Exchange)
Ni
Fe 3+
Fe 2+
Co
Al
Cr
Cu
Mg
Mn
Stream
g/L
g/L
g/L
g/L
g/L
g/L
mg/L
g/L
g/L
Heap leach PLS
1.94
8.56
10.89
0.23
4.10
0.24
12
10.63
1.74
Filtrate after Fe 3+
1.57
0.23
10.14
0.21
2.90
0.06
9
9.60
1.57
precipitation
ISEP ® feeding solution
1.39
0.20
8.81
0.19
1.94
0.05
1
8.34
1.32
after Cu 2+ scrubbing
ISEP ® Raffinate
0.10
0.10
8.29
0.15
2.02
0.05
0
7.85
1.28
ISEP ® Eluate
47.06
3.80
0
0.75
0.26
0.018
21
0.02
0.03 | A process for the recovery of nickel and/or cobalt from laterite or partially oxidised lateritic ores having a substantial proportion of the iron present in the ferrous state, said process including the steps of:
a) providing a laterite or partially oxidised laterite ore wherein a substantial proportion of the iron present in the ore is in the ferrous state; b) acid leaching the ore to provide a product leach solution containing at least ferrous iron, nickel and cobalt together with acid soluble impurities; and c) recovering the nickel and cobalt from the product leach solution with a selective ion exchange resin in an ion exchange process leaving the ferrous iron and other acid soluble impurities in the raffinate. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the priority date of provisional patent application Ser. No. 60/962,035, filed on Jul. 25, 2007, which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to semiconductor equipment and in particular to a machine for polishing semiconductor wafers.
BACKGROUND
Semiconductor integrated circuits are typically made from thin wafers cut from silicon ingots known as boules. Cutting a wafer from a boule generally leaves the surfaces of the wafer in a rough condition, so wafers are polished on wafer polishing machines prior to starting semiconductor processing operations. The difficulty in achieving desired values of flatness and surface roughness increases as the diameter of the wafer to be processed increases and as the size of semiconductor structures (also known as “feature size”) to be fabricated on the wafer decreases. Wafer diameters have steadily been increasing and feature sizes decreasing at the same time that manufacturers have been pressured by market forces to increase manufacturing throughput and reduce manufacturing costs.
In the past, the relatively small size of wafers permitted a single wafer polishing machine having one or more head assemblies, each head assembly adapted to hold a plurality of wafers, to flatten and smooth many wafers simultaneously. Polishing machines use an abrasive, corrosive slurry to mechanically and chemically remove microscopic projections from the surface of a wafer. Machines for polishing bare wafers and machines for polishing by a chemical and mechanical process are known in the art. A wafer polishing machine has a horizontal rotating platen in a table base with a polishing pad attached to the top of the platen. A lid attached to the table base has at least one head assembly that is rotated during polishing. A wafer carrier attached to a head assembly holds one or more wafers to be polished. Pumps deliver slurry at a selected rate to the polishing pad and motors rotate the platen and head assemblies. Parts of the head assembly for carrying wafers have vertical travel relative to the surface of the polishing pad and may be raised or lowered to contact the polishing pad and to apply a selected amount of pressure to the surface of the wafers to be polished.
One or more wafers to be polished are attached to a wafer carrier and a wafer carrier is attached to each head assembly. Next, slurry is deposited on the polishing pad. The lid with wafers attached to the carriers on the head assemblies is lowered to enclose a polishing envelope and bring wafers closer to the polishing pad, and slurry is deposited on the polishing pad. Separate drive motors for the platen and head assemblies enables independent control of speed and direction of rotation. Polishing continues until the wafers achieve a desired value of wafer material removal, a desired value of surface quality, or a combination of both.
A quality and a rate of wafer polishing depend in part on a magnitude and direction of motion of the wafers relative to the polishing pad. The relative motion between the wafers and the polishing pad includes a component of rotational motion from the platen combined with a component of rotational motion of the head assembly to which the wafer is attached. In the case of a head assembly having a carrier holding a plurality of wafers, rotation of the head assembly results in wafer rotation relative to the platen and orbital motion of each wafer to and from the center axis of the platen. As technology progresses, the diameter of processed wafers also increases and the number of wafers that fit onto a carrier is correspondingly reduced. Furthermore, as wafer diameter increases, an edge of the wafer moves closer to the rotational center of a head assembly. The contribution to the rate of polishing by the rotation of the head assembly decreases for those parts of the wafer that are closest to the center of rotation of the head assembly. Some wafers are large enough that only one wafer may be placed in the central area of a carrier on a head assembly, in which case the component of radial, orbital motion from rotation of the head assembly is effectively lost in the central area of the wafer, and the quality of polishing is significantly degraded.
To achieve high quality polishing for large wafers, for example wafers having a diameter of 300 millimeters (12 inches), some polishing machines have only one head assembly above the platen. However, having only one head assembly per platen significantly reduces a rate of production compared to machines adapted to polish many wafers simultaneously. Adding more machines to make up the production rate difference per machine requires a higher capital investment in equipment and more factory floor space.
What is needed is a polishing machine having high throughput and a complex relative motion between a surface of a wafer to be polished and a polishing pad on a platen, for all parts of the surface of a large wafer.
SUMMARY
Embodiments of the present invention comprise a wafer polishing machine adapted for polishing large wafers efficiently and economically. In one embodiment, a wafer polishing machine in accord with the invention comprises a rotating platen and polishing pad in a table base, above which is mounted a lid having a head moving assembly with four rotating head assemblies. During operation, the head moving assembly collectively moves the head assemblies in reciprocating linear motion in a plane parallel to an upper surface of the platen while the platen and head assemblies are rotating. Embodiments of the invention produce a complex relative motion between a surface of a wafer to be polished and the polishing pad. The complex relative motion, resulting from a combination of motions including rotation of the platen, rotation of the head assemblies, and translation of the head moving assembly including four head assemblies, improves a quality and a throughput of polishing and prolongs a service life of the polishing pad compared to wafer polishing machines known in the art.
The above summary of the present invention is not intended to represent each disclosed embodiment, or every aspect, of the present invention. Other aspects and example embodiments are provided in the figures and the detailed description that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention may be more completely understood in consideration of the following detailed description and accompanying drawings, in which:
FIG. 1 is a simplified pictorial view of a wafer polishing machine in accord with an embodiment of the invention;
FIG. 2 is a pictorial view of the embodiment of FIG. 1 , in which the lid is raised from the table base and the platen and head assemblies are visible;
FIG. 3 is a simplified top view of an embodiment of the invention, showing a lid on top of a table base and a head moving assembly comprising four head assemblies in a square pattern sliding across the platen in an aperture formed in the lid;
FIG. 4 is a simplified top view of the same embodiment as FIG. 3 , showing the head moving assembly moving in a direction opposite to the direction shown in FIG. 3 ; and
FIG. 5 is a simplified view of a drive box, a part of the head moving assembly used to cause the head assemblies to rotate together at a same rate of rotation.
FIG. 6 is a top view of the embodiment of FIG. 3 showing a reference position and a reference angle for motion of the head moving assembly.
DESCRIPTION
A wafer polishing machine adapted for polishing large wafers in accord with an embodiment of the invention is shown in FIG. 1 and FIG. 2 . The wafer polishing machine 100 comprises a table base 104 with a lid 102 , shown closed in FIG. 1 and with the lid 102 raised in FIG. 2 . Various electrical cables, slurry hoses, seals, switches, valves, and other support equipment have been omitted from the figures to facilitate a clearer view of the locations and functions of components discussed herein.
In FIG. 1 , a top cover 110 encloses a head moving assembly (see FIG. 3 and FIG. 4 ) that partially protrudes through an opening formed in the lid 102 . A head assembly drive motor 106 in FIG. 1 imparts rotation to four head assemblies 204 visible on the underside of the lid 102 in FIG. 2 . The head assembly drive motor 106 and four head assemblies 204 are parts of the head moving assembly. A head moving assembly drive motor 108 attached to a fixed part of the lid 102 imparts a reciprocating linear motion to the head moving assembly. A round platen 202 is mounted into the table base 104 and rotates during polishing. A polishing pad (not shown) is placed on the upper surface of the platen 202 to facilitate polishing of a work piece. Work pieces like semiconductor wafers are placed on wafer carriers 205 and attached to the ends of the four head assemblies 204 visible in FIG. 2 .
A simplified top view of an embodiment of the polishing machine 100 of FIG. 1 and FIG. 2 is shown in FIG. 3 and FIG. 4 . In FIG. 3 and FIG. 4 , the lid 102 is shown atop the table base 104 . The platen 202 , marked with a hidden line, is shown beneath the lid 102 in the table base 104 . An example of a platen rotation direction 306 is marked with an arrow drawn with a dashed line. The platen 202 may optionally be rotated in a direction opposite to the platen rotation direction 306 shown. The platen may be rotated at a selected rate of rotation in the selected direction of rotation.
The lid 102 is formed with a rectangular opening 301 in which a head moving assembly 302 slides back and forth above the platen 202 . The head moving assembly 302 comprises four head assemblies 204 . In some embodiments, the four head assemblies are attached to the head moving assembly in a square pattern, as shown in FIG. 3 , FIG. 4 , and FIG. 5 . An example of a first head moving assembly translation direction 308 is shown in FIG. 3 . An example of a second head moving assembly translation direction 402 , representing a direction opposite to the direction shown in FIG. 3 , is shown in FIG. 4 . The head moving assembly 302 may be constrained to move on a linear path by slides, rails, channels, the sides of the aperture in the lid 102 , or equivalent linear guiding means. Motion is imparted to the head moving assembly 302 by the head moving assembly drive motor 108 shown in FIG. 1 . A mechanical linkage (not illustrated) connected to the head moving assembly drive motor 108 and to the head moving assembly 302 converts a continuously rotating output from the drive motor to a reciprocating linear motion of the head moving assembly. In some embodiments, the linkage converts the motor's rotary output to an approximately sinusoidal linear motion. Linkages for converting rotary to linear motion, for example rotary to sinusoidal linear motion, are well known in the art and will not be described further here. The head moving assembly may be moved at a selected rate of translation in each of the directions of translation.
An example of a head assembly direction of rotation 304 is shown by an arrow drawn with a solid line in FIG. 3 and FIG. 4 . All four head assemblies 204 rotate in a same selected direction and at a same selected rate of rotation. In other embodiments, the head assembly direction of rotation 304 may be opposite to the direction shown in FIG. 3 and FIG. 4 . A means of causing all four head assemblies 204 to rotate at a same rate and in a same direction is shown in FIG. 5 . In FIG. 5 , a drive box 502 comprises mechanical support and components for driving the four head assemblies 204 . A drive motor pulley 504 is rotationally coupled to the head assembly drive motor 106 of FIG. 1 , either by direct attachment to the motor drive shaft or by additional gears, belts, or pulleys. A head assembly pulley 506 is attached to a shaft for each head assembly 204 . Rotating the head assembly pulley 506 causes the head assembly 204 connected to the pulley to rotate. A power coupling means 508 engages the drive motor pulley 504 and the head assembly pulleys 506 as shown in FIG. 5 such that a rotation of the drive motor pulley 504 causes a corresponding rotation of the head assembly pulleys 506 and correspondingly rotates the head assemblies 204 . In some embodiments, the power coupling means 508 is a double-sided timing drive belt having teeth and in other embodiments it can be a drive chain.
In the embodiment of FIG. 3 and FIG. 4 , the head moving assembly 302 is shown moving in a first translation direction 308 and a second translation direction 402 . The first translation direction 308 and the second translation direction 402 are collinear and in opposite directions. A direction of translation of the head moving assembly 304 is selected such that a tangent to a circular rotation path that is concentric with the platen's center of rotation is at an angle of 45 degrees to the direction of translation when the head moving assembly is in a reference position. The reference position referred to herein is defined as a middle or nominal position of the head moving assembly 304 . With the head moving assembly in the reference position, all four heads simultaneously have a tangent at 45 degrees to the direction of translation, as shown in FIG. 6 .
FIG. 6 shows a table base 102 , a lid 102 , and a head moving assembly 302 comprising four head assemblies 204 , as in FIG. 3 and FIG. 4 . A platen pad 610 on top of the platen 602 is represented by a phantom line. FIG. 6 further illustrates a reference position for the head moving assembly 302 and a direction of translation for the head moving assembly. A displacement of the head moving assembly 302 from the reference position illustrated in FIG. 6 , also referred to as a middle position of the head moving assembly, corresponds to a magnitude of translation of the head moving assembly, a maximum value for which is determined by the size of the opening 301 in the lid 102 . A platen circular rotation path 604 , indicated with a phantom line, is shown concentric with the center of rotation 606 of the platen 202 and intersecting all four centers 608 of the head assemblies 204 , thereby defining a reference position of the head assemblies and head moving assembly. Lines 602 A, 602 B, 602 C, and 602 D, each tangent to the platen circular rotation path 604 and each passing through a head assembly center or rotation 608 , represent a direction of wafer center motion from platen 202 rotation relative to the platen 202 . A direction of translation represented by a line 402 passing through the centers of rotation 608 of the head assemblies 204 , or alternately an opposite direction of translation represented by lines 308 , is selected such that a line representing the linear translation path for all four head assemblies is at an angle of 45 degrees to the rotational part of the wafer center motion relative to the platen. For example, tangent line 602 A is one of four lines tangent to the platen circular rotation path 604 . A translation direction is selected such that an angle of 45 degrees is formed between a line 402 representing the linear translation path of the head moving assembly 302 and the tangent line 602 A. Similarly, 45 degree angles are formed between line pairs ( 402 , 602 C), ( 308 , 602 B), and ( 308 , 602 D). The 45 degree angle described herein is to be formed for all four heads simultaneously when the head moving assembly is in the reference position illustrated in FIG. 6 .
Embodiments with four head assemblies in the head moving assembly have high throughput and provide high quality wafer polishing. Wafer polishing machines with one or two head assemblies process fewer wafers per unit time than embodiments of the invention. Wafer polishing machines with three head assemblies will not have the symmetries apparent from an examination of the four-head configuration of FIG. 3 , FIG. 4 , and FIG. 6 , leading to differences in polishing rates compared to embodiments of the invention, and three head assemblies will not simultaneously meet the preferred 45 degree direction of translation described herein and in FIG. 6 . Wafer polishing machines with more than four head assemblies in the head moving assembly will not simultaneously meet the preferred 45 degree direction of translation as defined in FIG. 6 and will not provide uniform optimal polishing conditions for the polishing process.
A method of polishing a plurality of wafers on a polishing machine in accord with an embodiment of the invention comprises mounting wafers to be polished to wafer carriers 205 and installing the wafer carriers 205 on the head assemblies 204 as shown in FIG. 2 . The platen 202 with a polishing pad attached is rotated in a selected direction 306 as in FIG. 3 and FIG. 4 . The head assemblies 204 with carriers 205 holding wafers are rotated at a selected rate and in a selected direction as in FIG. 3 and FIG. 4 . The head moving assembly 302 , also referred to as a drive box, is moved back and forth relative to the platen 202 within the opening 301 in a first translation direction 402 and a second translation direction 308 . Slurry is supplied to the polishing pad, the carriers 205 are lowered until the wafers contact the rotating platen 202 , and a separation distance between the wafers in the carriers 205 on the head assemblies 204 and the polishing pad on the platen 202 is adjusted to apply a selected amount of pressure between the wafers and the polishing pad. Pressure and motion continue until a selected quality of polish is achieved or until a selected amount of material is removed from the wafers. One skilled in the art will recognize that the steps above may optionally be performed in many different alternative sequences.
The present disclosure is to be taken as illustrative rather than as limiting the scope, nature, or spirit of the subject matter claimed below. Numerous modifications and variations will become apparent to those skilled in the art after studying the disclosure, including use of equivalent functional and/or structural substitutes for elements described herein, use of equivalent functional couplings for couplings described herein, or use of equivalent functional steps for steps described herein. Such insubstantial variations are to be considered within the scope of what is contemplated here. Moreover, if plural examples are given for specific means, or steps, and extrapolation between or beyond such given examples is obvious in view of the present disclosure, then the disclosure is to be deemed as effectively disclosing and thus covering at least such extrapolations.
Unless expressly stated otherwise herein, ordinary terms have their corresponding ordinary meanings within the respective contexts of their presentations, and ordinary terms of art have their corresponding regular meanings. | Embodiments of the invention comprise a machine adapted for polishing work pieces such as large silicon wafers. A wafer polishing machine in accord with the invention comprises a rotatable platen in a table base, above which is mounted a lid having a head moving assembly with four synchronously rotatable head assemblies. A motor and linkage connected to the head moving assembly imparts reciprocating linear motion to the head assemblies in a selected direction in a plane parallel to an upper surface of the platen. Embodiments of the invention produce a complex relative motion between a surface of a wafer to be polished and the platen. The complex relative motion, resulting from a combination of motions including rotation of the platen, rotation of the head assemblies, and translation of the head moving assembly, improves a uniformity of polish and a rate of polishing compared to wafer polishing machines known in the art. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is based upon and claims benefit of priority of Japanese Patent Application No. 2004-294738 filed on Oct. 7, 2004, the content of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a wireless transmitter-receiver device in which electric power is selectively supplied from a battery to wireless circuits.
[0004] 2. Description of Related Art
[0005] Recently, an automobile license plate on which a wireless device is mounted for wirelessly transmitting a license number and a vehicle identification number (a so-called smart plate) has been proposed. The wireless device is always exposed to water splash, sunshine or other hazardous atmosphere. Therefore, the wireless device including a battery for supplying power to wireless circuits has to be contained in a hermetically encapsulated casing. When the battery is contained in such a casing, it is impossible to connect or disconnect the battery to the wireless circuits (referred to as activation of the battery) from outside. Accordingly, the encapsulated battery has to be continuously kept activated after the wireless device is manufactured in a device manufacturer.
[0006] A considerably long period of time is required after the wireless device is manufactured until it is actually used. If the battery is continuously kept activated, battery power is consumed in vain. Usual processes in this period are as follows. The wireless device is inspected after completion of the manufacturing processes. The battery has to be activated for performing the inspection. Then, the wireless device is shipped to a license plate manufacturer to be mounted on the license plate. The battery has to be activated to store a vehicle identification number and a license number in a memory included in the wireless device. Then, the license plate on which the wireless device is mounted is sent to a place, such as a transportation authority, where the license plate is mounted on a vehicle. The battery has to be activated to store information regarding security or the like in the memory. Then, the vehicle is delivered to a user, and the wireless device is put into actual use. After that, the battery has to be continuously kept activated. However, it is not necessary to keep the battery activated in periods of transportation or waiting time between processes. Rather, it is most desirable to keep the battery inactivated to save battery power consumption.
[0007] Power saving of this sort is required not only in the wireless device for the license plate but in other devices which are put into actual use a considerably long time after they are manufactured.
SUMMARY OF THE INVENTION
[0008] The present invention has been made in view of the above-mentioned problem, and an object of the present invention is to provide a wireless device having a battery, wherein the battery is activated only when necessary to save power consumption.
[0009] A wireless device such as a transmitter-receiver device mounted on a license plate of an automobile includes a battery for supplying power to a wireless circuit included in the device. A substrate, on which components such as a wireless circuit, a memory for storing a vehicle identification number and a license number, and a switch for turning on and off power supply from the battery to the wireless circuit, is contained in a casing. A member for operating the switch is inserted into the casing, and the switch is turned on or off according to an insertion depth of the operating member.
[0010] The operating member includes a rod member inserted into the casing and an end disk integrally connected to the rod member. The rod member has a depression in which a pivoting member of the switch is accommodated to thereby turn off the switch when the operating member is inserted into the casing up to an intermediate depth. When the operating member takes depths, including an initial depth and a final depth, other than the intermediate depth, the switch is turned on to supply power from the battery to the wireless circuit. In other words, the power supply to the wireless circuit is turned on at the initial depth (a shallow depth), turned off at the intermediate depth and turned on again at the final depth. When the operating member is inserted into the casing up to the final depth, the end disk connected to the end of the rod member hermetically closes the casing so that the components of the device are protected from water splashes or the like.
[0011] A second depression may be additionally formed on the rod member, so that the switch is turned off again when the pivoting member is accommodated in the second depression. In this case, the switch is operated in a sequence of on, off, on, off and on according to the insertion depth of the operating member. A sealing member may be included in the end disk so that the casing is hermetically sealed when the operating member is inserted into the casing up to the final depth. A removable spacer may be disposed between the end disk and the casing so that the operating member is kept at a certain depth, e.g., at the intermediate depth. An anchoring portion engaging with the pivoting member may be formed in the depression so that the operating member is not able to be pulled back from the position where the pivoting member is accommodated in the depression.
[0012] According to the present invention, the battery power of the wireless device is prevented from being consumed in vain in periods of transportation or storage. The battery can be activated or inactivated (power supply is turned on or off) by simply controlling the insertion depth of the operating member. Other objects and features of the present invention will become more readily apparent from a better understanding of the preferred embodiment described below with reference to the following drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a cross-sectional view showing a wireless device to be mounted on a license plate;
[0014] FIG. 2 is a cross-sectional view showing a switch (OFF state) used in the wireless device, in an enlarged scale;
[0015] FIG. 3 is a cross-sectional view showing the switch (ON state);
[0016] FIG. 4 is a cross-sectional view showing an operating member used in the wireless device; and
[0017] FIG. 5A is a partial cross-sectional view showing the wireless device, in which the operating member takes a first position;
[0018] FIG. 5B is a partial cross-sectional view showing the wireless device, in which the operating member takes a second position;
[0019] FIG. 5C is a partial cross-sectional view showing the wireless device, in which the operating member takes a third position;
[0020] FIG. 5D is a partial cross-sectional view showing the wireless device, in which the operating member takes a fourth position; and
[0021] FIG. 5E is a partial cross-sectional view showing the wireless device, in which the operating member takes a fifth position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0022] A first embodiment of the present invention will be described with reference to FIGS. 1-4 . A wireless device 100 is mounted on a license plate of an automobile or installed in the vicinity of the license plate. The wireless device 100 is shaped in a rectangular box (e.g., 40 mm×40 mm×15 mm). FIG. 1 shows a cross-sectional view, assuming that the left side in FIG. 1 is the front side of the wireless device 100 . The wireless device 100 wirelessly transmits information such as a license number and a vehicle identification number to a roadside device.
[0023] Components of the wireless device 100 are contained in a casing 1 . A wireless circuit 3 , a memory 6 , a battery 5 and a switch 4 mounted on a substrate 2 are all contained in the casing 1 . The casing 1 is made of a resin or metallic material. At the rear end of the casing 1 , a hole 11 (e.g., 2 mm square) and a depressed portion 7 surrounding the hole 11 are formed. The depressed portion 7 is cylinder-shaped (viewed from the rear side of the casing 1 ) with a diameter of about 10 mm and a depth of about 5 mm. The hole 11 is positioned at a little eccentric position with respect to a center of the round depressed portion 7 . The casing 1 is structured to hermetically protect components contained therein.
[0024] The memory 6 is composed of a rewritable non-volatile memory such as a flash memory, and data are stored in the memory 6 and read out under control of the wireless circuit 3 . The substrate 2 is fixedly connected to the casing 1 with screws or the like. The wireless circuit 3 performs various functions such as amplification, modulation, de-modulation, D/A conversion and A/D conversion. Data are stored in the memory 6 and the stored data are transmitted to outside devices through an antenna (not shown) under control of the wireless circuit 3 . Operating power is supplied from the battery 5 to the wireless circuit 3 .
[0025] Power supply from the battery 5 to the wireless circuit 3 is turned ON or OFF by the switch 4 . As shown in FIG. 2 , the switch 4 is composed of a switch case 41 , a shaft 42 , a pivoting member 43 , a movable contact 44 , a stationary contact 45 , and a spring 46 . The switch case 41 is a box-shaped member made of a resin material, and is fixedly mounted on the substrate 2 . An upper surface of the switch case 41 and the lower surface of the hole 11 are positioned at the same level. An opening is formed in the upper surface of the switch case 41 so that a portion of the pivoting member 43 is able to expose, and a shaft 42 supporting the pivoting member 43 is fixed to the switch case 41 . The pie-shaped pivoting member 43 pivots around the shaft 42 .
[0026] The movable contact 44 is fixed to the pivoting member 43 , as shown in FIG. 2 , and the stationary contact 45 is fixed to a bottom wall of the switch case 41 , so that both contacts 44 , 45 are closed or opened according to movement of the pivoting member 43 . When the contacts 44 , 45 are closed, electric power is supplied from the battery 5 to the wireless circuit 3 (this situation is referred to as “the battery is activated” in this specification). On the other hand, when the contacts 44 , 45 are opened, power supply is discontinued (the battery is inactivated).
[0027] The pivoting member 43 is biased upward by the spring 46 , so that an upper portion of the pivoting member 43 exposes from the opening of the switch case 41 , as shown in FIG. 2 . The pivoting member 43 does not move upward beyond the position shown in FIG. 2 because the pivoting member 43 abuts the edge of the opening. When the pivoting member 43 is pushed downward, the pivoting member 43 moves downward against the biasing force of the spring 46 , and the contacts 44 , 45 are closed, as shown in FIG. 3 .
[0028] An operating member 9 shown in FIG. 4 is inserted into the casing 1 through the hole 11 , so that the pivoting member 43 is operated to close or open the contacts 44 , 45 according to a depth of insertion. The operating member 9 is made of a resin or metallic material and is composed of a rod member 91 and an end disk 92 connected to the rod member 91 . The rod member 91 has a square cross-section corresponding to the square shape of the hole 11 . The end disk 92 has a round circumference corresponding to the round shape of the depressed portion 7 .
[0029] On the lower surface of the rod portion 91 , depressions 93 , 94 are formed as shown in FIG. 4 . Each depression 93 , 94 has a sufficient size to accommodate the upper portion of the pivoting member 43 therein (refer to FIG. 5B ) . Each depression 93 , 94 has an anchoring portion 98 , 99 engaging with the pivoting member 43 and a sloped surface 96 , 97 . The anchoring portion 98 , 99 stands up from the bottom surface of the rod member 91 at an about right angle, and the sloped surface 96 , 97 is formed to make an angle of about 30 degrees with respect to the bottom surface of the rod member 91 . An O-ring 95 for sealing is disposed, surrounding a foot portion of the rod member 91 , in a groove formed on the end disk 92 .
[0030] Processes of handling the wireless device 100 after it is manufactured and until it is put into actual use will be explained with reference to FIGS. 5A-5E . As shown in FIG. 5A , for testing operation of the wireless device 100 after it is manufactured, the operating member 9 is inserted into the casing 1 so that it takes an initial depth Di. At this depth Di, the pivoting member 43 is pushed downward by the rod member 91 , and the contacts 44 , 45 are closed, thereby supplying electric power from the battery 5 to the wireless circuit 3 (the battery is activated) . The test is performed by activating the battery 5 in this manner.
[0031] Then, the wireless device 100 is shipped to a license plate manufacturer to mount the wireless device 100 on the license plate. Before shipping the wireless device 100 , the operating member 9 is further inserted into the casing 1 up to an intermediate depth Dm shown in FIG. 5B . The operating member 9 is inserted by pushing the end disk 92 with a finger. At this depth Dm, the pivoting member 43 moves up into the depression 93 by the biasing force of the spring 46 . The contacts 44 , 45 are opened and the battery 5 is inactivated. Power consumption of the battery during a period of transportation is saved in this manner. If the operating member 9 is pulled back toward the rear side when the operating member 9 is positioned at the intermediate depth Dm, the operating member 9 does not move toward the rear side because the anchoring portion 98 engages with the pivoting member 43 that cannot move beyond the present position. A U-shaped spacer 10 may be inserted between the end disk 92 and the casing 1 so that the operating member 9 is prevented from moving further toward the front side.
[0032] After the wireless device 100 arrived at the license plate manufacturer, the wireless device 100 is mounted on the license plate. The battery 5 has to be activated to memorize the vehicle identification number and the license plate number in the memory 6 of the wireless device 100 . The operating member 9 is further inserted up to a second intermediate depth Dm 2 shown in FIG. 5C after removing the spacer 10 . At this second intermediate depth Dm 2 , the pivoting member 43 is pushed downward by the rod member 91 to thereby close the contacts 44 , 45 . Thus, the battery 5 is activated. When the operating member 9 is moved from the intermediate position Dm shown in FIG. 5B to the second intermediate position Dm 2 shown in FIG. 5C , its movement is smooth because the pivoting member 43 easily moves out from the depression 93 along the sloped surface 96 which is not steep.
[0033] Then, the wireless device 100 is transferred to a place where the license plate with the wireless device 100 is mounted on a vehicle. Before the transportation, the battery 5 is inactivated. The operating member 9 is further pushed into the casing 1 up to a third intermediate depth Dm 3 shown in FIG. 5D . At the third intermediate position Dm 3 , the pivoting member 43 is accommodated in the depression 94 by the biasing force of the spring 46 to thereby open the contacts 44 , 45 . At this depth Dm 3 , the operating member 9 becomes impossible to be pulled back in the same manner as at the intermediate depth Dm shown in FIG. 5B . Power consumption in the battery 5 is saved during the transportation in this manner.
[0034] After the license plate with the wireless device 100 arrived at the place where the license plate is mounted on the vehicle, the battery 5 has to be activated again for memorizing security information or the like in the memory 6 . The operating member 9 is inserted up to a final depth Df shown in FIG. 5E . At the final depth Df, the pivoting member 43 is pushed by the rod member 91 to thereby close the contacts 44 , 45 . The end disk 92 is completely contained in the depressed portion 7 of the casing when the operating member 9 takes the final position Df. The O-ring 95 surrounding the foot portion of the rod member 91 is compressed between the bottom wall of the depressed portion 7 and the end disk 92 , so that the hole 11 is hermetically sealed. Since the end disk 92 is entirely accommodated in the depressed portion 7 , it becomes difficult to pull back the operating member 9 from the casing 1 . After the above process is completed, the operating member 9 is kept at the final position Df to put the wireless device 100 into actual use, while hermetically sealing the wireless device 100 .
[0035] As described above, the battery 5 is kept not to consume its power in vain during the period after completion of manufacture and until it is actually used. This is realized by inserting the operating member 9 into the casing 1 stepwise. The wireless device 100 is hermetically sealed by the O-ring 95 when the operating member 9 is inserted up to the final depth Df. Further, the stepwise insertion of the operating member 9 is easily done because the depressions 93 , 94 are discretely formed.
[0036] The present invention is not limited to the embodiment described above, but it may be variously modified. For example, the depressions 93 , 94 may be replaced with a single depression if such is suitable for actual handling processes of the wireless device 100 . The square cross-section of the rod member 91 may be replaced with other cross-sections such as a triangular cross-section as long as the pivoting member 43 is operated according to the insertion depth of the operating member 9 . The depressed portion 7 may be formed in other shapes. For example, it may be made in a tapered shape open to the outside and connected to the hole 11 so that the hole 11 is well sealed when the operating member 9 takes the final position Df. The O-ring 95 may be replaced with a sealing member such as a gasket. A projection may be formed on the end disk 92 to ease operation of the operating member 9 , and the projection may be removed after the operating member 9 is inserted up to the final depth Df.
[0037] The switch 4 may be structured differently. For example, the pivoting member 43 may be connected to the rod member 91 and the contacts may be separately positioned on the substrate 2 . Though the switch 4 is structured so that the battery is inactivated when the pivoting member 43 is accommodated in the depressions 93 , 94 in the foregoing embodiment, it is possible to inactivate the battery when the pivoting member 43 is pushed out of the depressions 93 , 94 . Though the removable spacer 10 is used when the operating member 9 takes the intermediate position Dm in the foregoing embodiment, it is possible to use another spacer which is thinner than the spacer 10 when the operating member 9 takes the third intermediate position Dm 3 . Alternatively, the U-shaped spacer 10 may divided into two spacers in the thickness direction, so that two spacers are used in the position Dm and one spacer is removed in the position Dm 3 .
[0038] While the present invention has been shown and described with reference to the foregoing preferred embodiment, it will be apparent to those skilled in the art that changes in form and detail may be made therein without departing from the scope of the invention as defined in the appended claims. | A wireless device to be mounted on a license plate of an automobile is composed of a casing, components contained in the casing and an operating member inserted into the casing. A battery for supplying power to the components is selectively turned on or off by controlling an insertion depth of the operating member into the casing. At an initial depth, the power supply is turned on for testing the wireless device at a manufacturing plant. At an intermediate depth, the power supply is turned off to save energy consumption in periods of transportation or storage. At a final depth, the power supply is finally turned on for actual use of the wireless device, and the casing is hermetically closed by the operating member. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a gas transportation method for grain, and more particularly to a method for transporting grain with low hardness such as rice by means of gas.
2. Description of Related Art
Conventionally, in rice polishing factories and boiled rice factories, delivered unpolished rice is usually polished by a rice polishing machine to be half-polished rice, and the half-polished rice is processed to be polished rice with its rice bran removed. This polished rice is stored, wrapped to be shipped after being blended with various kinds of polished rice, or is used immediately for boiled rice. In various transportation processes of transporting rice from an unpolished rice storage tank to the rice polishing machine, from the rice polishing machine to a rice bran removing machine, from the rice bran removing machine to a polished rice storage tank, from the polished rice storage tank to a blended rice accommodation tank, and so on, a number of transportation apparatus such as bucket conveyers, lifts, horizontal belt conveyers, and the like are usually used.
However, these transportation apparatus tend to become upsized as factories become large, which has resulted in difficulty in assembly, installation, and maintenance thereof. Furthermore, since rice bran remains in gap parts in these transportation apparatus, microbes such as mold may possibly grow to gather insects and so on eating the mold. This has brought about a problem that values of rice and boiled rice as products may possibly be lost. Since the transportation apparatus need to be frequently disassembled for cleaning in order to eliminate the problem, a problem has been further caused that maintenance cost is increased.
To solve these problems, apparatus for pneumatically transporting rice through pipes are known as are disclosed in Japanese Patent Laid-open No. Hei 7-330151, Japanese Patent Laid-open No. Hei 2-56255, and Japanese Patent Laid-open No. Sho 52-20582. In these apparatus, grain such as rice is transported by air streams which are generated in pipes with the use of blowers and compressors. The use of such a pneumatic transportation method makes it possible to avoid the problem that the rice bran remains halfway in the pipes since the rice and the air are transported in the pipes which are shielded from the outside.
However, in the conventional pneumatic transportation method, problems have often occurred that transported rice is crushed or each grain of rice cracks to reduce the value of the rice as a product. Since consumers demand high quality, particularly for rice to be used for boiled rice, sufficient quality control is required. However, it has been very difficult to transport rice pneumatically without causing any crush or crack to the rice.
The present invention is made in view of the conventional problems as described above and it is an object of the present invention to provide a gas transportation method and apparatus which are capable of preventing transported grain such as rice from crushing or cracking.
SUMMARY OF THE INVENTION
Transportation methods by means of gas such as air are generally divided into a high-pressure transportation method in which the pressure of supplied air is set at a value equal to 200 kPa (kilopascal) or more and a low-pressure transportation method in which the pressure of the supplied air is suppressed at a low value. In the high-pressure transportation method, pressurizing air flows through transportation pipes at a high speed when transportation is finished so that substances moving though the pipes may possibly collide with inner wall surfaces of the pipes to be crushed. Hardness of grain such as rice is generally in a lower range of 11≦Hv≦14 in terms of Vickers hardness Hv and since the occurrence of crush and crack of grain during transportation affect its quality, the low-pressure transportation method in which the pressure of the supplied air is suppressed at a low value is appropriate for pneumatic transportation of grain. However, when grain is transported through pneumatic transportation pipes in which transportation passages are long and curved, pressure loss is caused. Therefore, making allowance for this pressure loss, air pressure of a supplying source is generally set at approximately 50 kPa. Transportation of grain through the pipes under this pressure causes the possibility that the grain may be damaged, and therefore, a countermeasure for this problem is required.
Next, findings obtained by the inventors of the present invention are explained. As a result of various studies on correlation of a collision speed of polished rice with its crushing rate and cracking rate, the inventors of the present invention have found that a velocity V of transportation gas needs to be in a range from 10 m/s to 20 m/s. FIG. 1 is a graph showing correlation between a collision speed and rates of occurrence of crushed granules of polished rice and of occurrence of cracked plus crushed granules of polished rice. Here, the crushed granules of polished rice mean polished rice which is crushed to be broken into pieces and therefore, is difficult to be used as boiled rice and can be used only for materials for confectionary, rice crackers, or the like. The cracked granules mean polished rice which only has cracks therein and can be used as boiled rice. This experiment was conducted, using a device in which a blower 82 is disposed at one end of an acryl pipe 81 having length of 1000 mm and a stainless plate 83 is disposed vertically in a position 25 mm away from an exit at the other end of the acryl pipe 81 , as shown in FIG. 2 . Damage condition of polished rice 84 was examined after the polished rice 84 was put at an end part on a blower 82 side inside the acryl pipe 81 as shown in FIG. 2 and was pneumatically transported by the blower 82 to be collided with the stainless plate 83 at a collision angle of 90 degrees.
It is apparent from FIG. 1 that the occurrence rate of crushed granules or cracked and crushed granules of the polished rice suddenly increases when the collision speed exceeds 20 m/s. Therefore, the velocity V of the transportation air needs to be set at a value equal to 20 m/s or less. Meanwhile, in order to secure an amount of transported rice in pneumatic transportation, the velocity V of the transportation air needs to be set at a value equal to 10 m/s or more. Based on the above findings, it has been found that the velocity V of the transportation air needs to be set at a value in a range of 10 m/s≦V≦20 m/s.
The inventors of the present invention have also found it appropriate that a blending ratio μ which is expressed by a ratio of a flow amount of the polished rice (Kg/H) to a flow amount of the transportation air (Kg/H) is set at a value within the following range. Namely, the inventors of the present invention have obtained the result, after studying correlation between the velocity V (m/s) of the transportation air and the blending ratio μ, that appropriately, the blending ratio is within the range between the line P-R and the line Q-S in FIG. 3 . In FIG. 3, L 1 , L 2 , L 3 , and L 4 show results in cases where the length of the transportation pipe is 15 m, 50 m, 75 m, and 100 m respectively. A favorable result has been obtained that the polished rice can be transported without any crushed granules occurring therein in this range while an unfavorable result has been obtained that the occurrence rate of the crushed granules increases outside this range. Based on these results, it has been found appropriate that the blending ratio μ is in a range of (3 V−30)≦μ≦(3 V−20).
The inventors of the present invention have also confirmed in the experiment that the inside of the pipe is clogged when μ exceeds 10 under the condition that the velocity V of the transportation air is approximately 10 m/s, which does not allow pneumatic transportation to be performed. It has also been confirmed in the experiment that, when μ is 10 or less, since the inside of the pipe approximates to vacancy, the pipe is not clogged, which allows the rice to be sent smoothly, but since an amount of transported rice is small, the rice easily collides, and, under the condition of a high velocity of the transportation air, it easily crushes. Meanwhile, as the velocity V approaches 20 m/s, which results in an increased amount of the transportation air, even more amount of the rice can be transported and crushing is reduced owing to self-cushion among the rice. However, there is a limit that crushing increases drastically when the velocity V exceeds 20 m/s as described above.
Based on the above findings, the inventors of the present invention have found it appropriate that the blending ratio μ is within the range surrounded by the substantial parallelogram P, Q, R, S shown in FIG. 3 .
The inventors of the present invention have also obtained correlation of a difference in temperature between polished rice and transportation air with damage to the polished rice under the condition that the velocity V of the transportation air is fixed (V=20 m/s), using the experiment device shown in FIG. 2 . In this experiment, the polished rice 84 is put and kept unmoved in the air whose temperature is 20° C. and whose humidity is 70%, and thereafter, the polished rice 84 whose temperature has reached 20° C. is put at one end on the blower 82 side of the acryl pipe 81 , while an air stream generated by the blower 82 is supplied with its temperature adjusted by a heater 85 to vary its difference in temperature from that of the polished rice 84 . Similarly to the aforesaid experiment, the damage condition of the polished rice 84 was examined after the polished rice 84 was pneumatically transported by the blower 82 to be collided with the stainless plate 83 at the collision angle of 90 degrees.
The result of the experiment is shown in FIG. 4 . In FIG. 4, the horizontal axis shows a difference in temperature (° C.) between the polished rice and the transportation air and the vertical axis shows an occurrence rate of crushed granules and an occurrence rate of cracked granules of the polished rice. The occurrence rate of crushed granules is shown by the solid line A and the occurrence rate of cracked granules is shown by the broken line B.
It is apparent from FIG. 4 that a crushing rate of the polished rice varies depending on the temperature difference between the polished rice and the transportation air. For example, the result of the experiment in FIG. 1 shows that the crushing rate of the polished rice is approximately 15% under the condition of the velocity of V=20 m/s, but the result of the experiment in FIG. 4 shows that the crushing rate of the polished rice increases to approximately 22% or more under the condition that the temperature difference between the polished rice and the transportation air is 20° C. or more.
The inventors of the present invention have found from the experiment result shown in FIG. 4 that crushed granules do not occur when the temperature difference between the polished rice and the transportation air is 10° C. or less. Therefore, when the polished rice is transported by transportation air flowing through transportation pipes which are connected with tanks for accommodating the polished rice therein, it is appropriate that the transportation air whose temperature difference from that of the polished rice flowing into the tanks or the polished rice flowing out of the tanks is 10° C. or less is supplied into the transportation pipes to transport the polished rice. Basically, it is appropriate that the temperature of the transportation air is equal to the temperature of the polished rice, but it has been found that in an actual apparatus, the temperature difference of the transportation air from that of the polished rice may be within a range of ±15° C. and more appropriately, within a range of ±10° C.
The present invention, which is made based on the above findings, is a gas transportation method for grain having Vickers hardness Hv in a range of 11≦Hv≦14, and is characterized in that a velocity V of transportation gas is adjusted to be in a range of 10 m/s≦V≦20 m/s.
The present invention is also a gas transportation method for grain having Vickers hardness Hv in a range of 11≦Hv≦14, and is characterized in that a blending ratio μ expressed as a ratio of a flow amount of the grain (kg/H) to a flow amount of transportation gas (kg/H) is set in a range of (3 V−30)≦μ≦(3 V−20).
It is also a gas transportation method for grain having Vickers hardness Hv in a range of 11≦Hv≦14, and is characterized in that a velocity V of transportation gas is set to be in a range of 10 m/s≦V≦20 m/s and a blending ratio μ expressed as a ratio of a flow amount of the grain (kg/H) to a flow amount of the transportation gas (kg/H) is set to be in a range of (3 V−30)≦μ≦(3 V−20).
Furthermore, it is appropriate that the temperature of the transportation gas is controlled so that a difference between the temperature of the transportation gas and the temperature of the grain is within a predetermined range.
It is appropriate here that the difference between the temperature of the transportation gas and the temperature of the grain is 15° C. or less.
It is also appropriate that the humidity of the transportation gas is controlled to be at a value substantially equal to equilibrium temperature of the grain.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing correlation of a collision speed with an occurrence rate of crushed granules and of cracked plus crushed granules of polished rice when the polished rice is collided with a wall surface at a right angle;
FIG. 2 is an explanatory view of a device used for the experiment in FIG. 1;
FIG. 3 is a graph showing correlation between a velocity of transportation air and a blending ratio in pneumatic transportation of polished rice;
FIG. 4 is a graph showing correlation of a difference in temperature between the polished rice and the transportation air with the occurrence rate of the crushed granules and the cracked granules of the polished rice;
FIG. 5 is an explanatory block diagram of a transportation apparatus for rice showing one embodiment of the present invention; according to the present invention; and
FIG. 6 is a fragmentary enlarged view of the transportation apparatus for rice in FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A preferred embodiment of a gas transportation method for grain according to the present invention is explained in detail below with reference to the drawings.
FIG. 5, showing one embodiment of the gas transportation method for grain according to the present invention, is an explanatory block diagram of an apparatus in a case where the present invention is applied to pneumatic transportation of rice.
FIG. 5, a transportation apparatus 1 for rice has a structure in which four stages of transportation pipes 11 through which pneumatic transportation is performed are connected in series. The transportation apparatus 1 is composed of an unpolished rice storage section 2 for storing unpolished rice therein, a rice polishing section 3 for polishing the unpolished rice to make half-polished rice, a rice bran removing section 4 for removing rice bran from the half-polished rice to make polished rice, a polished rice storage section 5 for storing the polished rice therein, and a blending section 6 for blending various kinds of polished rice stored in the polished rice storage section 5 .
The transportation pipes 11 are composed of a first transportation pipe 11 a for connecting the unpolished rice storage section 2 with the rice polishing section 3 , a second transportation pipe 11 b for connecting the rice polishing section 3 with the rice bran removing section 4 , a third transportation pipe 11 c for connecting the rice bran removing section 4 with the polished rice storage section 5 , and a fourth transportation pipe 11 d for connecting the polished rice storage section 5 with the blending section 6 . It is necessary that curvature of passages of these transportation pipes 11 is set at a value at least equal to 500 mmR or more (more appropriately, about 1000 mmR) to prevent rice from colliding with inner walls of the pipes at an acute angle.
The transportation pipes 11 are provided at respective starting ends thereof with blowers 13 for sending an air stream and intercoolers 15 which are disposed inside the pipes on downstream sides of the blowers 13 , for heating or cooling transportation air according to the temperature of the rice to adjust the temperature of the transportation air. By putting the blowers 13 and the intercoolers 15 into operation, the air whose temperature is adjusted at a value appropriate for the rice moving toward terminal ends of the transportation pipes 11 is sent into the transportation pipes 11 . Moreover, humidifying/dehumidifying devices 17 are provided on downstream sides of the intercoolers 15 to adjust the humidity of the transportation air to be equal to equilibrium humidity of the rice. Here, the equilibrium humidity of the rice, which means the humidity at which rice does not absorb or discharge moisture, is approximately 70%.
Each of the transportation pipes 11 a , 11 b , 11 c , and 11 d is explained as follows. In the first transportation pipe 11 a , a first blower 13 a , a first intercooler 15 a , and a first humidifying/dehumidifying device 17 a are disposed; in the second transportation pipe 11 b , a second blower 13 b , a second intercooler 15 b , and a second humidifying/dehumidifying device 17 b are disposed; in a third transportation pipe 11 c , a third blower 13 c , a third intercooler 15 c , and a third humidifying/dehumidifying device 17 c are disposed; and in a fourth transportation pipe 11 d , a fourth blower 13 d , a fourth intercooler 15 d , and a fourth humidifying/dehumidifying device 17 d are disposed.
The unpolished rice storage section 2 is provided with a plurality of first storage tanks 21 for storing unpolished rice therein, and the first storage tanks 21 are connected with the first transportation pipe 11 a at parts on a downstream side of the first blower 13 a , the first intercooler 15 a , and the humidifying/dehumidifying device 17 a via respective rotary feeders 23 . When the transportation air is supplied to the first transportation pipe 11 a by the first blower 13 a , the unpolished rice discharged from the first storage tanks 21 by the respective rotary feeders 23 is transported toward the rice polishing section 3 which is disposed at a terminal end of the first transportation pipe 11 a.
All of first storage tanks 21 A, 21 B, 21 C . . . , and so on are provided with unpolished rice temperature sensors 25 for measuring respective temperatures of stored unpolished rice A, B, C . . . , and so on, and temperature signals indicating the temperatures measured by the unpolished rice temperature sensors 25 are transmitted to control means 31 . The control means 31 stores the temperatures of the first intercooler 15 a corresponding to the temperatures of the unpolished rice measured by the unpolished rice temperature sensors 25 and controls a difference in temperature between the unpolished rice and the transportation air to be within a predetermined range. Alternatively, feed back control is also appropriate in which a temperature sensor 29 (shown in FIG. 6) for measuring the temperature of the air is provided inside the first transportation pipe 11 a on a downstream side of the first intercooler 15 a and the humidifying/dehumidifying device 17 a as shown in FIG. 6, and the control means 31 receives a temperature signal indicating the measured temperature to adjust the temperature of the first intercooler 15 a . Furthermore, a humidity sensor 27 a for measuring the humidity of the transportation air from the first intercooler 15 a is also provided in the first transportation pipe 11 a , and a humidity signal indicating the humidity measured by the humidity sensor 27 a is transmitted to the control means 31 . Based on this humidity signal, the control means 31 outputs an instruction to the humidifying/dehumidifying device 17 a so that the humidity of the transportation air is adjusted to be equal to the equilibrium humidity (approximately 70%) of the rice, for example, by generation of vapor, and the control means 31 causes the transportation air to be supplied to the first transportation pipe 11 a.
The rice polishing section 3 is provided with a plurality of branch valves 33 which are disposed in series in the first transportation pipe 11 a , for sending the unpolished rice which is transported thereto to either one of branching-off passages. By an appropriate changeover operation of the branch valve 33 designated by an instruction from the control means 31 , the unpolished rice which has passed through either one of the branching-off passages is sent to a corresponding rice polishing machine 37 via a corresponding first accommodation tank 35 to be processed into half-polished rice. Incidentally, the structure in which the changeover operation is performed at a branching angle of 30° or less so as not to have branching lines make sharp curves at the branch valves 33 prevents the unpolished rice from crushing due to collision. Under the rice polishing machines 37 , a plurality of second accommodation tanks 39 for storing half-polished rice and storing various kinds of half-polished rice to be supplied to a starting end side of the second transportation pipe 11 b are disposed.
The plural second accommodation tanks 39 are connected with the second transportation pipe 11 b at parts on a downstream side of the second blower 13 b and the second intercooler 15 b via respective rotary feeders 23 . Supplying the transportation air to the second transportation pipe 11 b by the second blower 13 b causes the half-polished rice which is discharged from the second accommodation tanks 39 by the respective rotary feeders 23 to be transported to the rice bran removing section 4 which is disposed at a terminal end of the second transportation pipe 11 b . In the second accommodation tanks 39 , half-polished rice temperature sensors 41 for measuring the temperatures of the stored half-polished rice is provided and temperature signals indicating the temperatures measured by the half-polished rice temperature sensors 41 are transmitted to the control means 31 . Furthermore, a humidity sensor 27 b for measuring the humidity of the transportation air from the second intercooler 15 b is provided in the second transportation pipe 11 b and a humidity signal indicating the humidity measured by the humidity sensor 27 b is transmitted to the control means 31 . The control means 31 receives the temperature signals and the humidity signal to perform control operation in the same manner as previously described.
The rice bran removing section 4 is provided with a plurality of branch valves 33 which are connected in series in the second transportation pipe 11 b , for sending the half-polished rice which is transported thereto to either one of branching-off passages. By the changeover operation of the branch valve 33 designated by an instruction from the control means 31 , the half-polished rice which has passed through either one of the branching-off passages is sent to a corresponding rice bran removing machine 45 to be processed into polished rice with its rice bran removed. Under the rice bran removing machines 45 , a plurality of third accommodation tanks 47 for storing the polished rice from which rice bran has been removed and storing various kinds of polished rice to be supplied to a starting end side of the third transportation pipe 11 c are disposed.
The plural third accommodation tanks 47 are connected with the third transportation pipe 11 c at parts on a downstream side of the third blower 13 c and the third intercooler 15 c via respective rotary feeders 23 . Supplying the transportation air to the third transportation pipe 11 c by the third blower 13 c causes the polished rice which is discharged from the third accommodation tanks 47 by the respective rotary feeders 23 to be transported to the polished rice storage section 5 which is disposed at a terminal end of the third transportation pipe 11 c . In the third accommodation tanks 47 , polished rice temperature sensors 49 for measuring the temperatures of the stored polished rice is provided and temperature signals indicating the temperatures measured by the polished rice temperature sensors 49 are transmitted to the control means 31 . Furthermore, a humidity sensor 27 c for measuring the humidity of the transportation air from the third intercooler 15 c is provided in the third transportation pipe 11 c and a humidity signal indicating the humidity measured by the humidity sensor 27 c is transmitted to the control means 31 . The control means 31 receives the temperature signals and the humidity signal to perform control operation in the same manner as previously described.
The polished rice storage section 5 is provided with a plurality of branch valves 33 which are disposed in series in the third transportation pipe 11 c , for sending the polished rice which is transported thereto to either one of branching-off passages. By the changeover operation of the branch valve 33 designated by an instruction from the control means 31 , the polished rice which has passed through either one of the branching-off passages is stored in a predetermined polished rice storage tank 51 .
The plural polished rice storage tanks 51 are connected with the fourth transportation pipe 11 d at parts on a downstream side of the fourth blower 13 d and the fourth intercooler 15 d via respective rotary feeders 23 . Supplying the transportation air to the fourth transportation pipe 11 d by the fourth blower 13 d causes the polished rice which is discharged from the polished rice storage tanks 51 by the respective rotary feeders 23 to be transported toward the blending section 6 which is disposed at a terminal end of the fourth transportation pipe 11 d . In the polished rice storage tanks 51 , stored polished rice temperature sensors 53 for measuring the temperatures of the stored polished rice is provided and temperature signals indicating the temperatures measured by the stored polished rice temperature sensors 53 are transmitted to the control means 31 . Furthermore, a humidity sensor 27 d for measuring the humidity of the transportation air from the fourth intercooler 15 d is provided in the fourth transportation pipe 11 d and a humidity signal indicating the humidity measured by the humidity sensor 27 d is transmitted to the control means 31 . The control means 31 receives the temperature signals and the humidity signal to perform control operation in the same manner as described above.
The blending section 6 is provided with a plurality of branch valves 33 which are disposed in series in the fourth transportation pipe 11 d , for sending the stored polished rice which is transported thereto to either one of the branching-off passages. By the changeover operation of the branch valve 33 designated by an instruction from the control means 31 , the stored polished rice which has passed through the branching-off passage is accommodated in a corresponding measuring tank 57 . The measuring tanks 57 are provided with load sensors 59 attached thereto, which measure the weights of kinds of polished rice A, B, C . . . , and so on which are transported via the fourth transportation pipe 11 d and the branch valves 33 to transmit the measured weights to the control means 31 . When set specific amounts of various kinds of the polished rice A, B, C . . . , and so on are transported to and accommodated in the measuring tanks 57 , valves 61 are opened to send the polished rice to blending machines 63 . The blending machines 63 are driven by motors 63 a according to instructions from the control means 31 to be rotated and blend various kinds of the polished rice A, B, C, . . . , and so on to make blended rice. The blended rice is wrapped by wrapping machines 67 and shipped after being accommodated in blended rice accommodation tanks 65 .
Incidentally, the control means 31 is connected with not-shown driving devices for driving the first blower 13 a , the second blower 13 b , the third blower 13 c , and the fourth blower 13 d to control the respective blowers to start driving and stop driving. Furthermore, the control means 31 is connected with not-shown operating devices for operating the rotary feeders 23 and the branch valves 33 to control their starting and stopping operations and outputs instructions to these devices that the rice such as the unpolished rice, the half-polished rice, and the polished rice should be supplied to a predetermined one of the storage tanks, accommodation tanks, rice bran removing machines 45 , measuring tanks 57 , and so on from the pipes. The order of operations of the blowers 13 , the intercoolers 15 , the rotary feeders 23 , the branch valves 33 , the rice polishing machines 37 , the rice bran removing machines 45 , the blending machines 63 , and so on is determined by inputs to the control means 31 according to a required kind of blended rice, a required amount of rice, a shipment situation, and so on. The above-mentioned rotary feeders 13 are discharge devices which have space partitioned by blades arranged at equal spaced intervals on the circumferences thereof and are driven by not shown electric motors, and they are structured to discharge predetermined amounts of rice by their rotation. The branch valves 33 are disposed in series, among which only the branch valve 33 receiving an instruction signal from the control means 31 is changed over at the time of operation to transport the rice from the transportation pipes in a branching-off manner.
In this embodiment, unpolished rice is pneumatically transported from the unpolished rice storage section 2 for storing unpolished rice therein to the rice polishing section 3 which is disposed on a subsequent stage, for polishing unpolished rice, and half-polished rice is pneumatically transported from the rice polishing section 3 to the rice bran removing section 4 for removing rice bran to make polished rice, and furthermore, polished rice is pneumatically transported from the rice bran removing section 4 to the polished rice storage section 5 for storing polished rice therein. This pneumatic transportation is performed by each of the blowers 13 and each of the rotary feeders 23 in each of the processing sections as described above, and they are controlled by the control means 31 .
The velocity V of the transportation air generated by the blowers 13 and the blending ratio μ are controlled by the control means 31 and are controlled to be at the following values as described above. Namely, the velocity V of the transportation air supplied from each of the blowers 13 a , 13 b , 13 c , and 13 d is controlled to be within the following range:
[Numerical formula 1]
10 m/s≦V≦20 m/s
Furthermore, the blending ratio μ expressed as the ratio of the flow amount of the rice (kg/H) to the flow amount of the transportation air (kg/H) is controlled to be in the following range.
[Numerical formula 2]
(3 V−30)≦μ≦(3 V−20)
The blending ratio μ is defined as follows.
[Numerical formula 3]
μ=a flow amount of rice (g/H)/a flow amount of air (kg/H)
Showing specific values for the above by a graph as the blending ratio μ relative to the velocity V (m/s) of the transportation air, the result shown in FIG. 3 is obtained as previously described. The range surrounded by the substantial parallelogram P, Q, R, S including the lines at the lower limit value 10 m/s and the upper limit value 20 m/s of the velocity of the transportation air is a range where crushing and cracking of the rice do not occur. More specifically, when μ exceeds 10 under the condition that V (m/s) is approximately 10 m/s, the inside of the pipes is clogged, which does not allow gas transportation, and therefore, the flow amount of the rice cannot be increased. When μ is less than 10, the pipes are not clogged to allow the rice to be sent smoothly, but since the flow amount of the rice is small, the problem that collision easily occurs and the rice easily crushes is caused. Moreover, since transportation efficiency is low, this condition cannot be applied. As V approaches 20 m/s, which results in an increased amount of the air, even more amount of the grain is allowed to be transported. Even when the inside of the pipes are filled with a large amount of the grain, transportation can be performed, and the occurrence rate of crushing is low even at a high velocity owing to self-cushion among the grain. However, when the velocity V exceeds 20 m/s, the occurrence rate of crushing drastically increases, and therefore, the maximum value for μ is 40.
The control means 31 is connected with the first intercooler 15 a , the second intercooler 15 b , the third intercooler 15 c , and the fourth intercooler 15 d as shown in FIG. 5 and it outputs instructions to the intercoolers 15 so that differences between the rice temperatures received from the rice temperature sensors and the transportation air temperature are controlled to be within a predetermined range. In order to cool gas warmed in the blowers 13 , the intercoolers 15 generally output instructions to coolant valves 71 for controlling coolant to control the temperature of the transportation air. More specifically, the control means 31 stores the temperatures of the rice and the temperature of the transportation air whose temperature difference from the rice temperature is within a range of ±15° C. and controls the intercoolers 15 so that the difference in temperature between the rice and the transportation air is within the range of ±15° C. More appropriately, the difference in temperature is controlled to be within a range of ±10° C. This temperature control and the control of the velocity and the blending ratio can realize more efficient pneumatic transportation of rice.
The control means 31 is also connected with the humidifying/dehumidifying devices 17 a , 17 b , 17 c , and 17 d and outputs instructions to the humidifying/dehumidifying devices 17 a , 17 b , 17 c , and 17 d so that the humidity of the transportation air is controlled to be equal to the equilibrium humidity of the rice. At this time, the control means 31 stores the value of the humidity of the transportation air as approximately 70% which is the equilibrium humidity of the rice and controls the humidifying/dehumidifying devices 17 a , 17 b , 17 c , and 17 d so that the humidity of the transportation air is adjusted to be approximately 70% which is the equilibrium humidity of the rice after receiving the humidity signals of the transportation air from the humidity sensors 27 a , 27 b , 27 c , and 27 d.
Next, the procedure for supplying rice using the transportation apparatus 1 as structured above is explained.
First, the temperature of designated unpolished rice (for example, rice A) stored in the first storage tank 21 is measured by the corresponding unpolished rice temperature sensor 25 and a temperature signal indicating the measured temperature is transmitted to the control means 31 . The control means 31 determines the temperature of the transportation air according to the measured temperature of the unpolished rice, based on the result shown in FIG. 4, outputs an instruction to adjust the air flowing in the first intercooler 15 a to be at the determined temperature, and puts the coolant valve 71 of the first intercooler 15 a into operation. At this time, the control means 31 also outputs an instruction to the driving source for driving the first blower 13 a so that the transportation air whose velocity V is in the range of 10 to 20 m/s is generated. The transportation air flowing in the first intercooler 15 a is adjusted to be at the determined temperature and is supplied to the first transportation pipe 11 a . Furthermore, the humidity of the transportation air is measured by the humidity sensor 27 a and a humidity signal indicating the measured humidity is transmitted to the control means 31 . The control means 31 outputs the instruction to the humidifying/dehumidifying device 17 a so that the humidity of the transportation air is controlled to be equal to the equilibrium humidity (approximately 70%) of the rice, for example, by generation of vapor, and causes the transportation air to be supplied to the first transportation pipe 11 a.
When the transportation air flowing in the first transportation pipe 11 a is kept at the determined velocity, temperature, and humidity, the control means 31 puts the rotary feeder 23 a of the designated first storage tank 21 a into operation and causes the unpolished rice A to be supplied to the first transportation pipe 11 a . The rotary feeder 23 a is controlled so that this supply amount is within the range shown in FIG. 3 . This control can be performed by setting the supply amount at a value on the centerline in the parallelogram. More specifically, in FIG. 3, the blending ratio μ is controlled to be approximately 15, for example, when the velocity of the transportation air is set at 14 m/s. The unpolished rice A supplied to the first transportation pipe 11 a is transported by the transportation air through the first transportation pipe 11 a to flow into the rice polishing section 3 . Thereby, the unpolished rice transported through the first transportation pipe 11 a is transported under the condition that the temperature difference between the rice and the transportation air is within the set temperature range, regardless of variation in the temperature of the rice depending on seasons such as summer or winter and so on. This makes it possible to reduce the occurrence of crushed granules and cracked granules of the rice.
The unpolished rice A flowing into the rice polishing section 3 is accommodated in a predetermined one of the first accommodation tanks 35 from the first transportation pipe 11 a by the changeover operation of the branch valve 33 designated by the control means 31 . The accommodated unpolished rice A is polished by the corresponding rice polishing machine 37 provided on a downstream side thereof to be processed into half-polished rice. At this time, the temperature of the half-polished rice increases by approximately 20° C. due to the polishing operation by the rice polishing machine 37 . The half-polished rice whose temperature has increased is accommodated in the corresponding second accommodation tank 39 which is disposed on a downstream side of the rice polishing machine 37 .
When the rice is continued to be conveyed to a downstream process in the rice polishing process, the half-polished rice whose temperature has increased is supplied from the second accommodation tank 39 to the second transportation pipe 11 b via the rotary feeder 23 which is operated according to an instruction given by the control means 31 . At this time, the velocity V of the transportation air and the blending ratio μ are also determined. Furthermore, the temperature of the half-polished rice in the second accommodation tank 39 is measured by the half-polished rice temperature sensor 41 and a temperature signal indicating the measured temperature is transmitted to the control means 31 . The control means 31 determines the temperature of the transportation air according to the measured temperature of the half-polished rice whose temperature has increased so that the temperature difference between the half-polished rice and the transportation air is within the predetermined temperature range, and the control means 31 outputs an instruction that the transportation air flowing in the second intercooler 15 b should be adjusted at the determined temperature and puts the second intercooler 15 b into operation. Thereby, the rice transported through the second transportation pipe 11 b is transported under the condition that the difference in temperature between the transportation air and the rice is within the set temperature range even if its temperature increases by approximately 20° C. after being polished by the rice polishing machine 37 , which can reduce the occurrence of crushed granules and cracked granules. Furthermore, the humidity of the transportation air is measured by the humidity sensor 27 b and a humidity signal indicating the measured humidity is transmitted to the control means 31 . Then, the control means 31 controls the humidifying/dehumidifying device 17 b to adjust the humidity of the transportation air. The control means 31 also outputs an instruction to the driving device for driving the second blower 13 b to cause the transportation air to be generated. The transportation air flowing in the second intercooler 15 b is supplied to the second transportation pipe 11 b while being controlled to be at the determined temperature and humidity. Then, the control means 31 puts the rotary feeder 23 of the second accommodation tank 39 into operation and causes the half-polished rice to be discharged to the second transportation pipe 11 b . The half-polished rice discharged to the second transportation pipe 11 b is transported by the transportation air through the second transportation pipe 11 b and transported to the rice bran removing section 4 .
In a case where the rice is transported to the subsequent process after it is temporarily accommodated and kept in the second accommodation tank 39 , the rice is supplied to the second transportation pipe 11 b via the rotary feeder 23 which also operates according to the instruction from the control means 31 . At this time, the velocity V of the transportation air and the blending ratio μ are also determined. Furthermore, the temperature of the half-polished rice in the second accommodation tank 39 is measured by the half-polished rice temperature sensor 41 and a temperature signal indicating the measured temperature is transmitted to the control means 31 . The control means 31 determines the temperature of the transportation air according to the measured temperature of the half-polished rice whose temperature has increased, outputs an instruction that the air flowing in the second intercooler 15 b should be adjusted to be the determined temperature, and puts the second intercooler 15 b into operation. The humidity is also controlled by the humidity sensor 27 b and the control means 31 , and the half-polished rice is sent to the rice bran removing section 4 through the second transportation pipe lib.
Thereafter, similar processing is performed up to the process performed by the blending section 6 for polished rice.
As described hitherto, according to the present invention, the occurrence of crushed granules and cracked granules of the rice during transportation can be reduced when the rice is pneumatically transported from the unpolished rice storage tanks to the rice polishing machines, from the rice polishing machines to the rice bran removing machines, from the rice bran removing machines to the polished rice storage tanks, from the polished rice storage tanks to the blended rice accommodation tanks, and so on.
Incidentally, in the above-described embodiment, the case where rice is transported is explained, but the present invention is applicable to gas transportation of other grain such as wheat and corn other than rice. Moreover, the transportation gas is not limited to air, and nitrogen gas, which is filled in the pipes in order to prevent explosion, can also be used for transportation.
As described hitherto, according to the present invention, the occurrence of crushed granules and cracked granules can be reduced when grain is transported by means of gas. | It is an object of the present invention to provide a method for reducing crushing of grain when the grain having Vickers hardness Hv in a range of 11≦Hv≦14 is transported by means of gas. The present invention is a gas transportation method for grain having Vickers hardness Hv in a range of 11≦Hv≦14, and gas transportation is performed under the condition that a velocity V of transportation gas is set at a value in a range of 10 m/s≦V≦20 m/s. Alternatively or additionally, a blending ratio μ expressed as a ratio of a flow amount of the grain (kg/H) to a flow amount of the transportation gas (kg/H) is set at a value in a range of (3 V−30)≦μ≦(3 V−20). | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing a plastic article with a cavity enclosed in the same, comprising the following steps: injection of plastic material under pressure into a mould cavity, cooling the plastic material closest to the walls of the mould cavity, injection of gas under pressure into fluent plastic material, which is surrounded by the cooled plastic material, pressing out, by means of the injected gas, fluent plastic material to at least one spill chamber located outside the mould cavity and communicating with the mould cavity injected gas, to form a cavity in the plastic material, and separation of the plastic material in the spill chamber from the plastic material in the mould cavity.
The invention also relates to an injection moulding device with a mould cavity defined by movable walls, comprising means for injecting under pressure fluent plastic material into the mould cavity, means for injecting gas under pressure into the plastic material in the mould cavity, at least one spill chamber located outside the mould cavity and communicating with the mould cavity, said spill chamber being arranged to receive plastic material forced out by the injected gas, and means for opening and cutting off the communication with the spill chamber.
DESCRIPTION OF THE RELATED ART
The method of manufacturing hollow plastic articles by first filling the mould cavity completely as in normal injection moulding and thereafter, with the aid of the gas, pressing the core material out to a spill changer, so that the cavity in the article is formed, is usually called “blow-out gas injection” and is described, for example, in U.S. Pat. No. 5,204,051. In the known method, the communication between the mould cavity and the spill chamber is kept closed during the injection of the plastic material and is opened after the mould cavity has been completely filled, and only after the surface of the plastic material has hardened somewhat. The purging here is done by leakage between the mould halves, and this means that the counter-pressure against the plastic material will be relatively great.
In this process, all of the plastic material injected into the mould cavity will remain in the cavity. This means that the plastic material, which, at the beginning of the injection, is in and nearest to the nozzle of the mould injector and which has a lower temperature and/or poorer quality than the rest of the plastic material, especially when the flow channel areas are large, can end up in the mould cavity at a location farthest away from the inlet to the mould cavity. This can occur in particular when injecting thermosetting resins and/or so-called cross-linkable plastics.
SUMMARY OF THE INVENTION
The purpose of the present invention is to achieve a method and a device, through which the above mentioned disadvantage can be eliminated, so that more even wall thickness and uniform plastic quality can be achieved in the manufactured plastic article.
This is achieved by virtue of the fact that a communication with a predetermined flowthrough area is maintained between the mould cavity and the spill chamber during the injection of the fluent plastic material, and that a communication with a larger predetermined flowthrough area is maintained between the mould cavity and the spill chamber during the injection of the gas.
The communication with smaller flowthrough area is maintained for such a long time that all the air is pressed out of the cavity and possibly a small amount of the plastic material is pressed out to the spill chamber. The method according to the invention achieves not only a product with an even wall thickness and uniform plastic quality but also makes it possible to shorten the production cycle by virtue of the fact that purging of the mould cavity of air can be done much more rapidly than when the purging is done by normal leakage between two mould halves. More rapid purging also reduces the risk of small air bubbles forming in the plastic material.
An injection moulding device for carrying out the method is characterized in that a communication with a predetermined flowthrough area is maintained between the mould cavity and the spill chamber during the injection of the fluent plastic material, and that a communication with a larger predetermined flowthrough area is maintained between the mould cavity and the spill chamber during the injection of the gas.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described in more detail below with reference to examples shown in the accompanying drawings, where
FIG. 1 shows a section through a schematically represented injection moulding device according to the invention,
FIG. 2 shows a perspective view of the rear of a plastic panel in the form of a radiator grill for motor vehicles, which can be manufactured by using the method and the device according to the invention,
FIG. 3 shows a section along the line III—III in FIG. 2, and
FIG. 4 shows a section along the line IV—IV in FIG. 3 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Element 1 in FIG. 1 generally designates a mould, which comprises upper and lower mould halves 2 and 3 , respectively, which define together a mould cavity 4 and which can be moved away from each other, by means not shown in more detail here, from the position shown to open the mould cavity 4 . A nozzle 6 of a mould injector opens into a channel 5 through the upper mould half 2 . The mould injector has a cylinder 7 and a piston 8 axially movable in the cylinder, by means of which fluent plastic in the cylinder 7 can be pressed into the mould cavity 4 .
The mould halves 2 and 3 define, in addition to the mould cavity 4 , a pair of so-called spill chambers 9 , which communicate with the mould cavity 4 via individual channels 10 . A bore 11 opens into each channel 10 , and an ejector pin 12 is arranged displaceable in each bore 11 . A corresponding ejector pin 13 is arranged in a bore 14 , opening into each spill chamber 9 . A gas needle 15 extends directly opposite the channel 5 and is provided with an opening 15 a, through which gas can be injected into the plastic material in the mould cavity 4 . The gas needle 15 can be fixed in the position shown or be extractable out of the mould cavity 4 .
Element 16 in FIG. 1 designates a control unit, 17 designates a compressed gas source and 18 and 19 are drive means for driving the piston 8 and the ejector pins 12 , respectively. FIG. 1 is symmetrical relative to a center plane A and to the left of the plane A the state is illustrated after the piston 8 has come to the bottom of the cylinder 7 and the mould cavity 4 has been completely filled with fluent plastic “b” while air and a small amount of plastic material “c” have been pressed out to the spill chamber 9 . During the plastic injection phase, the control unit 6 keeps the ejector pins 12 in the position shown to the left in FIG. 1 via the drive means 19 , in which position the upper end surface 12 a of each ejector pin 12 leaves a narrow passage 10 a open, through which first air and then plastic material can pass to the spill chamber 9 .
When the injection of plastic is finished, all air, and possibly a small amount of plastic, has been evacuated to the spill chambers 9 . The control unit 16 then activates the compressed gas source 17 so that gas under pressure (preferably nitrogen) is introduced via the gas needle 15 and out through its openings 15 a into the plastic which is not yet hardened, which is then pressed out through the channels 10 and into the spill chambers 9 until they are completely filled, as is illustrated to the right in FIG. 1 . During the gas injection phase, the control unit 16 keeps the ejector pins 12 in the position shown to the right in FIG. 1, in which position the end surface 12 a is at a lower level to open the entire flowthrough cross-sectional area of the channel 10 .
When the plastic material has hardened, the mould cavity 4 is opened and the control unit 16 activates the drive means 19 of the ejector pins 12 to push the pins 12 up to lift the plastic article from the lower mould half 3 . As the pins 12 move through the channel 11 , the communication between the plastic material in the mould cavity 4 is cut off from the plastic material in the spill chamber 9 , so that the latter can then be ejected with the ejector pin 13 .
FIGS. 2, 3 and 4 illustrate a plastic article in the form of a radiator grill 20 for a motor vehicle, which can be manufactured with the method and gas injector moulding device described above.
The radiator grill shown comprises a rectangular frame, generally designated 21 , which consists of a horizontal upper frame member 22 , a horizontal lower frame member 23 and two vertical side frame members 24 , which connect the upper and lower frame members 22 and 23 to each other. Between the frame members 22 and 23 , a pair of vertical mouldings 25 extend and between these and each respective side frame member 24 a pair of horizontal mouldings 26 and 27 extend. Finally, a horizontal moulding 28 extends via the vertical mouldings 25 from one side frame member 24 to the other 24 .
All of the components 22 - 28 shown and described are made in one piece with each other in a gas injection moulding process m the above described manner, so that cavities are formed in the frame members 22 and 23 , respectively, and in the mouldings 26 , 27 and 28 , respectively. These cavities, which extend over the entire length of the frame members and the mouldings are designated 29 , 30 , 31 , 32 and 33 in FIG. 3 .
Element 40 in FIG. 2 designates the holes formed after the gas needles 15 , through which gas under pressure is blown into the still not hardened plastic material during the gas injection moulding process. By using, as can be seen in FIG. 1, a mould cavity which has a gradually decreasing cross-sectional area towards the ends, a more balanced filling of the mould is assured than would be the case if the channels had had the same cross-sectional area along their entire length. Thus, if the plastic material on one side of the needle 15 should tend to flow out more rapidly towards the end of the mould cavity than the plastic material on the other side of the needle, the counter-pressure against the former plastic material would increase when it reaches the tapered portion of the mould cavity, so that the gas pressure increases against the latter plastic material which has still not reached the corresponding opposite tapered portion of the mould cavity, thus balancing the filling. | A gas injection moulding device with a mould cavity which communicates via a valve with spill chambers. The injection moulding process is controlled by a control unit so that the valve is first kept partially open during the injection of fluent plastic material for purging the mould cavity of air and for spilling a first small amount of plastic material to the spill chambers, whereas during the subsequent injection of gas, the valve is completely opened. | 1 |
RELATED APPLICATIONS
The present application claims priority from U.S. Provisional Application Nos. 61/139,209, filed Dec. 19, 2008, and 61/222,233, filed Jul. 1, 2009, the disclosures of which are hereby incorporated herein in their entireties.
FIELD OF THE INVENTION
The present invention relates generally to networks and, more particularly, to network patching systems.
BACKGROUND
A network patching system is typically used to interconnect the various communication lines within a closet or computer room. In a conventional network patching system, the communication lines are terminated within a closet in an organized manner via one or more patch panels mounted on a rack or frame. Multiple ports are included in the patch panel, typically in some type of organized array. Each of the different ports is connected with a communications line. In small patching systems, all communications lines may terminate on the patch panels of the same rack. In larger patching systems, multiple racks may be used, wherein different communications lines terminate on different racks. Interconnections between the various communications lines are made connecting patch cords to the ports. By selectively connecting the various communications lines with patch cords, any combination of communications lines can be interconnected.
In many businesses, employee computers are assigned an IP address so that the employee, via the computer, can interface with a network. When an employee changes office locations, it may not be desirable to assign a new IP address. Rather, to preserve consistency in communications, it may be preferred that the IP address previously associated with the employee be transferred to the network port(s) in the employee's new office. To accomplish this task, patch cords in a communication closet are rearranged so that the previous IP address is now associated with his/her new office.
As employees move, and/or change positions, and/or add or subtract lines, the patch cords in a typical closet may require frequent rearrangement. Network patching systems that have the ability to sense a plug in a patch panel port or sense a connection between two patch panel ports are referred to as intelligent patching systems. Intelligent patching systems are described in U.S. Pat. No. 6,222,908, which is incorporated herein by reference in its entirety. Another current intelligent patching solution is the IPatch system, available from Systimax Solutions, Inc. (Richardson, Tex.). In the IPatch system, a circuit board is connected to the system to provide the capability of determining whether a patch cord is plugged into a particular port. Also, the circuit board is connected with a push button and an LED associated with each port to provide connectivity information and guide a technician who is tracing a connection.
This product has some potential areas for improvement, largely due to the trend in the market to increase port density from 24 ports per Rack Mounting Unit (RMU—defined as a space 19 inches in width and 1.75 inches in height) to 36 ports/RMU. The additional ports and the circuitry required for them reduce the space available for the circuit board. Also, the circuit board is mounted in the front of the panel and has a single connection to a panel bus at the rear of the rack. This connection limits the panel to only a single orientation, as opposed to the dual “Alpha/Beta” orientation shown in, for example, U.S. Pat. No. 7,416,347 to Livingston et al.
It may be desirable to provide an intelligent patching system that can offer higher port density.
SUMMARY
As a first aspect, embodiments of the present invention are directed to a datacommunications patching system. The patching system comprises: a mounting frame; a first module mounted in the mounting frame and including a plurality of connector ports on one side thereof and first and second connectors on another side thereof; and a backplane that is mounted in the mounting frame. The backplane electrically connects to the first module via the first connector when the first module is mounted in the mounting frame in a first orientation, and wherein the backplane electrically connects to the first module via the second connector when the first module is mounted in the mounting frame in a second orientation that is inverted from the first orientation. This configuration can enable the patching system to automatically detect an Alpha or Beta orientation of the module, which can then be used on conjunction with an intelligent patching system to track connectivity.
As a second aspect, embodiments of the present invention are directed to a datacommunications patching system, comprising: a mounting frame; a module mounted in the mounting frame and including a plurality of connector ports on one side thereof and first and second connectors on an opposite side thereof, wherein one of a plurality of tracer lights is associated with a respective one of each of the connector ports; and at least one dust cap inserted into one of the plurality of connector ports, the dust cap formed of a material that provides a visual indication when illuminated with a respective one of the plurality of tracer lights, and that permits the passage of infrared radiation.
As a third aspect, embodiments of the present invention are directed to a datacommunications patching system, comprising: a mounting frame; a first module mounted in the mounting frame and including a plurality of connector ports on one side thereof and first and second connectors on another side thereof; and a backplane that is mounted in the mounting frame. The backplane electrically connects to the first module via the first connector when the first module is mounted in the mounting frame in a first orientation, and wherein the backplane electrically connects to the first module via the second connector when the first module is mounted in the mounting frame in a second orientation that is inverted from the first orientation. The backplane includes circuitry configured to recognize whether the first module is in the first orientation or the second orientation. The backplane further includes a tab, and each of the first and second connectors includes a slot configured to receive the backplane tab.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is an exploded front perspective view of an intelligent patching system according to embodiments of the present invention.
FIG. 2 is an exploded front perspective view of the shelf and backplane of the patching system of FIG. 1 .
FIG. 3 is a greatly enlarged front perspective view of an exemplary port module of the patching system of FIG. 1 .
FIG. 4 is a greatly enlarged rear perspective view of the port module of FIG. 3 .
FIG. 5 is a schematic top view of the backplane of FIG. 2 .
DETAILED DESCRIPTION
The present invention will be described more particularly hereinafter with reference to the accompanying drawings. The invention is not intended to be limited to the illustrated embodiments; rather, these embodiments are intended to fully and completely disclose the invention to those skilled in this art. In the drawings, like numbers refer to like elements throughout. Thicknesses and dimensions of some components may be exaggerated for clarity.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In addition, spatially relative terms, such as “under”, “below”, “lower”, “over”, “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “under” or “beneath” other elements or features would then be oriented “over” or “above” the other elements or features. Thus, the exemplary term “under” can encompass both an orientation of over and under. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. As used herein, “vertical” has the conventional meaning, i.e., upright; or at a right angle to the horizon.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein the expression “and/or” includes any and all combinations of one or more of the associated listed items.
Where used, the terms “attached”, “connected”, “interconnected”, “contacting”, “mounted” and the like can mean either direct or indirect attachment or contact between elements, unless stated otherwise.
Also, as used herein the term “port” is intended to encompass telecommunications connectors and devices employed to facilitate the interconnection of telecommunications cords and cables for the transmission of signals therebetween. A connector may include an adapter that facilitates the interconnection of two termination devices (as may be employed in the interconnection of fiber optic cords and cables, particularly within a connector block), a jack or the like typically employed with copper cables and cords, or other devices that provide a location or site for the interconnection of cables and cords.
Further, as used herein, it will be understood that, as used herein, the term “Alpha/Beta” when referring the orientation of a communications module indicates that the module may be oriented in one of two orientations (the “Alpha” orientation being 180 degrees inverted from the “Beta” orientation), wherein cords and cables may be connected with the module in either orientation, but the numbering system of the ports of the module and the connectivity with other devices differs with the orientation. An exemplary “Alpha/Beta” orientation is described in greater detail in U.S. Pat. No. 7,416,347 to Livingston et al., supra.
Turning now to the figures, a patching system, designated broadly at 10 , is illustrated in FIG. 1 . The patching system 10 includes a shelf 12 and three port modules 40 (more or fewer modules 40 may be included in other embodiments). These components are described in greater detail below.
Turning now to FIGS. 1 and 2 , the shelf 12 includes a generally horizontal main panel 14 , a rear wall 16 , side walls 18 , and a cover 22 . Together these panels form a box structure with an open front end. Slide members 20 are attached to each of the side walls 18 and enable the shelf to slide forward from a rack on which it is mounted (not shown) for work by a technician. Four module guides 32 are mounted to the main panel 14 generally parallel to the side walls 18 and spaced apart from each other. With the cover 22 in place, the shelf 12 has a height of approximately 2 RMU.
A trough 24 is attached to the front edges of the side walls 18 and main panel 14 . The trough 24 has three module openings 26 that are configured to receive modules 40 . Also, the trough 24 includes a pair of cable loops 28 on each side that are configured and oriented to receive cables and cords inserted into adapters 42 in the modules 40 . A front window 27 is positioned below and in front of the module openings 26 . FIGS. 1 and 2 also illustrate module doors 29 that can be placed over the module openings 26 when a module 40 is not present.
Those skilled in this art will appreciate that, although the shelf 12 is illustrated and described herein, mounting frames of different configurations may also be employed with embodiments of the present invention.
Referring still to FIG. 2 , a backplane 34 is mounted to and positioned above the rear portion of the main panel 14 . The backplane 34 includes three connection tabs 36 on its front edge 35 . As can be seen in FIG. 5 , the backplane 34 comprises a printed wiring board that includes circuitry that monitors the connectivity of ports 42 in the modules 40 . Exemplary circuitry for “intelligent” patching is known to those of skill in this art and need not be described in detail herein.
The backplane 34 further includes circuitry that can detect the orientation (i.e., Alpha or Beta) of the modules 40 . Such circuitry may comprise, for example, contact pads that are positioned to detect different mating contacts in connectors of the module 40 (described in greater detail below). Other configurations may also be suitable for other embodiments of the present invention.
Referring now to FIG. 3 , each of the modules 40 includes a plurality of fiber optic adapters 42 . In the illustrated embodiment, the adapters 42 are disposed in an array of 6 rows and 4 columns, although other arrangements may be employed. The individual adapters 42 are oriented such that they are vertically oriented. A “vertically oriented” adapter is one in which its keyway, which accepts a mating key on a mating terminal, is located in a vertical wall or edge of it opening. This arrangement is a 90 degree re-orientation from conventional adapters. Those skilled in this art will recognize that, although fiber optic adapters are shown herein, other varieties of datacommuncations ports and/or connectors may also be employed.
In this embodiment, each adapter 42 is monitored by an infrared (IR) sensor that detects the presence of a connector in the adapters 42 . Each adapter 42 also has a corresponding LED 43 that helps to guide a technician to the correct adapter 42 during maintenance and a push button 45 that assists with connectivity operations.
Referring now to FIG. 4 , the rear surface of each of the modules 40 includes two different connector slots 44 a, 44 b. Each of the connector slots 44 a, 44 b is sized to receive one of the connection tabs 36 . The connector slots 44 a, 44 b are located on the module 40 so that, when the module 40 slides through one of the module openings 26 and toward the backplane 34 , one of the connector slots 44 a, 44 b is positioned to receive the connection tab 36 . If the module 40 is in an “Alpha” orientation, the connection tab 36 is inserted in the connector slot 44 a; if instead the module 40 is in a “Beta” orientation (i.e., inverted 180 degrees from the Alpha orientation), the connection tab 36 is inserted into the connector slot 44 b. The module guides 32 are positioned to encourage straight-line entry of the module 40 into and through the module openings 26 so that the proper connector slot 44 a, 44 b aligns with and enables insertion of the connection tab 36 .
FIG. 4 also illustrates fiber optic adapters 49 , which are attached to cables (not shown) and are mounted on the rear side of the module 40 .
Those skilled in this art will appreciate that, although the adapters 42 and the connector slots 44 a, 44 b are shown on the front and rear of the module 40 , these components may be positioned on other sides of the module 40 (for example, on the top and bottom of the module).
Connection of the connection tab 36 with a connector slot 44 a, 44 b allows the backplane 34 to recognize the Alpha/Beta orientation of the module 40 . For example, the connector slot 44 a may include a contact in one position (e.g., the leftmost portion), whereas the connector slot 44 b may include a contact in another location (e.g., the rightmost portion). When the connector slot 44 a receives a tab 36 with multiple contact pads. a mating contact pad on the tab 36 can detect the contact of the connector slot 44 a and thus determine that the module 40 is in an Alpha orientation. Conversely, if the connector slot 44 b receives the tab 36 , a different mating contact pad on the tab 36 detects the differently located contact of the connector slot 44 and determines that the module 40 is in a Beta configuration. This information about the module orientation can then be used in conjunction with intelligent patching circuitry on the backplane 34 to correctly track and monitor the connectivity of the ports 42 of the module 40 .
As discussed, the adapters 42 are fiber optic adapters that receive fiber optic connectors. Such adapters typically include some means, such as dust caps 50 ( FIGS. 3 and 4 ). for preventing dust from entering the adapter when the adapter is not in use. A conventional dust cap is inserted into the adapter to prevent the accumulation of dust. However, when an IR-based port detection technique is employed by an intelligent patching system, the system can misinterpret a typical dust cap inserted in an adapter as a connector. To address this issue, in some embodiments the dust caps are formed of a material that is translucent to IR radiation. Such dust caps can allow an IR beam transmitted across the adapter 49 to pass and avoid signaling the presence of an object to the backplane 34 .
In some embodiments, it may be desirable for the dust cap material to compliment the intelligent system during installation, maintenance and connection. Some patching systems include a tracer light (often red) to indicate the status of the particular adapter. The dust cap material may be chosen to reveal the tracer light, or to glow, when the tracer light is activated. Such a configuration can enable an operator to see the light without removing the dust cap, which can significantly simplify installation.
Exemplary materials for the dust cap include a thermoplastic elastomer (TPE), and in particular ethylene-propylene copolymers. A particularly suitable material is DYNAFLEX® G2780-001 TPE, available from GLS Corporation. McHenry, Ill. This material is also ROHAS compliant, and meets zero halogen requirements demanded in some applications.
The foregoing embodiments are illustrative of the present invention, and are not to be construed as limiting thereof. Although exemplary embodiments of this invention have been described, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the claims. The invention is defined by the following claims, with equivalents of the claims to be included therein. | A datacommunications patching system includes: a mounting frame; a first module mounted in the mounting frame and including a plurality of connector ports on one side thereof and first and second connectors on another side thereof; and a backplane that is mounted in the mounting frame. The backplane electrically connects to the first module via the first connector when the first module is mounted in the mounting frame in a first orientation, and wherein the backplane electrically connects to the first module via the second connector when the first module is mounted in the mounting frame in a second orientation that is inverted from the first orientation. | 7 |
BACKGROUND—PRIOR ART
[0001] The following is a tabulation of some prior art that presently appears relevant:
[0000]
U.S. Patents
Pat. No.
Kind Code
Issue Date
Patentee
4,256,945
B1
Mar. 17, 1981
Philip S. Carter
5,003,145
B1
Mar. 26, 1991
Eugen Nolle et al.
7,942,987
B1
May 17, 2011
S. Scott Crump et al.
5,121,329
B1
Jun. 9, 1992
S. Scott Crump
6,238,613
B1
May 29, 2001
John S. Batchelder
6,142,207
B1
Nov. 7, 2000
Francis Richardot
7,194,885
B1
Mar. 27, 2007
Daniel J. Hawkes
U.S. Patent Application Publications
Publication Number
Kind Code
Publ. Date
Applicant
20120070523
A1
Sep. 22, 2012
Swanson et al.
Foreign Patent Documents
Foreign
Doc. Nr.
Cntry Code
Kind Code
Pub. Date
App or Patentee
2156715
EP
B1
May 2, 2012
Mcdonald
Non-patent Literature Documents
Jacob Bayless, UBC-Rapid.com, “Induction Heating Extruder”,
March 2012
Reprap.org, “Arcol.hu Hot End Version 4”, January 2013
INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
[0002] Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57. This application is a divisional of U.S. application Ser. No. 13/843,843 filed Mar. 15, 2013, entitled “Inductively Heated Extruder Heater”.
[0003] One class of 3-D printers or additive manufacturing systems uses thermoplastic filament or rod heated to a softened, molten, or liquid state and extruded through a small hole in a nozzle to build up a part or model. The extruder nozzle is moved relative to a platform, under computer control, to lay down a bead of the thermoplastic on the platform as a feeder mechanism pushes the filament or rod into the extruder heater. The computer interprets a file of movement instructions to drive three axes of motion while starting and stopping the flow of heated plastic. The part or model is built up layer by layer on the platform.
[0004] Prior art heater designs for 3-D printers fall into two categories. The vast majority of filament-type 3-D printers use simple resistance heaters wrapped around or encased in a metal nozzle or heating body (often simply called the “hot end”). The resistance heating element is supplied with direct current or line-frequency (50 or 60 Hz) alternating current, turned on and off by an electronic or mechanical thermostat device to maintain proper temperature. The heating body assembly must be physically large to accommodate a suitably high-wattage resistance heater element. The heater/nozzle assembly is wrapped in insulation to prevent other components in the printer from overheating. The Stratasys U.S. published patent application 2012/0070523 is typical of this approach. Another typical resistively heated extruder nozzle assembly is the Arcol unit.
[0005] Resistance heated extruders are by nature relatively heavy. We have found that the weight of the extruder heater, the large heated zone and the slow response time to temperature set point changes are major limitations on the speed and accuracy of current 3-D printers.
[0006] If the temperature sensor, thermostatic device, or control circuit in a prior art conventional resistive extruder heater fails, we have observed that the heater may overheat or even catch fire. Extra circuitry is needed to detect heater control failure.
[0007] A few printer designs have used or proposed to use an induction heating method (also sometimes called “eddy current heating”). Conventional induction heaters consist of a helical coil of wire surrounding an electrically conductive metal heating block. An oscillator creates a high-frequency alternating current that is applied to the wire coil. The magnetic field created by this current couples to the metal heating block, which heats up due to eddy currents in its internal resistance. We have determined that the magnetic field may also radiate all around the outside of the coil of wire, causing electromagnetic interference and undesired heating of nearby metallic objects. The plastic filament to be melted is fed into an orifice in the heater block. Because the heater block is entirely surrounded by the wire coil, it is difficult to make direct temperature measurements of the heater block so as to properly control the melt temperature. A thermocouple, resistive temperature device, or thermostat placed on the heater block inside the straight-line coil will experience eddy current and hysteresis heating itself, causing errors in temperature measurement. If the heater block is extended far enough beyond the ends of the coil to provide a measurement location not adversely affected by the magnetic field of the straight-line coil, the temperature measured will not accurately reflect the temperature at the center of the heater block where the plastic filament is melted.
[0008] Resistance heaters and straight-coil induction heaters are also the current state of technology in hot-glue adhesive dispensers, both manual hand-operated dispensers and industrial automatic dispensers. We have observed that the large heater blocks necessitated by resistance heating make it difficult to regulate the temperature at the nozzle tip. We have found that heating is slow, and cooling is also slow, leading to dripping of adhesive after the dispenser is turned off.
[0009] We have also observed that the large, hot blocks of metal in conventional resistance heaters in 3-D printers and adhesive dispensers are hazardous to operators because of the large area of exposed nozzle and their long cool-down time after power is removed.
SUMMARY
[0010] One embodiment of our inductively heated extruder heater or adhesive dispenser uses an electrically conductive nozzle of minimal size, with an inlet orifice and an outlet orifice connected by a passage, inserted into a gap or hole through a magnetic core formed in the shape of a loop. A high-frequency magnetic field is created in the core by a helical coil of wire wrapped through the center and around the core and connected to a source of high-frequency alternating current. The high-frequency magnetic field in the core gap induces eddy currents in the metal nozzle, rapidly heating it to the melting temperature of the filament or feedstock to be extruded. Another embodiment uses a ferrous material for the nozzle. The magnetic field will cause heating of the nozzle from both eddy current losses due to the electrical conductivity, and hysteresis losses due to the magnetic properties of the ferrous material.
[0011] The soft magnetic core material is selected to have a Curie temperature below the maximum safe operating temperature of the extruder or dispenser.
Advantages
[0012] Because there is no excess mass in the inductively heated nozzle of an embodiment of our extruder heater, the time to heat up and cool down is very short, and the power required is much lower than conventional resistively heated extruders or dispensers. In 3-D printers using prior art extruder heaters, we have observed that the slow rate of heating and cooling causes the melted plastic to begin to flow after the extruder head or build platform has begun to move, and continues to flow after the motion has ceased. This lag causes inaccuracies in the parts printed with prior art extruder heaters.
[0013] In addition, the combined mass of the nozzle, magnetic core, and wire in the present invention is much lower than prior art conventional resistive extruder heaters, allowing much higher acceleration of a print head for higher 3-D printing speeds.
[0014] The Curie temperature property of the magnetic core material, selected below the maximum safe operating temperature of the extruder or dispenser makes an embodiment of the heater passively safe in the event of temperature sensor or control circuit failure. No extra circuitry is needed to monitor the temperature sensor or controller.
[0015] In one embodiment, the small mass of the inductively heated nozzle cools off quickly when the high-frequency alternating current is removed, eliminating the dripping and oozing problems we have observed with conventional 3-D printer extruders and adhesive dispensers. Conventional extruders must pull back the filament to prevent dripping or oozing, which adds mechanical complexity and undesirable changes in plastic properties. The present invention can be handled by operators much sooner after turning off, with reduced danger of burns.
[0016] Because the magnetic field induced by the coil is concentrated by the magnetic core onto two small areas on either side of the nozzle heating body, in one embodiment, there are areas not within the magnetic field for easy measurement of the nozzle temperature. Thermocouples or resistive temperature devices attached to the nozzle in these areas outside of the magnetic field region will not experience eddy current or hysteresis heating effects, and thus will provide an accurate indication of the temperature inside the nozzle. Because the nozzle heating body can be made very small, the temperature at the surface being measured will also be very close to the temperature inside the nozzle.
[0017] The inductively heated nozzle in one embodiment has such a small surface area that only a small amount of thermal insulation is required to protect the operator of the 3-D printer or adhesive dispenser and keep the temperature of adjacent components of a 3-D printer cool, reducing the size and cost.
DRAWINGS
[0018] Figures
[0019] FIGS. 1A and 1B show embodiments illustrating different nozzle shapes.
[0020] FIG. 1C is a cross-sectional view of the first embodiment.
[0021] FIGS. 2A, 2B, and 2C show embodiments illustrating different shaped magnetic cores.
[0022] FIGS. 3A, 3B and 3C show embodiments illustrating different nozzle orifices.
[0023] FIG. 4 shows a dual heat zone embodiment.
[0024] FIGS. 5A and 5B show cross-sectional views illustrating tapered nozzle embodiments.
[0025] FIG. 6 shows a dual wire coil embodiment.
[0026] FIGS. 7A and 7B show embodiments incorporating temperature sensing and control.
[0027] FIG. 8 shows one embodiment in a 3-D printer.
DRAWINGS
Reference Numerals
[0028] 10 —filament, rod or other feedstock, omitted in some figures for clarity [0029] 20 —insulated wire coil or coils, omitted in some figures for clarity [0030] 30 —electrically and thermally conductive nozzle or nozzles [0031] 31 —inlet orifice or orifices [0032] 32 —outlet orifice or orifices [0033] 33 —passage or passages, omitted in some figures for clarity [0034] 34 —heat sink flange present in some embodiments [0035] 40 —magnetic non-conductive core [0036] 41 —air gap present in some embodiments [0037] 42 —path of magnetic flux in magnetic core and nozzle [0038] 50 —temperature sensor, omitted in some figures for clarity [0039] 51 —thermostat, omitted in some figures for clarity [0040] 60 —high-frequency alternating current source, omitted in some figures for clarity [0041] 70 —temperature control circuit, omitted in some figures for clarity [0042] 71 —signal from temperature control circuit to alternating current source
DETAILED DESCRIPTION
First Embodiment—FIGS. 1 A, 1 B and 1 C
[0029] The embodiment shown in FIGS. 1A to 1C is an inductively heated extruder heater. The nozzle 30 consists of a heating body made of an electrically and thermally conductive material, such as steel, with an inlet orifice 31 and an outlet orifice 32 . The inlets and outlets are connected by a passage 33 (not visible in FIGS. 1A-1C ). The nozzle 30 fits into a hole or gap cut or formed through a loop of high-permeability soft magnetic material such as ferrite or pressed iron powder, forming a core 40 .
[0030] Electrically conductive wire is coiled around and through this loop to form one or more coils 20 . An high-frequency alternating current source 60 applies a high-frequency alternating current to the wire coil or coils 20 . There may optionally be small air gaps 41 A and 41 B present between the nozzle 30 and the magnetic core 40 .
[0031] A filament, rod, wire or other feedstock 10 of meltable or flowable material is introduced to inlet orifice 31 when the nozzle 30 has reached operating temperature. The force required to push feedstock 10 into the extruder heater is provided by external mechanisms. The melted material exits outlet orifice 32 after traveling through the passage 33 (not visible in FIGS. 1A-1C ).
Operation—FIGS. 1 A, 1 B, and 1 C Embodiment
[0032] The high-frequency alternating current flowing in the wire coil or coils 20 creates a strong magnetic field within the core 40 of high-permeability material, around path 42 . Because it is a closed loop, the magnetic field is nearly all contained within the loop. Very little electromagnetic radiation leaks from the coil to cause interference to nearby electronics or radio devices, a problem we have observed with prior art inductive heater designs. Ferrite, iron powder and other known magnetic core materials exhibit only very small internal energy losses, because the magnetic particles are very small and insulated from each other by extremely thin layers of non-magnetic, non-conductive material. The conductive nozzle 30 inserted into the loop, however, will have high losses (in the form of heat) from eddy currents created by the magnetic field. In the case of nozzles 30 formed from ferrous materials, additional heating takes place from hysteresis losses. These losses are used by this embodiment to melt the filament, rod, or other feedstock 10 to be extruded. The loop of magnetic material forming core 40 will often be in the general shape of a toroid, although other shapes can also work, as long as they form a closed magnetic circuit.
[0033] In some embodiments, there will be present air gaps 41 A and 41 B, either due to manufacturing variations in the core 40 or the nozzle 30 , or by design. The air gaps 41 A and 41 B will lower the permeability and increase the reluctance of the magnetic circuit through core 40 and nozzle 30 . A higher alternating current amplitude from alternating current source 60 or more turns of wire in coil 20 will maintain a sufficiently high magnetic field to heat nozzle 30 to the desired temperature.
[0034] Non-magnetic nozzle materials that could work in some embodiments might include tungsten, graphite, copper, or aluminum. Additional electrically and thermally conductive materials are possible.
[0035] In some embodiments, a flange 34 is formed at the top of nozzle 30 to reduce the flow of heat up the filament 10 . The flange 34 , if present, will radiate some of the heat flowing up the filament 10 by conduction, keeping down the temperature of filament 10 before it enters inlet orifice 31 . The flange 34 could also be formed near the outlet orifice 31 to cool the molten material as it exits. Flange 34 could also be formed elsewhere on nozzle 30 to provide selective or localized cooling as desired.
Description—Additional Embodiments—FIGS. 2 - 6
[0036] A circular toroidal shape of core is not the only possible configuration. FIG. 2A shows a rectangular shaped magnetic core 40 . Any shape is possible, as long as it forms a continuous magnetic circuit. The soft magnetic material can be made in bulk and cut to the desired shape, or can be pressed, molded, or sintered in the final shape. The magnetic core 40 could be fabricated in segments and fused or held together by high temperature adhesives or mechanical methods. The nozzle 30 may be inserted in a hole in core 40 that does not completely sever the core. FIG. 2B is a cross-section illustrating such an embodiment. FIG. 2C shows an embodiment with a more complicated magnetic circuit. There is still a continuous magnetic path 42 through core 40 and nozzle 30 . Magnetic flux, created by the high frequency current from source 60 flowing in coil 20 will substantially follow magnetic path 42 to heat nozzle 30 by induced eddy currents.
[0037] The nozzle 30 must have at least one inlet orifice 31 and one outlet orifice 32 to extrude feedstock material 10 . FIG. 3A illustrates an embodiment with two inlet orifices 31 A and 31 B and two outlet orifices 32 A and 32 B with two separate passages 33 A and 33 B to extrude two beads of material simultaneously and independently. Two inlets 31 A and 31 B and one outlet 32 , connected by passages 33 A and 33 B, shown in FIGS. 3B and 3C , embody a blending arrangement to extrude one bead from two feedstock filaments 10 A and 10 B. Passages 33 A and 33 B can take different forms in different embodiments, or be combined into one mixing chamber, to achieve specific mixing characteristics. In another embodiment represented by FIG. 3B and FIG. 3C two different feedstocks 10 A and 10 B are alternately fed into inlets 31 A and 31 B, such that only one at a time is extruded from outlet orifice 32 . FIG. 3C is a cutaway view of FIG. 3B making passages 33 A and 33 B visible.
[0038] Multiple magnetic cores 40 A and 40 B can share a common nozzle 30 for purposes of multi-zone heating. FIG. 4 illustrates such an embodiment. This is advantageous for feedstock materials 10 that require a preheating step to alter some material properties, such as viscosity or moisture content, before final melting. Multiple cores 40 A and 40 B may also provide faster heating response time. Core 40 A will be wrapped with coil 20 A and connected to high-frequency alternating current source 60 A. Core 40 B will be wrapped with coil 20 B and connected to high frequency alternating current source 60 B, which could have a different amplitude or frequency than source 60 A. Coil 20 B could have a different number of turns than coil 20 A, and core 40 B could have a different Curie temperature than core 40 A.
[0039] In one embodiment, the air gaps 41 A and 41 B due to dimensional variations that could occur in manufacturing magnetic core 40 and nozzle 30 are eliminated by foaming the nozzle 30 and the gap in core 40 with matching tapers, as shown in FIGS. 5A and 5B . Variability of magnetic field from heater assembly to heater assembly during manufacturing may be reduced with air gaps 41 A and 41 B eliminated.
[0040] Another embodiment, FIG. 6 , has more than one coil of wire. Two coils 20 A and 20 B may permit a two-phase alternating current drive circuit 60 A and 60 B with fewer components than a typical single-phase circuit. Three coils could permit a three-phase alternating current drive circuit, which may have some efficiency benefits. Embodiments with additional coils are possible. An embodiment with a single coil with a center-tap may permit simplified drive electronics, equivalent to the two-coil circuit illustrated in FIG. 6 .
Description—Additional Embodiments—FIG. 7 A
[0041] One embodiment includes a temperature sensor 50 , such as a thermocouple, resistive temperature device, or thermistor, to measure the temperature of the nozzle 30 , and communicate that temperature to a control circuit 70 , which controls the alternating current source 60 by signal 71 .
Operation—FIG. 7 A Embodiment
[0042] In the embodiment of FIG. 7A , the alternating current source 60 has adjustable frequency or amplitude. The adjustment is performed by signal 71 from temperature control circuit 70 in response to changes in the temperature of nozzle 30 as measured by sensor 50 . A person skilled in the art is familiar with suitable temperature control circuits. The magnetic field strength in magnetic core 40 is directly related to and controlled by the amplitude and frequency of the alternating current in coil 20 .
Description and Operation—FIG. 7 B Embodiment
[0043] Another embodiment uses a thermostatic device 51 in contact with the nozzle 30 to turn the alternating current on and off in coil 20 to control the temperature in nozzle 30 . The thermostat 51 may either disconnect the supply of high-frequency alternating current to the coil 20 , as shown in FIG. 7B , or it may alternatively disconnect the power source to the alternating current source 60 .
Operation—FIGS. 7 A and 7 B Embodiments
[0044] The magnetic permeability of ferrite and iron powder materials varies somewhat with temperature. As the temperature of the material rises, it eventually reaches a point called the Curie temperature. Above the Curie temperature, the permeability drops to negligible levels. This causes the magnetic field to also drop to very low levels. A thin layer of the soft magnetic core that is in contact with the nozzle will heat up to the temperature of the nozzle by thermal conduction. When this exceeds the Curie temperature, the permeability of this thin layer will drop. The magnetic field will then drop, reducing the eddy current and hysteresis losses that are heating the nozzle. Inductive heaters for soldering irons have used this property to regulate the temperature of their heating elements. In the embodiments shown in FIGS. 7A and 7B , the Curie temperature is used as a safety measure. If the control circuitry 70 or sensor 50 or thermostat 51 malfunctions, the magnetic core 40 temperature cannot exceed the Curie temperature because the magnetic field in magnetic core 40 will drop, lowering the eddy and hysteresis currents in nozzle 30 , which will lower the temperature in nozzle 30 to a temperature close to the Curie temperature of core 40 . Choosing a core material with a Curie temperature lower than the maximum safe temperature of the heater assembly and feedstock material makes this embodiment passively safe from overheating or fire, which we have found to be a serious problem with prior art extruder heaters.
Description and Operation—FIG. 8 Embodiment
[0045] A 3-D printer or additive manufacturing system may consist of a build bed 80 , where the part is printed or formed, layer by layer, the filament feeder 90 , the extruder heater 100 , and a mechanism 110 to move the extruder relative to the build bed 80 . A control circuit 70 actuates the movement of the extruder relative to the build bed 80 , the temperature of the extruder 100 , and the feed rate of the filament feeder 90 . The smaller the extruder heater 100 the smaller the printer can be, and the lighter the extruder heater 100 , the faster extruder heater 100 can be moved relative to the build bed 80 . The smaller the mass being heated in the extruder 100 , the faster the filament feed rate can be changed. Printing a 3-D part requires the filament feed to be started and stopped many times for each layer deposited. Our inductive extruder heater focuses the heating energy to the smallest possible mass in the nozzle, permitting much faster operation than prior art 3-D printers. Because the heating body in some embodiments of our extruder heater is very small, with a very short passage for the filament 10 to pass through, much less force is required to push the filament 10 into and through the nozzle (not shown in this FIG. 8 ). Less force required permits smaller feed mechanisms than necessary for prior art extruder heaters.
[0046] We have found it desirable to have multiple filament feeders 90 and extruder heaters 100 in 3-D printers, permitting a part to be formed with more than one color or type of plastic filament 10 . Prior art extruders were too heavy and bulky to permit multiple filaments in a compact printer. An embodiment of our extruder heater is small enough that multiple extruders can be easily installed in even very compact 3-D printers.
CONCLUSION, RAMIFICATIONS, AND SCOPE
[0047] Accordingly, at least one embodiment of this inductively heated extruder heater is much lighter, more compact, and more energy efficient than conventional extruder heaters, reaches operating temperature in far less time, and responds to temperature set point changes much quicker, while possessing inherent safety not present in prior art extruder heaters. The material costs to produce this design are lower than conventional resistance heaters, and the components are well suited to low-cost, automated manufacturing.
[0048] Despite the specific details present in our descriptions above, these should not be construed as limitations on the scope. Rather they serve as exemplification of several embodiments. Many other variations are possible. For example, the tapered nozzle may be used with either circular or non-circular soft magnetic cores. The inlet and outlet orifices in the nozzle do not have to be concentric. The nozzle does not need to be positioned perpendicular to the plane of the toroidal core. The nozzle may be inserted into a hole through the core, without the core being completely severed. The wire used in the coil may be of round or rectangular cross-section, and may have any type of insulation between turns, including air, that is compatible with the operating temperatures. The shape and size of the inlet and outlet orifices may be adjusted to suit the materials being extruded. Instead of filament or rod feedstock, a tube may deliver granular or viscous material to the heater, which will be melted or heated to a reduced viscosity condition before exiting the outlet. The soft magnetic core may have a complex three-dimensional shape, resulting in a magnetic path that does not lie in a plane. The heat sink flange, if present, may be in many different forms and shapes, as needed, to radiate heat away from the feedstock.
[0049] Accordingly, the scope should be determined not by the embodiments illustrated, but by the appended claims and their legal equivalents. | Methods related to inductive heating in extruders. In some embodiments, a method for heating a feedstock or liquid material can include providing a heating body having inlet and outlet orifices connected via a passage or passages or mixing chamber to define a nozzle, and forming a magnetic loop with a coil of conductive wire wound through the center and around the outside of a core of magnetic but electrically non-conductive or low-conductivity material. The method can further include a high-frequency alternating current applied to the coil, producing a magnetic flux locally heating the nozzle. Some embodiments have passive regulation or limiting of nozzle temperature by selection of a core material with an appropriate Curie temperature. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to compressors and refers more particularly to a protective coating that reduces corrosion for a compressor.
[0003] 2. Discussion of the Related Art
[0004] The outer shell of most compressors is composed of either a low carbon hot or cold rolled steel stamping or gray cast iron. The steel or cast iron, without a corrosion protectant coating, would typically corrode at a fast rate even in a non-marine environment. For conventional compressor applications, the outer surface of the compressor body is painted to minimize corrosion. Corrosion mitigation is important not only to extend the useable life of the compressor, but also to prevent premature failure of the pressurized shell which may result in personal injury.
[0005] The steel compressor's outer surface is composed of several stamped steel components that are assembled together primarily by welding. Welding, in itself, causes the surface of the steel be even more prone to corrosion due to several metallurgical factors, two of which are hindering paint adhesion and forming pinholes. The cast iron compressor version is composed of several iron castings assembled together by fasteners. In the case of gray cast iron, corrosion is also prone mainly because of the intrinsic presence of graphite within the cast iron. Graphite encourages corrosion because of the galvanic difference between iron and graphite, which causes preferential corrosion of the iron matrix. Therefore, it is obvious to any expert in the corrosion field that the aforementioned compressor types are highly likely to corrode, especially in extreme environments.
[0006] The painting process mentioned as the prior art, has the following sequence of events associated with it's application: Liquid chemical cleaning of the steel or iron surface to remove organic and inorganic contamination, phosphatizing the cleaned surface (creating an iron phosphate layer that aids in the adhesion of the paint), sealing the phosphated coating (sealing controls the phosphating reaction and prepares the surface for painting), painting the compressor (either with a powder electrostatic spraying, dipping or liquid spraying methods), curing the paint either at room temperature or at elevated temperatures.
[0007] Typically, the painted compressor must pass several standard test methods to be considered acceptable. ASTMB-117 is one such standard test method. With the paint quality associated with the prior art, it is conceivable that the compressor would pass the standard test methods and still have signs of corrosion of the underlying steel or iron (red rust) visible at localized regions on the painted surface. For most applications, this sporadic red rust is normal and would not affect the functionality of the compressor for the life of the compressor.
[0008] However, certain compressor applications require very high reliability and can not succumb to a corrosion failure without great loss. These stringent applications require no visible red rust corrosion on the surface for an extended period of time (as mentioned: despite the fact that it passed ASTM testing). An example of such an application would be climate controlled marine containers that are transported across the ocean. Marine environments are especially corrosion causing because of the presence of salts and other corrosion enhancing constituents found in seawater. The “containers” may be exposed to marine mist or even periodically come in contact with seawater due to splashing. Temperature fluctuations and direct sun light may also be present (which includes the deleterious effect of ultraviolet rays). These containers need to be refrigerated uninterrupted for the entire journey to protect the enclosed cargo. These are high reliability requiring applications, where failure of the compressor would not be easily repairable and would result in large monetary damages if the climate control system ceased to function. This represents an extraordinary challenge considering the especially corrosion inducing marine environment.
[0009] The painting procedure described as the prior art does not have a high enough corrosion preventative property associated with it. The prior art, although acceptable for most applications, does not fulfill the requirements of preventing “no visible red rust” during the life of the compressor. The prior art has a weakness in that when nicks or dings occur due to, for example, accidental impact or scratching damage during compressor handling or preventative maintenance, the paint cracks and exposes bare steel which then corrodes at an accelerated rate. The prior art paint process serves only to provide a weak barrier coating. Once this coating is penetrated to the underlying steel, corrosion immediately occurs. Bare metal exposed in this manner will corrode quickly because there is no strong “cathodic protection” provided by the prior art's paint. This is a weakness of the prior art especially because of the long hours the compressors are exposed to corrosive environments.
SUMMARY OF THE INVENTION
[0010] In accordance with the teachings of the present invention, a compressor system is provided which is coated with an environmental protective coating. The coating is comprised of two or three layers, the first being a sprayed porous metallic layer disposed on the compressor. The second layer being a organic based surface layer disposed on the sprayed metallic layer for sealing the metallic layer pores and the optional third layer being an organic based topcoat finish used for cosmetic reasons as well as to further enhance corrosion resistance.
[0011] The sprayed metallic layer is formed by powder flame spraying, wire flame spraying, or electric arc spraying. The metallic layer thickness should be between 0.010 to 0.015 thousandths of an inch. The sprayed metallic layer should have a tensile bond adhesion level of at least 1,000 psi.
[0012] Also disclosed is a method of having the steps of treating the surface of the compressor with an abrasive grit to a suitable finish. After the surface of the compressor is treated, a metallic coating is thermally sprayed onto the treated surface of the compressor. A organic-based sealer and an optional top coat finish are then applied to the metallic coating to seal the pores within the thermally sprayed layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Still other advantages of the present invention will become apparent to those skilled in the art after reading the following specification and by reference to the drawings in which: FIGS. 1 - 3 show parts of the compressor main body in various stages of the processing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] FIGS. 1 - 3 show the parts of the compressor main body 10 in the various stages of processing. As can be seen, the spray head 11 from the thermal sprayer apparatus is shown applying the metallic coating layer 12 onto the surface of the compressor.
[0015] The coating system of the present invention provides a strong “barrier” property because of the sprayed metallic layer 12 . The form and composition of the sprayed metallic layer 12 described herein is ductile and very adherent to the underlying steel. Therefore, if accidental impact occurs, such as with a wrench, the aluminum will just dent and smear and still remain basically in tact and still cover or protect the steel. The sprayed metallic layer 12 , of course, must be thick enough to supply this property.
[0016] Moreover, the electrochemical galvanic potential relationship between the sprayed metallic layer 12 and steel are such that the steel or iron compressor housing 10 becomes protected even when bare steel or iron regions are locally exposed to the corrodant. The sprayed metallic, which is preferably an aluminum coating, is sacrificial to the steel and therefore protects the steel from corroding. The approximate relationship describing this is as follows:
Service Life in Years=(0.64×Aluminum Coating Thickness (micrometers))/Percent Surface Area As Bare Steel.
[0017] The first step in the present invention is to clean the outer surfaces of the compressor body 10 to be coated of all grease, oil or other organic contamination. An aqueous alkaline cleaning system will suffice. In the case of gray cast iron an additional step may be needed depending upon condition of the cast iron surface. Graphite present on the surface of the cast iron may inhibit adhesion of the metallic coating. A special chemical treatment may be necessary to remove some or most of the exposed surface graphite. One such method is known in the industry as Kolene Electrolytic Salt process. It is understood that there may be other methods that are more economical in the industry that will serve the same purpose. In certain cases, this graphite removal step may not be necessary depending upon the quality of the casting surface and the effectiveness of the grit blasting.
[0018] It is preferable that the compressor's outer surface is first thoroughly treated by abrasive grit blasting. The blasting must be sufficient enough to satisfy the surface finish requirements of SSPC SP 5 or NACE #1 “White Metal”. Proper surface preparation by blasting is critical to produce a well adhering thermally sprayed metallic coating. This roughened surface texture not only removes surface contamination by exposing fresh steel or iron, but also serves to mechanically anchor the aluminum coating firmly to the substrate. Angular hard steel grit of mesh size of about 25-40 can be used, but the preferred grit media is aluminum oxide with a mesh size of about 16-30. It is preferred that the indentation that the shot makes on the surface of the steel or iron is angular in shape and not spherical. Better adhesion of the aluminum occurs with an irregular surface texture formed by angular-shaped grit particles. The resulting surface finish of the substrate after blasting shall have an anchor tooth pattern with a surface profile of about 50-75 micrometers (0.002-0.003 inch) measured by ASTM D 4417 Method A or B. The use of steel shot, typically used in shot peening or for other routine cleaning purposes may not supply the needed angular surface finish defined herein and may cause lack of good adhesion of the aluminum coating. Blasting shall not be so severe as to distort any part of the compressor. It is critical that 100% of the surfaces to be metallized be cleaned.
[0019] Regions of the compressor body 10 that should not be blasted should be masked. An example of such a component would be an electrical connection, a site glass, or internal coupling threads.
[0020] After the compressor body 10 is blasted, it must be thermally sprayed within a certain maximum time limit of four hours to obtain the best coating adhesion. This is to avoid the formation of flash rust or other forms of surface contamination that would otherwise inhibit adhesion of the aluminum. The surface quality of the ferrous substrate must be SSPC SP 5 “white metal” just prior to spraying.
[0021] The substrate to be sprayed may be sprayed at room temperature, but to assure no moisture is present, local heating of the area to be sprayed shall be done. The surface temperature of the substrate should not exceed 250 Fahrenheit. As an alternative, the compressor body 10 may be placed in an oven at 250F. to eliminate any surface moisture prior to aluminizing. The ambient air temperature shall be about 5 degrees Fahrenheit minimum above the dew point.
[0022] As shown in FIGS. 1 - 3 , the incident angle of the metallic spray should be as close to 90 degrees as possible. The angle should not be less than 45 degrees. It has been shown that coating porosity increases as the incident angle is reduced below 90 degrees. Distance of the spray gun to compressor body 10 shall not farther than 8 inches for similar reasoning.
[0023] The most preferred composition is pure aluminum (99.9% minimum purity). The metal system deposited on the steel may be an aluminum alloy, having less then about 10% magnesium. An alloyed aluminum metal system preferably has less then about 5% magnesium, which has good corrosion resistance. Aluminum/Zinc alloys should be avoided in marine corrosion conditions, because they have less corrosion resistance because of its solubility in salt water. The thickness of the aluminum shall be such that there is no interconnected porosity from the atmosphere to the base steel or iron substrate. This condition helps to prevent corrosion of the substrate. To help avoid this porosity problem, the thickness of aluminum must be about 0.010 to 0.015 inch in thickness. The aluminum coating thickness should be measured with an eddy current, ultrasonic or magnetic induction type instruments. The tensile bond adhesion strength of the aluminized coating must be 1000 PSI minimum as checked with the Elcometer Model 106 adhesion tester in accordance with ASTM D 4514. The wire diameter of the aluminum shall be about 0.0625 inch. The nozzle gas pressure during aluminizing shall be about 55 PSI.
[0024] The metallic coating can be Powder Flame Sprayed or Wire Flame Sprayed, but the preferred method is by Electric Arc Wire Spraying. Electric Arc Wire Spraying exhibits a higher quality coating and is more economical than flame spraying for this application. Electric Wire Arc Spraying is performed by contacting two aluminum wires which are at a potential to each other and generating a melt inducing arc. This arc is in proximity to a forced gas or air jet. The gas may be an inert gas, but for economic reasons, dry and cleaned compressed air may be used.
[0025] The aluminum wire becomes molten in the vicinity of the arc and the gas jet atomizes the aluminum and forces the droplets to impinge upon the steel or iron substrate. The droplets of aluminum impinge upon the steel and build up layer-by-layer until the desired thickness is achieved. The droplets start to cool and partially solidify prior to impingement. The kinetic energy of the droplets cause deformation and flattening of the aluminum particles as they hit the steel forming a uniform layer of aluminum on the steel or iron surfaces. Because of the nature of this deposition process, a small amount of porosity forms between the particles of aluminum. To maximize corrosion resistance, interconnected porosity (porosity that connects the marine atmosphere with the underlying ferrous substrate), must not exist. To prevent this, a sufficient amount of aluminum must be deposited and an adequate sealer must be employed to block the pores. The coating must be applied in multiple, thin even coatings and not heavily applied in one spray. It has been found advantageous, for completeness of coating, to perform spray strokes at 90 degrees from each other and to allow some overlap for each subsequent spray stroke. The practical application of this process dictates that it be automated and applied by a robot or similar technology. This will assure consistency and completeness of the coating. The grit blasting, described above, shall also be automated for the same reasons. The complex shape of a compressor makes it difficult to consistently coat or blast manually. Automation assures that all areas of the compressor are adequately treated.
[0026] After thermal spraying the compressor, a seal coating is applied. The purpose of a sealing step is to fill any porosity present in the thermally sprayed metal coating and to further enhance corrosion resistance. If a sealer is used without a top coat finish, it shall exhibit ultraviolet radiation stability from exposure to the sun. This step enhances the corrosion resistance of the metallized coating and increases the useable life of the aluminized compressor. When only a sealer is used, the sealer also serves to produce a cosmetically acceptable aluminized compressor. The aluminized compressor must not exhibit dark blotches, which occur if improperly sealed or if an inadequate sealer is used.
[0027] Several properties of the sealer must be unique to this compressor application. Therefore a special custom formulated sealer has been invented. The viscosity of the seal must be low enough so that the coating wicks into the pores and does not agglomerate on the surface. The thickness of the seal coat should not be greater than about 0.002 inch dry film thickness over the top of the aluminized coating. No moisture should be present on the surface of the metallized compressor prior to sealing unless the sealer is a water-based type. If moisture is present, the compressor shall be heated to 250° F. to remove moisture prior to the application of the sealant. Application of the seal coat should take place within about 24 hours of metallizing for optimal results. Ultraviolet protection properties should also be incorporated into the seal coat if no topcoat is used.
[0028] In addition, the chosen seal coat type must be such that it will withstand a constant compressor operating temperature of 300° F. Only certain regions of the compressor's surface may reach this magnitude of temperature, therefore the sealer must not discolor in the heated region and remain uncolored in the non-heated region so as to produce a two-tone appearance. After long term exposure to 300 F., the sealant must not degrade it's corrosion preventing sealing properties. Moreover, the sealer must retain it's all of the stated properties after exposure to normal compressor oils such as; polyol ester, mineral oils, etc. Accidental spillage of these oils may occur that exposes the aluminized and sealed surface to such oils.
[0029] The application of the sealant may be by brushing, spraying or dipping into the sealant. For the same reasons as above, the sealer shall be applied in a consistent manner that preferably utilizes automation. The curing process for the sealant should not exceed 300 F. as to not damage the internal components of the compressor due to excessive thermal degradation. The sealant should coat the compressor uniformly without agglomeration, which exceeds the required sealer thickness.
[0030] There are several chemical families that will meet the aforementioned requirements. Generally, the customized sealant described herein will have a carrier, an organic component, and an inorganic component. The first sealer consists of a silicon resin acrylic sealant containing: parachlorobenzotriflouride, phenyl; propyl silicone, mineral spirits, high solids silicone, acrylic resin and cobalt compounds. Additionally, particulates such as aluminum and/or silica can be incorporated. The silicon resin coating has good U.V. stability and is stable at 300° F. Applying two coats of about 0.001 inch dry film thickness each has been found to achieve better results than one coat at about 0.002 inch thickness.
[0031] Another possible sealant coating is an epoxy polyamide with n-butyl alcohol, C8,C10 aromatic hydrocarbons, zinc phosphate compounds and amorphous silica.
[0032] The final coating considered acceptable for this application is a cross-linked epoxy phenolic with an alkaline curing agent. The adherence and performance of this sealant shall be enhanced by first applying an aluminum conversion coating on top of the thermally sprayed aluminum. Two such conversion coatings known in the industry are Alodine or Iridite. The epoxy phenolic is then applied over the conversion coating.
[0033] Top coat finishes shall be of higher viscosity and similar in nature to paints. The maximum topcoat thickness shall be about 0.004 inch. The topcoat is applied over the sealer. The topcoat shall not be too thick as to negate the cathodic protective properties of the underlying thermally sprayed coating. For cosmetic reasons, it is preferable that dark coloring agents such as carbon black be added to the sealant or top coat to achieve a black or gray color. Moreover, the topcoat must be compatible with the sealer to maintain good adhesion. Top coat finishes should not be applied over an un-sealed aluminized coating.
[0034] The following are topcoat finishes that comply with the cosmetic and functional requirements setforth herein: The first topcoat finish is a polyurethane polymer with curing agents containing ethyl acetate, hexamethylene diisocyanate, homopolymer of HDI, n-butyl acetate and fine aluminum particles. This sealant also complies with the requirements of this application. The color of this top coat is gray-black.
[0035] Yet another top coat coating is a neutral urethane base acrylic with ethyl benzene, methyl keytone, xylene, aromatic naphtha, barium sulfate, and 1,2,4 trimethyl benzene and a polyisocyanate curing agent. The color of this product is black. The final top coat finish considered is an epoxy polyamide which contains magnesium silicate, titanium dioxide, black iron oxide, butyl alcohol and naptha. The color of this product is haze gray.
[0036] A wide variety of features can be utilized in the various materials disclosed and described above. The foregoing discussion discloses and describes a preferred embodiment of the present invention. One skilled in the art will readily recognize from such discussion, and from the accompanying drawings that various changes, modifications, and variations can be made therein without departing from the true spirit and fair scope of the invention. | A compressor having a corrosive resistant coating is disclosed. The coating has a first spray coated metallic layer. A sealant layer is disposed over the sprayed metallic coating which has an organic component, a solvent component, and an inorganic phase. | 8 |
The Government has rights in this invention pursuant to Contract No. DE-AC08-83NV10282 awarded by the U.S. Department of Energy.
BACKGROUND OF THE INVENTION
This invention relates to systems for amplifying optical signals and, more particularly, to a system and method for linearly amplifying optical analog signals by backward stimulated Raman scattering.
There are instances where weak electromagnetic energy, especially optical signals, must be amplified after the signals have traveled a long distance. Such application may include the detection and measurement of optical signals which are generated in a deep hole or a tunnel. These optical signals may be generated, for example, by an underground explosion. One of such optical signals may be the intensity of radiation of chemical compounds.
A conventional technique is to use an opto-electrical transducer for transforming such optical signals into the appropriate electrical signals. The electrical signals are then transmitted on a conventional metallic coaxial cable the other end of which is connected to a conventional detector. Such a technique has several disadvantages. One disadvantage is that such a metallic cable has an inherent characteristic of eliminating the high frequency components of a signal, resulting in the distortion of the time duration of the signal after it has traveled through the entire length of the coaxial cable, e.g., one kilometer. An analog electrical signal having a time duration of one nanosecond could be stretched into a signal of a few tens of nanoseconds; a signal having a time duration of one nanosecond is generally stretched to three nanoseconds after travelling approximatel 300 feet. In addition, the amplitude of the signal will also be lost after travelling such a long distance. Moreover, metallic cables tend to add noise to the desired electrical signal. In addition to the fact that metallic cables are expensive and heavy, it is capable of conducting lightning into the underground test site, causing damage to other equipment.
A second technique in detecting analog optical signals is to use optic fibers in conjunction with equipment such as spectral equalizers. One inherent disadvantage of such an optic fiber is its propensity to stretch out the time duration of the broad-spectrum optical signal. In addition, the optical signals generated by the underground explosion invariably have insufficient intensity such that detecting that intensity at one frequency is frequently impossible. Spectral equalizers are therefore used to compensate for the lack of intensity. A conventional spectral equalizer utilizes 10 fibers each of which is conducting a particular frequency of the generated optical signal. The optical signal is first grated into ten frequencies before each of the frequencies is fed into a fiber. Each of the fibers has a different length so as to compensate for the velocity of each frequency such that all frequencies of the optical signal arrive at the detector of the spectral equalizer at the same time. The intensities of all the frequencies are then accumulated such that the combined intensity can be detected. The combined intensity, however, is not a true amplification of the optical signal, but rather, an accumulation of the intensities of that signal. This technique is capable of increasing the intensity by approximately three times. Since the spectral equalizer is only capable of slightly increasing the intensity of the optical signal, informational contents of the optical signal are frequently lost. For example, if the optical signal is the intensity of radiation of a chemical compound, that signal contains spectral information that could be deciphered by spectroscopic equipment. Another disadvantage in using spectral analyzers is that such equipment requires extensive calibration and manpower support.
A third technique is to digitize the detected optical signal. In such a technique, the presence of such a digital optical signal represents the occurrence of an optical event. It, however, is incapable of presenting other informational contents of the optical signal such as the fast-varying, detailed spectral data or the time profile of that signal when that information is desired. In amplifying such a digital optical signal, the signal is transmitted in a conventional optic fiber the other end of which is connected to a laser source. In conjunction with the emitted laser beam from the laser source, the optic fiber facilitates amplification of the digital optical signal by stimulated Raman scattering. Another disadvantage of such a technique is its inherent inability to digitize high frequency optical signals.
SUMMARY OF THE INVENTION
An ideal system for linearly amplifying optical analog signals must be capable of maintaining the time profiles of the optical analog signals, i.e., amplifying an optical analog signal in a linear fashion. Linearity in the present invention is defined as the amplified replication of an original signal. Since the intensity of the optical analog signal is generally faint after having travelled a long distance, the ideal system should also be capable of amplifying optical analog signals in the range of a few microwatts to several milliwatts. Moreover, the ideal system should be capable of having gains of at least approximately 30 dB.
It is a major object of the present invention to provide a system for linearly amplifying optical analog signals by backward stimulated Raman scattering, that is, the preservation of the timing profile of an optical analog signal.
It is another object of the present invention to provide a system for linearly amplifying optical analog signals by backward stimulated Raman scattering in which optical analog signals in the range of a few microwatts to several milliwatts are amplified.
It is a further object of the present invention to provide a system for linearly amplifying optical analog signals by backward stimulated Raman scattering that is capable of amplifying the optical analog signals by at least approximately 30 dB.
In order to accomplish the above and still further objects, a system for linearly amplifying optical analog signals by backward stimulated Raman scattering is provided. The system comprises a laser source for generating a pump pulse, and an optic fiber having two opposed apertures, a first aperture for receiving the pump pulse and a second aperture for receiving the optical analog signal, wherein the optical analog signal is linearly amplified to an amplified optical analog signal. The gain of the system is at least 30 dB. In the preferred embodiment, the system comprises a beamsplitter, a first lens for coupling the pump pulse into the optic fiber, a second lens for coupling the optical analog signal into the optic fiber, a narrowband filter for filtering the amplified optical analog signal, a detector and an oscilloscope.
Other objects, features and advantages of the present invention will appear from the following detailed description of the best mode of a preferred embodiment, taken together with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatical block diagram of a system for linearly amplifying optical analog signals by backward stimulated Raman scattering of the present invention;
FIGS. 2A and 2B are graphs illustrating the linearity capability of the system of FIG. 1; and
FIG. 3 is a graph illustrating the amplification capability of the system of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, there is shown a system for linearly amplifying optical analog signals by backward stimulated Raman scattering, designated 12. System 12 includes a conventional tunable laser 14, a conventional beamsplitter 16, a first lens 18, an optic fiber 20, a second lens 22, a narrowband filter 24, a detector 26, and an oscilloscope 28. More particularly, tunable laser 14 is a conventional tunable dye laser for generating a pump pulse. Laser 14 in the preferred embodiment is a flashlamp-pumped dye laser that is tuned to a wavelength λ 0 of 595 nanometers. The pulse width of the pump pulse is approximately 4 microseconds in duration. The pulse width in the present invention is defined as the full width, half maximum (FWHM) amplitude of a pulse. The pump pulse passes through conventional beamsplitter 16 and enters into lens 18 which is used to couple the pump pulse into optic fiber 20. Optic fiber 20 in the preferred embodiment is a conventional glass fiber of approximately 500 meters in length and 65 microns in diameter. Fiber 20 in the preferred embodiment is also the Raman medium.
Positioned at the other end of fiber 20 is lens 22 which is used to couple an input, optical analog pulse into fiber 20. Input pulse in the preferred embodiment has a wavelength λ 1 of approximately 612 nanometers and a pulse width, i.e., FWHM, of approximately 10 nanoseconds. Input pulse may be a single, high frequency, optical analog signal generated by an underground explosion. Such a single input pulse is generally referred to as a single transient. The input pulse contains informational contents such as the spectral data relating to the intensity of radiation of a chemical compound. In such spectra data, the profile of the optical analog signal is of the utmost importance.
Pump pulse generates stimulated Raman scattering in fiber 20 such that the analog input pulse is amplified as it travels through the entire length of fiber 20. The opposed directions of travel of the pump pulse and the input pulse engender the nomenclature "backward Raman scattering." Raman scattering occurs when the pump pulse excites the molecules of the Raman medium to higher excited energy states such that the input pulse induces the excited medium to a lower state. The energy released by the molecules as they travel from the highest energy state to the lower state amplify the input pulse. The lower state, however, is still higher than the initial ground state of the Raman medium. The pump pulse in the preferred embodiment should be kept below one kilowatt so as to prevent the self-generation of unnecessary Raman scattering such that it interferes with the detection of the amplified input pulse. The capability of a high-energy pump pulse to generate Raman scattering without the assistance of the Raman medium is a phenomenon understood by those skilled in the art.
The amplified input pulse then travels through lens 18 and is reflected by beamsplitter 16. The amplified input pulse, filtered by narrowband filter 24, is then detected by a detector 26. In the preferred embodiment, filter 24 is set to transmit radiation at a wavelength of 612 nanometers so as to eliminate undesired scattered light. Detector 26 in the preferred embodiment is a conventional photodiode. Photodiode 26 then linearly transduces the amplified optical input pulse to an electrical signal and forwards it to oscilloscope 28 for display.
The relationship of the wavelength of the pump pulse, λ 0 , and the wavelength of the input pulse, λ 1 , is as follows: ##EQU1## where k R is the Raman shift in wave numbers, i.e., the difference between the energy of the initial ground state and the ultimate lower state. The wavelength of the input pulse is the first order Stokes shift of the wavelength of the pump pulse. Since the wavelength of the input pulse, λ 1 , and the relationship of the Stokes shift are known quantities, only the wavelength of the pump pulse λ 0 , needs to be adjusted. Such adjustments are readily accomplished by using tunable laser 14.
In addition, the essential relationship between the length of optic fiber 20 and the time durations of pump pulse, T 0 , and input pulse, T 1 , is as follows: ##EQU2## where L is the length of fiber 20,
n is the index of refraction of fiber 20, and
c is the speed of light. The latter two equations represent the necessary conditions for linear amplification.
FIGS. 2A and 2B illustrate the linearity capability of the present invention. An input pulse of approximately 60 millivolts in amplitude and 15 nanoseconds in duration, designated "A," is shown in FIG. 2A. Waveform A has two peaks which could be representing spectral data. After amplification in fiber 20, an amplified input pulse of approximately 150 millivolts and a time profile of approximately 15 nanoseconds is generated, designated "B". The 200 mV amplified input pulse of FIG. 2B does not represent the actual amplification of the input signal. In actuality, the original input pulse was amplified 1000 times, and then attentuated 400 times so as to permit waveform B to be graphed in this side-by-side comparison. Waveform B also contains the two peaks, illustrating the preservation of the time profile.
As illustrated in FIG. 3, the present invention is capable of amplifying the input signal to gains of 30 dB or higher. For example, a pump pulse having a peak power of approximately 0.6 kilowatt can amplify an input pulse to approximately 30 dB. The input pulse is generally in the range of a few microwatts to several milliwatts.
It will be apparent to those skilled in the art that various modifications may be made within the spirit of the invention and the scope of the appended claims. For example, although the wavelength illustrated in the present invention is in the visible range, this invention can be used in the infrared wavelength region. To minimize slight frequency degradation of the signals in fiber 20, fiber 20 may be selected to have the appropriate multimode or single mode characteristics. Or, a fiber 20 of smaller diameter may be used with higher frequency signals. Moreover, the length of fiber 20 is dependent on the application; for example, 700-1000 meters. | A system for linearly amplifying an optical analog signal by backward stimulated Raman scattering comprises a laser source for generating a pump pulse; and an optic fiber having two opposed apertures, a first aperture for receiving the pump pulse and a second aperture for receiving the optical analog signal, wherein the optical analog signal is linearly amplified to an amplified optical analog signal. | 7 |
BACKGROUND
Thermal imaging cameras are used in a variety of situations. For example, thermal imaging cameras are often used during maintenance inspections to thermally inspect equipment. Example equipment may include rotating machinery, electrical panels, or rows of circuit breakers, among other types of equipment. Thermal inspections can detect equipment hot spots such as overheating machinery or electrical components, helping to ensure timely repair or replacement of the overheating equipment before a more significant problem develops.
Depending on the configuration of the camera, the thermal imaging camera may also generate a visible light image of the same object. The camera may display the infrared image and the visible light image in a coordinated manner, for example, to help an operator interpret the thermal image generated by the thermal imaging camera. Unlike visible light images which generally provide good contrast between different objects, it is often difficult to recognize and distinguish different features in a thermal image as compared to the real-world scene.
Thermal noise, especially in low contrast thermal images, may pose additional problems when attempting to distinguish features within the images. Noise comparable with the temperature differences across an image may significantly alter the appearance of an image, making distinguishing between features even more difficult. While image averaging techniques have been used in the past to attempt to eliminate some of this random noise, these techniques have created additional image issues such as blurred edges and ghosting effects.
SUMMARY
In general, this disclosure is directed to a thermal imaging camera and method for providing thermal images wherein random noise is reduced through an averaging technique designed to reduce the negative byproducts of existing technology.
Various methods and devices fall within the scope of the present invention. Certain embodiments of the invention comprise a thermal imaging camera with at least one infrared (IR) sensor comprising a plurality of pixels. In some embodiments, each pixel may have a unique coordinate location. Certain cameras further comprise a display adapted to display at least a portion of an IR image detected from a target scene. In some embodiments of the invention, a thermal imaging camera comprises a processor that is programmed to capture a plurality of IR frames of a target scene. In certain embodiments, the processor further comprises instructions to average the plurality of frames in order to improve the overall image quality.
It may be that within the plurality of frames, a substantially fixed feature within the scene will be shifted in pixel coordinates from frame to frame. Accordingly, in certain embodiments of the invention a processor may be further programmed with steps to perform an alignment calculation in order to adjust the frames in such a way so that the substantially fixed feature is located in the same pixel coordinates amongst the plurality of frames. In yet further embodiments of the invention, the averaging performed by the processor is done on frames that have undergone such alignment calculation and adjustment.
Additional embodiments of the invention may further comprise a visible light (VL) sensor for detecting VL images of a target scene. A display may be configured to display at least a portion of this VL image and/or a portion of an alternatively or additionally captured IR image. In certain embodiments of the invention, a plurality of both VL and IR frames are captured by a thermal imaging camera. The IR frames may be averaged as described previously. In further embodiments, however, the IR frames may be aligned by means of an alignment calculation performed on the plurality of VL images.
Certain embodiments of the invention comprise a method for producing an IR image. In certain embodiments this image may comprise an average of a plurality of IR frames of a target scene. In further embodiments of the invention, an alignment calculation may be performed on the plurality of captured IR frames to adjust the frames in such that any substantially fixed feature within the plurality of frames is located in substantially the same pixel coordinates in each of the frames. In additional embodiments the plurality of frames are averaged after they are adjusted based on the alignment calculation.
The details of one or more examples are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a perspective front view of a thermal imaging camera according to some embodiments.
FIG. 2 is a perspective back view of the thermal imaging camera of FIG. 1 .
FIG. 3 is a functional block diagram illustrating components of thermal imaging cameras according to some embodiments.
FIGS. 4 a and 4 b are examples of pixel coordinate systems defined in an image.
FIG. 5 shows a set of frames showing the effects of averaging on random noise.
FIG. 6 illustrates the shortcomings of some averaging techniques by providing an example of an averaging calculation of four frames.
FIG. 7 illustrates the averaging of four frames with an additional correction made by an embodiment of the invention.
FIG. 8 the result of a correction and additional adjustment made by an embodiment of the invention.
FIG. 9 a is a process flow diagram outlining the basic operation of an embodiment of the invention.
FIG. 9 b is a process flow diagram detailing the post-processing of a series of infrared images.
FIG. 9 c is a process flow diagram detailing the post-processing of a series of infrared images using a corresponding series of visible light images.
DETAILED DESCRIPTION
The following detailed description is exemplary in nature and is not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the following description provides some practical illustrations for implementing various embodiments of the present invention. Examples of constructions, materials, dimensions, and manufacturing processes are provided for selected elements, and all other elements employ that which is known to those of ordinary skill in the field of the invention. Those skilled in the art will recognize that many of the noted examples have a variety of suitable alternatives.
A thermal imaging camera may be used to detect heat patterns across a scene, including an object or objects, under observation. The thermal imaging camera may detect infrared radiation given off by the scene and convert the infrared radiation into an infrared image indicative of the heat patterns. In some embodiments, the thermal imaging camera may also capture visible light from the scene and convert the visible light into a visible light image. Depending on the configuration of the thermal imaging camera, the camera may include infrared optics to focus the infrared radiation on an infrared sensor and visible light optics to focus the visible light on a visible light sensor.
Various embodiments provide methods and systems for producing thermal images with reduced noise using averaging techniques. To further improve image quality and eliminate problems that may arise from averaging (e.g. blurring, ghosting, etc.), an image alignment process is performed on the thermal images prior to averaging.
FIGS. 1 and 2 show front and back perspective views, respectively of an example thermal imaging camera 100 , which includes a housing 102 , an infrared lens assembly 104 , a visible light lens assembly 106 , a display 108 , a laser 110 , and a trigger control 112 . Housing 102 houses the various components of thermal imaging camera 100 . The bottom portion of thermal imaging camera 100 includes a carrying handle for holding and operating the camera via one hand. Infrared lens assembly 104 receives infrared radiation from a scene and focuses the radiation on an infrared sensor for generating an infrared image of a scene. Visible light lens assembly 106 receives visible light from a scene and focuses the visible light on a visible light sensor for generating a visible light image of the same scene. Thermal imaging camera 100 captures the visible light image and/or the infrared image in response to depressing trigger control 112 . In addition, thermal imaging camera 100 controls display 108 to display the infrared image and the visible light image generated by the camera, e.g., to help an operator thermally inspect a scene. Thermal imaging camera 100 may also include a focus mechanism coupled to infrared lens assembly 104 that is configured to move at least one lens of the infrared lens assembly so as to adjust the focus of an infrared image generated by the thermal imaging camera.
In operation, thermal imaging camera 100 detects heat patterns in a scene by receiving energy emitted in the infrared-wavelength spectrum from the scene and processing the infrared energy to generate a thermal image. Thermal imaging camera 100 may also generate a visible light image of the same scene by receiving energy in the visible light-wavelength spectrum and processing the visible light energy to generate a visible light image. As described in greater detail below, thermal imaging camera 100 may include an infrared camera module that is configured to capture an infrared image of the scene and a visible light camera module that is configured to capture a visible light image of the same scene. The infrared camera module may receive infrared radiation projected through infrared lens assembly 104 and generate therefrom infrared image data. The visible light camera module may receive light projected through visible light lens assembly 106 and generate therefrom visible light data.
In some examples, thermal imaging camera 100 collects or captures the infrared energy and visible light energy substantially simultaneously (e.g., at the same time) so that the visible light image and the infrared image generated by the camera are of the same scene at substantially the same time. In these examples, the infrared image generated by thermal imaging camera 100 is indicative of localized temperatures within the scene at a particular period of time while the visible light image generated by the camera is indicative of the same scene at the same period of time. In other examples, thermal imaging camera may capture infrared energy and visible light energy from a scene at different periods of time.
Visible light lens assembly 106 includes at least one lens that focuses visible light energy on a visible light sensor for generating a visible light image. Visible light lens assembly 106 defines a visible light optical axis which passes through the center of curvature of the at least one lens of the assembly. Visible light energy projects through a front of the lens and focuses on an opposite side of the lens. Visible light lens assembly 106 can include a single lens or a plurality of lenses (e.g., two, three, or more lenses) arranged in series. In addition, visible light lens assembly 106 can have a fixed focus or can include a focus adjustment mechanism for changing the focus of the visible light optics. In examples in which visible light lens assembly 106 includes a focus adjustment mechanism, the focus adjustment mechanism may be a manual adjustment mechanism or an automatic adjustment mechanism.
Infrared lens assembly 104 also includes at least one lens that focuses infrared energy on an infrared sensor for generating a thermal image. Infrared lens assembly 104 defines an infrared optical axis which passes through the center of curvature of lens of the assembly. During operation, infrared energy is directed through the front of the lens and focused on an opposite side of the lens. Infrared lens assembly 104 can include a single lens or a plurality of lenses (e.g., two, three, or more lenses), which may be arranged in series.
As briefly described above, thermal imaging camera 100 includes a focus mechanism for adjusting the focus of an infrared image captured by the camera. In the example shown in FIGS. 1 and 2 , thermal imaging camera 100 includes focus ring 114 . Focus ring 114 is operatively coupled (e.g., mechanically and/or electrically coupled) to at least one lens of infrared lens assembly 104 and configured to move the at least one lens to various focus positions so as to focus the infrared image captured by thermal imaging camera 100 . Focus ring 114 may be manually rotated about at least a portion of housing 102 so as to move the at least one lens to which the focus ring is operatively coupled. In some examples, focus ring 114 is also operatively coupled to display 108 such that rotation of focus ring 114 causes at least a portion of a visible light image and at least a portion of an infrared image concurrently displayed on display 108 to move relative to one another. In different examples, thermal imaging camera 100 may include a manual focus adjustment mechanism that is implemented in a configuration other than focus ring 114 , or may, in other embodiments, simply maintain a fixed focus.
In some examples, thermal imaging camera 100 may include an automatically adjusting focus mechanism in addition to or in lieu of a manually adjusting focus mechanism. An automatically adjusting focus mechanism may be operatively coupled to at least one lens of infrared lens assembly 104 and configured to automatically move the at least one lens to various focus positions, e.g., in response to instructions from thermal imaging camera 100 . In one application of such an example, thermal imaging camera 100 may use laser 110 to electronically measure a distance between an object in a target scene and the camera, referred to as the distance-to-target. Thermal imaging camera 100 may then control the automatically adjusting focus mechanism to move the at least one lens of infrared lens assembly 104 to a focus position that corresponds to the distance-to-target data determined by thermal imaging camera 100 . The focus position may correspond to the distance-to-target data in that the focus position may be configured to place the object in the target scene at the determined distance in focus. In some examples, the focus position set by the automatically adjusting focus mechanism may be manually overridden by an operator, e.g., by rotating focus ring 114 .
Data of the distance-to-target, as measured by the laser 110 , can be stored and associated with the corresponding captured image. For images which are captured using automatic focus, this data will be gathered as part of the focusing process. In some embodiments, the thermal imaging camera will also detect and save the distance-to-target data when an image is captured. This data may be obtained by the thermal imaging camera when the image is captured by using the laser 110 or, alternatively, by detecting the lens position and correlating the lens position to a known distance-to-target associated with that lens position. The distance-to-target data may be used by the thermal imaging camera 100 to direct the user to position the camera at the same distance from the target, such as by directing a user to move closer or further from the target based on laser measurements taken as the user repositions the camera, until the same distance-to-target is achieved as in an earlier image. The thermal imaging camera may further automatically set the lenses to the same positions as used in the earlier image, or may direct the user to reposition the lenses until the original lens settings are obtained.
During operation of thermal imaging camera 100 , an operator may wish to view a thermal image of a scene and/or a visible light image of the same scene generated by the camera. For this reason, thermal imaging camera 100 may include a display. In the examples of FIGS. 1 and 2 , thermal imaging camera 100 includes display 108 , which is located on the back of housing 102 opposite infrared lens assembly 104 and visible light lens assembly 106 . Display 108 may be configured to display a visible light image, an infrared image, and/or a combined image that is a simultaneous display of the visible light image and the infrared image. In different examples, display 108 may be remote (e.g., separate) from infrared lens assembly 104 and visible light lens assembly 106 of thermal imaging camera 100 , or display 108 may be in a different spatial arrangement relative to infrared lens assembly 104 and/or visible light lens assembly 106 . Therefore, although display 108 is shown behind infrared lens assembly 104 and visible light lens assembly 106 in FIG. 2 , other locations for display 108 are possible.
Thermal imaging camera 100 can include a variety of user input media for controlling the operation of the camera and adjusting different settings of the camera. Example control functions may include adjusting the focus of the infrared and/or visible light optics, opening/closing a shutter, capturing an infrared and/or visible light image, or the like. In the example of FIGS. 1 and 2 , thermal imaging camera 100 includes a depressible trigger control 112 for capturing an infrared and visible light image, and buttons 116 , which form part of the user interface, for controlling other aspects of the operation of the camera. A different number or arrangement of user input media are possible, and it should be appreciated that the disclosure is not limited in this respect. For example, thermal imaging camera 100 may include a touch screen display 108 which receives user input by depressing different portions of the screen.
FIG. 3 is a functional block diagram illustrating components of an example of thermal imaging camera 100 . Thermal imaging camera 100 includes an IR camera module 200 , front end circuitry 202 . The IR camera module 200 and front end circuitry 202 are sometimes referred to in combination as front end stage or front end components 204 of the infrared camera 100 . Thermal imaging camera 100 may also include a visible light camera module 206 , a display 108 , a user interface 208 , and an output/control device 210 .
Infrared camera module 200 may be configured to receive infrared energy emitted by a target scene and to focus the infrared energy on an infrared sensor for generation of infrared energy data, e.g., that can be displayed in the form of an infrared image on display 108 and/or stored in memory. Infrared camera module 200 can include any suitable components for performing the functions attributed to the module herein. In the example of FIG. 3 , infrared camera module 200 is illustrated as including infrared lens assembly 104 and infrared sensor 220 . As described above with respect to FIGS. 1 and 2 , infrared lens assembly 104 includes at least one lens that takes infrared energy emitted by a target scene and focuses the infrared energy on infrared sensor 220 . Infrared sensor 220 responds to the focused infrared energy by generating an electrical signal that can be converted and displayed as an infrared image on display 108 .
Infrared lens assembly 104 can have a variety of different configurations. In some examples, infrared lens assembly 104 defines an F-number (which may also be referred to as a focal ratio or F-stop) of a specific magnitude. An approximate F-number may be determined by dividing the effective focal length of a lens assembly by a diameter of an entrance to the lens assembly (e.g., an outermost lens of infrared lens assembly 104 ), which may be indicative of the amount of infrared radiation entering the lens assembly. In general, increasing the F-number of infrared lens assembly 104 may increase the depth-of-field, or distance between nearest and farthest objects in a target scene that are in acceptable focus, of the lens assembly. An increased depth of field may help achieve acceptable focus when viewing different objects in a target scene with the infrared optics of thermal imaging camera 100 set at a hyperfocal position. If the F-number of infrared lens assembly 104 is increased too much, however, the diffraction effects will decrease spatial resolution (e.g., clarity) such that a target scene may not be in acceptable focus. An increased F-number may also reduce the thermal sensitivity (e.g., the noise-equivalent temperature difference will worsen).
Infrared sensor 220 may include one or more focal plane arrays (FPA) that generate electrical signals in response to infrared energy received through infrared lens assembly 104 . Each FPA can include a plurality of infrared sensor elements including, e.g., bolometers, photon detectors, or other suitable infrared sensor elements. In operation, each sensor element, which may each be referred to as a sensor pixel, may change an electrical characteristic (e.g., voltage or resistance) in response to absorbing infrared energy received from a target scene. In turn, the change in electrical characteristic can provide an electrical signal that can be received by a processor 222 and processed into an infrared image displayed on display 108 .
For instance, in examples in which infrared sensor 220 includes a plurality of bolometers, each bolometer may absorb infrared energy focused through infrared lens assembly 104 and increase in temperature in response to the absorbed energy. The electrical resistance of each bolometer may change as the temperature of the bolometer changes. With each detector element functioning as a pixel, a two-dimensional image or picture representation of the infrared radiation can be further generated by translating the changes in resistance of each detector element into a time-multiplexed electrical signal that can be processed for visualization on a display or storage in memory (e.g., of a computer). Processor 222 may measure the change in resistance of each bolometer by applying a current (or voltage) to each bolometer and measure the resulting voltage (or current) across the bolometer. Based on these data, processor 222 can determine the amount of infrared energy emitted by different portions of a target scene and control display 108 to display a thermal image of the target scene.
Independent of the specific type of infrared sensor elements included in the FPA of infrared sensor 220 , the FPA array can define any suitable size and shape. In some examples, infrared sensor 220 includes a plurality of infrared sensor elements arranged in a grid pattern such as, e.g., an array of sensor elements arranged in vertical columns and horizontal rows. In various examples, infrared sensor 220 may include an array of vertical columns by horizontal rows of, e.g., 16×16, 50×50, 160×120, 120×160 or 650×480. In other examples, infrared sensor 220 may include a smaller number of vertical columns and horizontal rows (e.g., 1×1), a larger number vertical columns and horizontal rows (e.g., 1000×1000), or a different ratio of columns to rows.
In certain embodiments a Read Out Integrated Circuit (ROIC) is incorporated on the IR sensor 220 . The ROIC is used to output signals corresponding to each of the pixels. Such ROIC is commonly fabricated as an integrated circuit on a silicon substrate. The plurality of detector elements may be fabricated on top of the ROIC, wherein their combination provides for the IR sensor 220 . In some embodiments, the ROIC can include components discussed elsewhere in this disclosure (e.g. an analog-to-digital converter (ADC)) incorporated directly onto the FPA circuitry. Such integration of the ROIC, or other further levels of integration not explicitly discussed, should be considered within the scope of this disclosure.
As described above, the IR sensor 220 generates a series of electrical signals corresponding to the infrared radiation received by each infrared detector element to represent a thermal image. A “frame” of thermal image data is generated when the voltage signal from each infrared detector element is obtained by scanning all of the rows that make up the IR sensor 220 . Again, in certain embodiments involving bolometers as the infrared detector elements, such scanning is done by switching a corresponding detector element into the system circuit and applying a bias voltage across such switched-in element. Successive frames of thermal image data are generated by repeatedly scanning the rows of the IR sensor 220 , with such frames being produced at a rate sufficient to generate a video representation (e.g. 30 Hz, or 60 Hz) of the thermal image data.
The front end circuitry 202 includes circuitry for interfacing with and controlling the IR camera module 200 . In addition, the front end circuitry 202 initially processes and transmits collected infrared image data to a processor 222 via a connection therebetween. More specifically, the signals generated by the IR sensor 220 are initially conditioned by the front end circuitry 202 of the thermal imaging camera 100 . In certain embodiments, as shown, the front end circuitry 202 includes a bias generator 224 and a pre-amp/integrator 226 . In addition to providing the detector bias, the bias generator 224 can optionally add or subtract an average bias current from the total current generated for each switched-in detector element. The average bias current can be changed in order (i) to compensate for deviations to the entire array of resistances of the detector elements resulting from changes in ambient temperatures inside the thermal imaging camera 100 and (ii) to compensate for array-to-array variations in the average detector elements of the IR sensor 220 . Such bias compensation can be automatically controlled by the thermal imaging camera 100 or software, or can be user controlled via input to the output/control device 210 or processor 222 . Following provision of the detector bias and optional subtraction or addition of the average bias current, the signals can be passed through a pre-amp/integrator 226 . Typically, the pre-amp/integrator 226 is used to condition incoming signals, e.g., prior to their digitization. As a result, the incoming signals can be adjusted to a form that enables more effective interpretation of the signals, and in turn, can lead to more effective resolution of the created image. Subsequently, the conditioned signals are sent downstream into the processor 222 of the thermal imaging camera 100 .
In some embodiments, the front end circuitry 202 can include one or more additional elements for example, additional sensors 228 or an ADC 230 . Additional sensors 228 can include, for example, temperature sensors, visual light sensors (such as a CCD), pressure sensors, magnetic sensors, etc. Such sensors can provide additional calibration and detection information to enhance the functionality of the thermal imaging camera 100 . For example, temperature sensors can provide an ambient temperature reading near the IR sensor 220 to assist in radiometry calculations. A magnetic sensor, such as a Hall effect sensor, can be used in combination with a magnet mounted on the lens to provide lens focus position information. Such information can be useful for calculating distances, or determining a parallax offset for use with visual light scene data gathered from a visual light sensor.
An ADC 230 can provide the same function and operate in substantially the same manner as discussed below, however its inclusion in the front end circuitry 202 may provide certain benefits, for example, digitization of scene and other sensor information prior to transmittal to the processor 222 via the connection therebetween. In some embodiments, the ADC 230 can be integrated into the ROIC, as discussed above, thereby eliminating the need for a separately mounted and installed ADC 230 .
In some embodiments, front end components can further include a shutter 240 . A shutter 240 can be externally or internally located relative to the lens and operate to open or close the view provided by the IR lens assembly 104 . As is known in the art, the shutter 240 can be mechanically positionable, or can be actuated by an electro-mechanical device such as a DC motor or solenoid. Embodiments of the invention may include a calibration or setup software implemented method or setting which utilize the shutter 240 to establish appropriate bias levels for each detector element.
Components described as processors within thermal imaging camera 100 , including processor 222 , may be implemented as one or more processors, such as one or more microprocessors, digital signal processors (DSPs), application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), programmable logic circuitry, or the like, either alone or in any suitable combination. Processor 222 may also include memory that stores program instructions and related data that, when executed by processor 222 , cause thermal imaging camera 100 and processor 222 to perform the functions attributed to them in this disclosure. Memory may include any fixed or removable magnetic, optical, or electrical media, such as RAM, ROM, CD-ROM, hard or floppy magnetic disks, EEPROM, or the like. Memory may also include a removable memory portion that may be used to provide memory updates or increases in memory capacities. A removable memory may also allow image data to be easily transferred to another computing device, or to be removed before thermal imaging camera 100 is used in another application. Processor 222 may also be implemented as a System on Chip that integrates all components of a computer or other electronic system into a single chip. These elements manipulate the conditioned scene image data delivered from the front end stages 204 in order to provide output scene data that can be displayed or stored for use by the user. Subsequently, the processor 222 (processing circuitry) sends the processed data to a display 108 or other output/control device 210 .
During operation of thermal imaging camera 100 , processor 222 can control infrared camera module 200 to generate infrared image data for creating an infrared image. Processor 222 can generate a digital “frame” of infrared image data. By generating a frame of infrared image data, processor 222 captures an infrared image of a target scene at a given point in time.
Processor 222 can capture a single infrared image or “snap shot” of a target scene by measuring the electrical signal of each infrared sensor element included in the FPA of infrared sensor 220 a single time. Alternatively, processor 222 can capture a plurality of infrared images of a target scene by repeatedly measuring the electrical signal of each infrared sensor element included in the FPA of infrared sensor 220 . In examples in which processor 222 repeatedly measures the electrical signal of each infrared sensor element included in the FPA of infrared sensor 220 , processor 222 may generate a dynamic thermal image (e.g., a video representation) of a target scene. For example, processor 222 may measure the electrical signal of each infrared sensor element included in the FPA at a rate sufficient to generate a video representation of thermal image data such as, e.g., 30 Hz or 60 Hz. Processor 222 may perform other operations in capturing an infrared image such as sequentially actuating a shutter 240 to open and close an aperture of infrared lens assembly 104 , or the like.
With each sensor element of infrared sensor 220 functioning as a sensor pixel, processor 222 can generate a two-dimensional image or picture representation of the infrared radiation from a target scene by translating changes in an electrical characteristic (e.g., resistance) of each sensor element into a time-multiplexed electrical signal that can be processed, e.g., for visualization on display 108 and/or storage in memory. Processor 222 may perform computations to convert raw infrared image data into scene temperatures (radiometry) including, in some examples, colors corresponding to the scene temperatures.
Processor 222 may control display 108 to display at least a portion of an infrared image of a captured target scene. In some examples, processor 222 controls display 108 so that the electrical response of each sensor element of infrared sensor 220 is associated with a single pixel on display 108 . In other examples, processor 222 may increase or decrease the resolution of an infrared image so that there are more or fewer pixels displayed on display 108 than there are sensor elements in infrared sensor 220 . Processor 222 may control display 108 to display an entire infrared image (e.g., all portions of a target scene captured by thermal imaging camera 100 ) or less than an entire infrared image (e.g., a lesser port of the entire target scene captured by thermal imaging camera 100 ). Processor 222 may perform other image processing functions, as described in greater detail below.
Independent of the specific circuitry, thermal imaging camera 100 may be configured to manipulate data representative of a target scene so as to provide an output that can be displayed, stored, transmitted, or otherwise utilized by a user.
Thermal imaging camera 100 includes visible light camera module 206 . Visible light camera module 206 may be configured to receive visible light energy from a target scene and to focus the visible light energy on a visible light sensor for generation of visible light energy data, e.g., that can be displayed in the form of a visible light image on display 108 and/or stored in memory. Visible light camera module 206 can include any suitable components for performing the functions attributed to the module herein. In the example of FIG. 3 , visible light camera module 206 is illustrated as including visible light lens assembly 106 and visible light sensor 242 . As described above with respect to FIGS. 1 and 2 , visible light lens assembly 106 includes at least one lens that takes visible light energy emitted by a target scene and focuses the visible light energy on visible light sensor 242 . Visible light sensor 242 responds to the focused energy by generating an electrical signal that can be converted and displayed as a visible light image on display 108 .
Visible light sensor 242 may include a plurality of visible light sensor elements such as, e.g., CMOS detectors, CCD detectors, PIN diodes, avalanche photo diodes, or the like. The number of visible light sensor elements may be the same as or different than the number of infrared light sensor elements.
In operation, optical energy received from a target scene may pass through visible light lens assembly 106 and be focused on visible light sensor 242 . When the optical energy impinges upon the visible light sensor elements of visible light sensor 242 , photons within the photodetectors may be released and converted into a detection current. Processor 222 can process this detection current to form a visible light image of the target scene.
During use of thermal imaging camera 100 , processor 222 can control visible light camera module 206 to generate visible light data from a captured target scene for creating a visible light image. The visible light data may include luminosity data indicative of the color(s) associated with different portions of the captured target scene and/or the magnitude of light associated with different portions of the captured target scene. Processor 222 can generate a “frame” of visible light image data by measuring the response of each visible light sensor element of thermal imaging camera 100 a single time. By generating a frame of visible light data, processor 222 captures visible light image of a target scene at a given point in time. Processor 222 may also repeatedly measure the response of each visible light sensor element of thermal imaging camera 100 so as to generate a dynamic thermal image (e.g., a video representation) of a target scene, as described above with respect to infrared camera module 200 .
With each sensor element of visible light camera module 206 functioning as a sensor pixel, processor 222 can generate a two-dimensional image or picture representation of the visible light from a target scene by translating an electrical response of each sensor element into a time-multiplexed electrical signal that can be processed, e.g., for visualization on display 108 and/or storage in memory.
Processor 222 may control display 108 to display at least a portion of a visible light image of a captured target scene. In some examples, processor 222 controls display 108 so that the electrical response of each sensor element of visible light camera module 206 is associated with a single pixel on display 108 . In other examples, processor 222 may increase or decrease the resolution of a visible light image so that there are more or fewer pixels displayed on display 108 than there are sensor elements in visible light camera module 206 . Processor 222 may control display 108 to display an entire visible light image (e.g., all portions of a target scene captured by thermal imaging camera 100 ) or less than an entire visible light image (e.g., a lesser port of the entire target scene captured by thermal imaging camera 100 ).
As noted above, processor 222 may be configured to determine a distance between thermal imaging camera 100 and an object in a target scene captured by a visible light image and/or infrared image generated by the camera. Processor 222 may determine the distance based on a focus position of the infrared optics associated with the camera. For example, processor 222 may detect a position (e.g., a physical position) of a focus mechanism associated with the infrared optics of the camera (e.g., a focus position associated with the infrared optics) and determine a distance-to-target value associated with the position. Processor 222 may then reference data stored in memory that associates different positions with different distance-to-target values to determine a specific distance between thermal imaging camera 100 and the object in the target scene.
In these and other examples, processor 222 may control display 108 to concurrently display at least a portion of the visible light image captured by thermal imaging camera 100 and at least a portion of the infrared image captured by thermal imaging camera 100 . Such a concurrent display may be useful in that an operator may reference the features displayed in the visible light image to help understand the features concurrently displayed in the infrared image, as the operator may more easily recognize and distinguish different real-world features in the visible light image than the infrared image. In various examples, processor 222 may control display 108 to display the visible light image and the infrared image in side-by-side arrangement, in a picture-in-picture arrangement, where one of the images surrounds the other of the images, or any other suitable arrangement where the visible light and the infrared image are concurrently displayed.
For example, processor 222 may control display 108 to display the visible light image and the infrared image in a combined arrangement. In a combined arrangement, the visible light image and the infrared image may be superimposed on top of one another. An operator may interact with user interface 208 to control the transparency or opaqueness of one or both of the images displayed on display 108 . For example, the operator may interact with user interface 208 to adjust the infrared image between being completely transparent and completely opaque and also adjust the visible light image between being completely transparent and completely opaque. Such an example combined arrangement, which may be referred to as an alpha-blended arrangement, may allow an operator to adjust display 108 to display an infrared-only image, a visible light-only image, of any overlapping combination of the two images between the extremes of an infrared-only image and a visible light-only image. Processor 222 may also combined scene information with other data, such as radiometric data, alarm data, and the like.
Additionally, in some embodiments, the processor 222 can interpret and execute commands from user interface 208 , an output/control device 210 . This can involve processing of various input signals and transferring those signals to the front end circuitry 202 via a connection therebetween. Components (e.g. motors, or solenoids) proximate the front end circuitry 202 can be actuated to accomplish the desired control function. Exemplary control functions can include adjusting the focus, opening/closing a shutter, triggering sensor readings, adjusting bias values, etc. Moreover, input signals may be used to alter the processing of the image data that occurs in the processor 222 .
Processor can further include other components to assist with the processing and control of the infrared imaging camera 100 . For example, as discussed above, in some embodiments, an ADC can be incorporated into the processor 222 . In such a case, analog signals conditioned by the front-end stages 204 are not digitized until reaching the processor 222 . Moreover, some embodiments can include additional on board memory for storage of processing command information and scene data, prior to transmission to the display 108 or the output/control device 210 .
An operator may interact with thermal imaging camera 100 via user interface 208 , which may include buttons, keys, or another mechanism for receiving input from a user. The operator may receive output from thermal imaging camera 100 via display 108 . Display 108 may be configured to display an infrared-image and/or a visible light image in any acceptable palette, or color scheme, and the palette may vary, e.g., in response to user control. In some examples, display 108 is configured to display an infrared image in a monochromatic palette such as grayscale or amber. In other examples, display 108 is configured to display an infrared image in a color palette such as, e.g., ironbow, blue-red, or other high contrast color scheme. Combination of grayscale and color palette displays are also contemplated.
While processor 222 can control display 108 to concurrently display at least a portion of an infrared image and at least a portion of a visible light image in any suitable arrangement, a picture-in-picture arrangement may help an operator to easily focus and/or interpret a thermal image by displaying a corresponding visible image of the same scene in adjacent alignment.
A power supply (not shown) delivers operating power to the various components of thermal imaging camera 100 and, in some examples, may include a rechargeable or non-rechargeable battery and a power generation circuit.
During operation of thermal imaging camera 100 , processor 222 controls infrared camera module 200 and visible light camera module 206 with the aid of instructions associated with program information that is stored in memory to generate a visible light image and an infrared image of a target scene. Processor 222 further controls display 108 to display the visible light image and/or the infrared image generated by thermal imaging camera 100 .
While post-processing and performing calculations on digital images, it is often convenient to assign coordinates to each pixel within said images. This allows for localization of features contained within the image, and a consistent means by which to reference various features within an image to one another or a particular location such as a the center or an edge of a frame. Implementing a coordinate system into a set of pixels may be done in several ways. FIGS. 4 a and 4 b exemplify two such ways, but it should be appreciated that methods are not limited to those disclosed herein.
FIG. 4 a illustrates a two-dimensional pixel coordinate system. In this case, there are two axes representing a two-dimensional image, with each pixel being associated with a pair of coordinates, for example (1,1). Shifting one pixel to the right increases the first coordinate by one, while shifting to the left decreases the first coordinate by one. Similarly, shifting one pixel up increases the second coordinate by one, and shifting one pixel down decreases the second coordinate by one. In this particular example, the pixel in the bottom-left corner of the image is associated with coordinates (0,0). Accordingly, the pixel with coordinates (1,1) is one pixel above and one pixel to the right of the bottom-left corner.
FIG. 4 b illustrates a pixel coordinate system wherein each pixel is assigned a single number. In this particular 25-pixel example, shifting one pixel to the right increases the coordinate by one, and shifting one pixel to the left decreases the coordinate by one, as was also the case in the previous example. However, in this arrangement, shifting one pixel up increases the coordinate by five and shifting one pixel down decreases the coordinate by five. In this example, the pixel in the bottom-left corner of the image is assigned location 0. Accordingly, the coordinate one pixel above and one pixel to the right of pixel 0 is 0+1 (one pixel to the right)+5 (one pixel up)=6. More complicated arithmetic is necessary to find the location of a pixel given its coordinate in this arrangement, however.
Thermal scenes with low temperature contrast throughout can cause problems for thermal imaging cameras. If there is little temperature contrast (i.e., only small temperature differences) across an entire thermal scene, a small amount of noise in the data may obscure the actual temperature differences that are present. For example, if the camera has a noise equivalent temperature difference (NETD) of 50 mK (equivalently 0.050° C.), no two points within 0.050° C. from one another are readily distinguishable. Put another way, if, along with this NETD, the highest and lowest sensed temperatures are separated by 1° C. and the camera is displaying a range of 100 colors or shades to visually differentiate between temperatures, no five consecutive colors in this range can be differentiated with any reliability. This is because at any given point on the image, there could be up to 5 colors (or shades) of “noise” affecting the measurement and the display. This noise will obscure any temperature differences in the scene that are below the noise level.
Such noise may vary with time, being present at one point in one frame and gone or different the next. With this being the case, a temporal average of the data in multiple frames can serve to reduce this noise, thereby reducing the NETD and improving the signal to noise ratio. As more frames are taken into the average, the effective NETD of the scene decreases, increasing the thermal sensitivity of the device and the potential contrast of the scene. A thermal scene averaged from n individual frames decreases the NETD of the resulting image by a factor of √n.
FIG. 5 illustrates this reduction in noise with increased averaging. Shown are four representations of imaged noise (only data representing noise on each pixel is shown, no signal from thermal scene), shown as frame 501 , frame 502 , frame 503 , and frame 504 . Assuming the noise is completely random in time, eight five-pixel by five-pixel “images” (i.e. frames) were generated with pixels having a randomly populated number between −100 and 100 representing random amounts of thermal noise. Each image represents the same thermal image of a scene at a different point in time. Frame 501 represents the noise data from a single frame with no averaging, only random noise data. Frame 502 represents the average of two frames with random noise, reducing the NETD of the scene by a factor of √2. Frame 503 represents the average of four frames, reducing the NETD by a factor of 2 from the original scene. Frame 504 represents the average of eight random frames, again reducing the NETD, this time by a factor of √8 from the original frame. Each frame is color-coded to more clearly display differences in the noise signal—darker pixels represent lower values of noise. It is evident the wide range of noise present in frame 501 is greatly reduced via the averaging steps, as comparatively, frame 504 has very little contrast between pixels. This amounts to significantly reduced noise differences among pixels as the number of averaged frames increases, allowing for greater temperature resolution of a low-contrast thermal scene.
Certain embodiments of the invention employ an approach to averaging that entails capturing a plurality of scenes of an image, wherein each pixel of the scene has a value corresponding to the measured temperature associated with that pixel. Over the plurality of scenes, the values from the same pixel coordinates are averaged together, resulting in a calculated average value for each pixel. These averaged pixels are assembled together to construct an average image. Averaging, however, can be a source of additional error and/or undesirable image artifacts.
A common problem with averaging images is that the resulting image may contain blurred edges or ghosting artifacts due to misalignments of the frames being averaged. This is illustrated in FIG. 6 , wherein a two pixel by two pixel square of uniform intensity representing a substantially fixed feature appears near the center of the frame in each of the four frames 601 , 602 , 603 and 604 that are to be averaged. The number in each square is meant as an exemplary value corresponding to a temperature associated with each pixel, while the shade of each square is meant to be a visual representation of the temperature associated with each pixel. The figure illustrates a situation in which, during the process of capturing of the four frames to be used, the location of the square object shifted in pixel coordinates, causing the resulting averaged image 605 to be a three pixel by three pixel square of varying intensity. This averaged image 605 is very different from any one of the individual frames, and therefore shows an inaccurate representation of the true scene. An alignment step in which like features are shifted to like coordinate locations prior to averaging will help fix this problem. One possible alignment step is outlined below.
If each frame is shifted with respect to its pixel coordinates by a proper amount, then the object in the image will be appropriately aligned in each frame prior to averaging, and this inaccuracy will not occur. For example, if using the two-dimensional coordinate system shown in FIG. 4 a , the two-by-two box in each frame will have a definable location. In this case, the box comprises pixels:
(1,2), (2,2), (1,3), and (2,3) in frame one 601
(1,1), (2,1), (1,2), and (2,2) in frame two 602
(2,1), (3,1), (2,2), and (3,2) in frame three 603
(2,2), (3,2), (2,3), and (3,3) in frame four 604
After performing an alignment calculation, the imaging device decides how best to shift the pixel coordinates of the non-reference frames to most accurately align these frames with the reference frames. Examples of such calculations are known in the art, and may include a correlation or similar calculation. Additional alignment methods are disclosed in the paper entitled “Computational Re-Photography” by Bae et al. (ACM Transactions on Graphics, Vol. 29, No. 3, Article 24, Publication date: June 2010), as well as, by way of the transformation matrix, in the publication US2007/0247517 or by way of calculating a similarity figure as in U.S. Pat. No. 7,924,312, each of which are hereby incorporated by reference.
If, for example, the device chooses frame one 601 to be a reference frame, aligning the remaining frames with the reference frame requires the following coordinate shifts, calculated by subtracting the pixel location of a particular feature in one frame from the pixel location of the same feature in the reference frame. In this example, the feature used is the bottom-left corner of the imaged square:
frame one 601 : no shift since it is the reference frame frame two 602 : (1,2)−(1,1)=(0,1); add (0,1) to all coordinates of frame two 602 prior to averaging frame three 603 : (1,2)−(2,1)=(−1,1); add (−1,1) to all coordinates of frame three 603 prior to averaging frame four 604 : (1,2)−(2,2)=(−1,0); (−1,0) to all coordinates of frame four 604 prior to averaging
FIG. 7 shows the frames 701 , 702 , 703 and 704 , representing the shifted result of the original frames 601 , 602 , 603 and 604 respectively. Averaged frame 705 shows the resulting image averaged from the shifted frames 701 - 704 . As illustrated, performing these shifts prior to averaging the frames will cause the object, in this case the two-by-two square, to fall in the same pixel coordinate location in each of the frames 701 , 702 , 703 and 704 , with a subsequent averaging calculation resulting in the averaged image 705 —a more accurate representation of the original scene.
If a frame is shifted to be aligned with a reference frame, the borders of the two frames will not coincide, and the frames will not entirely overlap. This will result in portions of the non-reference frames to be “hanging off” the edge of the reference frame after they have been shifted to align the elements of the scene. This is shown in FIG. 8 , where a secondary frame 802 is shifted onto the reference frame 801 and the two are averaged. It can be seen, however, that there are “extra” pixels, shown here in a lighter grey, that do not fit into the reference frame. In certain embodiments of the invention, these pixels may simply be disregarded by the camera or somehow incorporated into the border of the image. In other embodiments, these “extra” pixels may be handled in other ways. FIG. 9 a shows a flow diagram illustrating the general procedure of an embodiment of the invention as described thus far. A user chooses 901 to enable burst mode and post processing within the thermal imaging camera. If not enabled, the camera may operate as a traditional thermal imaging camera 999 . If enabled, the user may select the number of frames to average 902 to form the resulting image. The selection may be made from a list, possibly comprising options of 2, 4, 8 . . . n images to be averaged together. In some embodiments, enabling of burst mode and the selection of the number of frames to average may be done via the user interface 116 . In general, averaging more frames should be more effective at removing noise, but at the expense of processing time. In an alternative embodiment, the user may select the number of frames to average 902 prior to choosing 901 to enable burst mode.
Next, the user may capture 903 a series of infrared (IR) images for averaging using the user interface 116 and trigger control 112 to command the processor 222 to capture a plurality of frames. These frames are preferably taken consecutively, but in some embodiments they may not be. For example, in an embodiment, the camera may choose to discard a frame if it does not meet certain criteria. A visible light (VL) image of the scene may be additionally captured via the aforementioned visible light camera module 206 . The camera, such as via its processor 222 running a programmed algorithm, then performs post processing steps 904 , aligning and averaging the images. During the calculation process, the user may experience an hourglass or other icon or image on the display 108 indicating the camera is performing processing steps. A live thermal image may not be shown on display 108 during processing. In certain circumstances, this situation may be undesirable to the user. In other embodiments, a live thermal image may be available to view on display 108 during processing. During processing, the user may abort 997 the calculation, resulting in the return of live thermal imagery to the display 108 and readying the device for further use 998 . If the calculation is not aborted, the camera will align and average the IR images, resulting 905 in an averaged thermal scene. In some embodiments, the averaged thermal scene may have a visible light image associated therewith. The processing steps of alignment and averaging of an embodiment of the invention are detailed further in FIG. 9 b . After a camera has acquired 910 a series of n IR images, it selects 911 one of said images to be a reference image. In certain embodiments, the processor selects the first of the series of acquired images as the reference image. In other embodiments, other images from the series may be selected. The processor 222 next performs an alignment calculation 912 such as those mentioned above to determine how much, if any, the n−1 frames other than the reference frame are shifted from the reference frame. In other words, if there is an object within a scene that is substantially fixed, i.e. a non-moving object with respect to the camera, its pixel coordinates in each frame should match. However, they may not always do so due to instability of the object, camera, operator, or any other factor that may introduce unintended position changes of elements within the scene. Accordingly, the calculation for alignment is done to determine the degree of shift each of the n−1 non-reference frames must go through in order to be properly aligned with the reference frame. Although image correlation and other methods are noted above, any known method of determining spatial shifts between images may be employed.
Upon calculation 912 , n−1 new versions of the non-reference images are created, each now being aligned with the reference image. These images are averaged together 913 , via processor 222 , for instance, to create 914 a final, temporally averaged IR image with a NETD reduced from the original image by a factor of √n and, as discussed previously, may also include an associated VL image.
In some embodiments, the thermal imaging device may capture both infrared (IR) and visible light (VL) images. In further embodiments, these VL and IR images may be captured substantially simultaneously, wherein the pixel coordinates of elements within the scene will not have changed between the capturing of the VL and IR frames. In such an embodiment, the camera may use the VL images to perform the alignment of multiple frames prior to the averaging of the IR data. Since the IR and VL scenes were taken at least substantially simultaneously, any misalignment among IR scenes should be similarly manifested within the VL scenes. Accordingly, determining the misalignment among the VL scenes results in knowing the misalignment among the associated IR scenes, thereby allowing for them to be adequately aligned and averaged appropriately. Since VL images often provide better contrast between different objects than is provided by IR images, it is sometimes much easier to determine the spatial shifts between captured frames by analyzing (e.g., correlating or performing some other alignment calculation) the VL images rather than by analyzing the IR images for. This process of using both VL and IR images is detailed in FIG. 9 c.
In this embodiment, a camera captures 920 a series of n IR and n associated VL images, with each IR and its associated VL image being captured substantially simultaneously as one another. Next, one VL image is selected 921 , by the processor 222 for instance, to be the reference image. Subsequently, a calculation 922 similar to the one discussed in the description of FIG. 9 b is carried out, only this time calculating the offset in position of each of the n−1 non-reference VL images. Upon determining the deviation from the reference image for each of the additional n−1 VL images, each IR image is shifted 923 by its corresponding VL image misalignment amount. Since the IR and VL images were taken substantially simultaneously and the optics of each are fixed relative to each other, any offset in the VL images from the reference image will likely be equally present in the IR images. As such, performing this shift of IR images will act to align them just as it would align the VL images. Once aligned, the IR images are averaged 924 as described in the description of FIG. 9 b , resulting 925 in an averaged IR image with a NETD reduced by a factor of √n from a non-averaged IR image. This image has associated with it a VL image, namely the reference VL image used in the alignment step.
This embodiment may be preferable in the situation where there is low thermal contrast, such as the situation described above when a reduction in noise may greatly aid the quality of the image. This embodiment may be advantageous because elements helpful in defining position such as edges and corners may not be very abrupt or clear in the IR image of low contrast. It may be the case that, while the thermal contrast is low, these edges and corners are very clear and distinct within the VL image. If this is the case, the alignment calculation may be much more accurate or made much more easily while using the VL images as opposed to the IR images.
In other embodiments, IR and associated VL images need not be captured substantially simultaneously in order to perform the aforementioned process of aligning IR images by performing calculations on the VL images. Rather, using the VL images in order to align the IR images may be possible using factors such as frame capture times of and physical separation between the VL and IR camera modules. Using these or other known values, a reasonable IR image alignment may be calculated from VL images captured at substantially different times as the associated IR images.
Example thermal image cameras and related techniques have been described. The techniques described in this disclosure may also be embodied or encoded in a computer-readable medium, such as a non-transitory computer-readable storage medium containing instructions. Instructions embedded or encoded in a computer-readable storage medium may cause a programmable processor, or other processor, to perform the method, e.g., when the instructions are executed. Computer readable storage media may include random access memory (RAM), read only memory (ROM), a hard disk, optical media, or other computer readable media.
Various examples have been described. These and other examples are within the scope of the following claims. | Devices and methods for generating infrared (IR) images with improved quality are disclosed. In embodiments of the invention, temporal averaging techniques are used to reduce temporal noise that may be present in thermal images. This is especially useful in low-contrast thermal scenes, where a relatively small amount of thermal noise may become exceedingly prevalent. In order to average properly, some embodiments of the invention provide methods or means for aligning multiple images that are to be averaged together to eliminate inaccuracies and misrepresentations that may result from averaging misaligned images. | 6 |
FIELD AND BACKGROUND OF THE INVENTION
[0001] The present invention relates to the fields of transportation and tourism and specifically to a motor vehicle having a passenger controlled entertainment system.
[0002] Taxi cabs are well-known features of modern urban settings. People who hire taxi cabs, the passengers, often find themselves in a cab for an extended period of time whether because a specific trip is very long or due to traffic jams. The long period of time in which a passenger is found in a taxi cab is a source of irritation.
[0003] A variety of devices have been installed in motor vehicles to allow the driver to make these extended periods of time more enjoyable. Such devices include radio receivers and audio players such as cassette tape players, 8-track tape players and compact disk players. These devices are under control of the driver, the person invariably found in a motor vehicle. However, the fact that the driver controls the choice of music rarely assuages the irritation of a passenger.
[0004] It would be highly advantageous to have a device that provides added-value to a taxi-cab passenger in the form of a passenger-controlled entertainment system.
SUMMARY OF THE INVENTION
[0005] The above and other objectives are achieved by the present invention.
[0006] According to the teachings of the present invention there is provided a device exceptionally useful for use as a taxi-cab comprising a motor vehicle having an entertainment system, a driver position and at least one passenger position and a control system to control the entertainment system, wherein the control system is operable by a person (the passenger) located at the at least one passenger position.
[0007] According to a feature of the present invention, the entertainment system includes at least one of the devices from a group consisting of audio playback devices, audiovisual playback devices, two-way wireless communication devices, geographical location indication devices and goods/services information devices.
[0008] According to a further feature of the present invention, the device also includes an activation switch for the entertainment system, the activation switch having at least two states, a first state where said entertainment system is activated for operation by the passenger; and a second state where the entertainment system is inactivated for operation by the passenger and a payment collection device, configured to toggle the activation switch from the second state (inactivated) to the first state (activated) upon collection of a payment. In such a way, a passenger can use the entertainment system only upon payment of a fee.
[0009] According to a still further feature of the present invention, the device also includes a passenger door switch, configured to toggle the switch device from the first state (activated) to the second state (inactivated) when a passenger door is opened. In such a way, the entertainment system is reset every time a passenger leaves and every succeeding passenger must pay in order to use the entertainment system.
[0010] There is also provided according to the teachings of the present invention a method of providing transport services comprising offereing for hire a device as described above (a motor vehicle with passenger-operated entertainment system) together with a driver, in the manner of a taxi cab.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The invention is herein described, by way of example only, with reference to the accompanying drawings, wherein:
[0012] [0012]FIG. 1 is a partially cut-out top view of a device of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention is of a device that includes a motor vehicle wherein a entertainment system operable by a passenger, as opposed to a driver, is installed in the motor vehicle. Such a motor vehicle is exceptionally suited for use as a taxi-cab. The present invention is also of a method for operating a business of supplying motor vehicles for hire. Since the added value provided by a device of the present invention is so high, a typical customer of taxi cabs will be interested in paying a premium for a business operating according to the teachings of the present invention.
[0014] In FIG. 1 a device 10 of the present invention is depicted, a motor vehicle 12 having a driver position 14 , a passenger position 16 and a passenger door 18 . Device 10 is depicted from a top-view where the roof and trunk cover of motor vehicle 12 have been removed to allow a view into the internal volume of motor vehicle 12 . Device 10 is equipped with a entertainment system 20 (in FIG. 1, a compact disc player having a magazine of twelve compact discs) an entertainment system controller 22 , an activation switch 24 , a payment collection device 26 and a passenger door switch 28 .
[0015] Activation switch 24 has at least two states: a first state where entertainment system 20 and entertainment system controller 22 are activated for operation by the passenger and a second state where entertainment system 20 and entertainment system controller 22 are inactivated for operation by the passenger.
[0016] Payment collection device 26 is similar to prior art payment collection devices as often implemented in pay phones, parking payment devices and the like. Payment collection device 26 is configured to accept payment according to some method. Payment methods known in the art and which are exceptionally suitable for implementation in the present invention include but are not limited to coins, bills, debit cards, credit cards, punch cards and tokens. Payment collection device 26 is configured, upon receipt of sufficient payment, to toggle activation switch 24 from the second state where entertainment system 20 and entertainment system controller 22 are inactivated for operation by the passenger to the first state where entertainment system 20 and entertainment system controller 22 are activated for operation by the passenger.
[0017] In some embodiments of the present invention payment collection device 26 is equipped with a timer 27 . Timer 27 acts as a prior-art time meter and causes collection device 26 to toggle activation switch 24 from the first (activated) state to the second (inactivated) state after a certain period of time, where the period of time is determined by the amount of payment.
[0018] Passenger door switch 28 is connected to payment collection device 26 . Passenger door switch 28 is configured so as to detect if passenger door 18 is opened. If passenger door 18 is opened, passenger door switch 28 sends a signal to payment collection device 26 indicating that payment is insufficient. As a consequence, when passenger door 18 is opened, payment collection device 26 causes activation switch 24 to toggle to the second state where entertainment system 20 and entertainment system controller 22 is activated for operation.
[0019] Operation of device 10 is as follows. A person 30 interested in hiring a taxi cab, hails device 10 . A taxi cab driver 32 sitting in driver position 14 stops device 10 and allows person 30 to board through passenger door 18 and to sit in passenger position 16 . While riding in device 10 , person 30 notices entertainment system controller 22 . Person 30 pays a required sum using payment collection device 26 , causing activation switch 24 to toggle to the first state where entertainment system 20 and entertainment system controller 22 are activated for operation. Person 30 proceeds to use entertainment system controller 22 to select music to be played by entertainment system 20 listen to while riding in device 10 . In such a way person 30 is entertained while riding and the travel with device 10 is a positive and calming experience.
[0020] It is clear to one skilled in the art that entertainment system 20 can be implemented as any one of the devices known in the art and is not limited to a compact device player as depicted in FIG. 1. A partial non-limiting list of devices that can be used to implement the entertainment system of the present invention include audio playback devices such as tape players, compact disk players, mini-disk players and MP3 players. Also useful in implementing the entertainment system of the present invention are audiovisual playback devices such as television receivers, video players, DVD players or interactive audiovisual playback devices (“video games”). Also useful in implementing the entertainment system of the present invention are two-way wireless communication devices such as internet communication devices and electronic mail communication devices. Also useful in implementing the entertainment system of the present invention are geographical location indication devices such as global-positioning system satellite receivers. Also useful in implementing the entertainment system of the present invention are goods/services information devices such as tour guides, telephone/address directories and events directories.
[0021] The use of the device of the present invention allows for an improved method of running a transport service hiring business. In general, transport service hiring businesses are based on providing a motor vehicle and driver for hire. The added value of the entertainment system makes it so that potential passengers prefer to be clients of a taxi cab business providing a device of the present invention for hire instead of a prior art motor vehicle. In addition, such a transport service hiring business has an added source of income when providing a device of the present invention for hire.
[0022] The present invention is not limited to the embodiment described herein but also relates to all kinds of modifications thereof, insofar as they are within the scope of the claims. | A device for reducing-stress during travel is provided, namely a motor vehicle having an entertainment system controlled by the passenger. Also, a method of providing hired transport services is provided where a motor vehicle, such as a taxi cab, is provided having a passenger controlled entertainment system. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This patent application is a continuation-in-part of U.S. application Ser. No. 12/477,190 filed Jun. 3, 2009 which is incorporated by reference herein.
BACKGROUND
[0002] 1. Field
[0003] This patent specification relates to allocating commingled oil production. More particularly, this patent specification relates to methods and systems for allocating commingled oil production in real-time based on measurements made at or near the wellsite.
[0004] 2. Background
[0005] Commingling is a common practice in the oil industry for sharing facilities and equipment to reduce costs. Examples of commingling include: producing two or more reservoirs through a single tubing string, mixing gas/oil/water from several wells in a single separator tank, and using a single pipeline for transporting production from several fields. Crude oils originating from different producing zones, wells, platforms or fields are mixed through commingling operations. See, Hwang R. J., Baskin D. K., Teerman S. C., Allocation of commingled pipeline oils to field production , Organic Geochemistry, vol. 31 pp 1463-1474, 2000 (hereinafter “Hwang et al., 2000”).
[0006] There are several reasons that accurate assessment of the individual field contributions may be desirable or necessary. For example, it may be desirable to have an accurate assessment of the amount of producible oil or gas (See, Peters K. E., Fowler M. G., Application of Petroleum Geochemistry to Exploration and Reservoir Management , Organic Geochemistry, vol. 33, pp 5-36, 2002), and to effectively plan future directions, so as to avoid costly exploration failures (See, International Patent Application No. WO 2008/002345). Another example is the matching of current allocation data with historical data to assess production and plan remedial operations on the well (e.g. pipeline leaks, cement bond failures, non productive zones), to use in a workflow leading to critical management and investment decisions (See, International Patent Application No. WO 2008/002345; and Kaufman R. L., Ahmed A. S., Hempkins W. B., A New Technique for the Analysis of Commingled Oils and its Application to Production Allocation Calculations , Organic Geochemistry vol. 31 pp 1463-1474, 2000 (hereinafter “Kaufmann et al. 1990”)). Finally, petroleum sales value and tax dues often depends on the quality of oil, varying ownership and tax regimes among different zones or neighboring fields (Hwang et al., 2000).
[0007] Back-allocation of commingled production or transport is conventionally being carried out though wireline logging (e.g. Production Logging Tool (PLT), Reservoir Sampling with MDT/DST), and production metering coupled with modeling and simulation. Recently, gas chromatographic analysis coupled with matrix mathematics has been employed to back allocate commingled pipeline crude from multiple contributing fields. In most cases, the use fluid geochemistry is used as an accompaniment to the more traditional techniques mentioned above.
[0008] Several studies discuss the potential of using gas chromatograms as a means of differentiating and allocating hydrocarbon fluids. For discussions of employing gas chromatography analysis to perform zonal and well-to-well allocation, see: Kaufmann et al. 1990, Bazan L. W., The Allocation of Gas Well Production Data using Isotope Analysis , SPE 40032, Gas Technology Symposium, Calgary, Canada, March 1998; Hwang et al 2000; Milkov A. V., Goebel E., Dzou L., Fisher D. A., Kutch A., McCaslin N., Bergman D. F., Compartmentalization and Time - lapse Geochemical Reservoir Surveillance of the Horn Mountain oil field, Deep - water Gulf of Mexico , AAPG Bulletin vol. 91, No 6 pp 847-876, 2007; Wen Z., Zhu D., Tang Y., Li Y., Zhang G., The application of gas chromatography fingerprint technique in calculating oil production allocation of single layer in the commingled well , Chinese Journal of Geochemistry, Vol. 24 No. 3, 2005; McCaffrey M. A., Legarre H. A., Johnson S. J., Using Biomarkers to improve Heavy Oil Reservoir Management: An example from the Cymric field Kern Count, California , AAPG Bulletin, Vol. 80 No. 6 pp 898-913, June 1996; and Nengkoda A, Widojo S, Mandhari M. S., Hinai Z, The Effectiveness of Geochemical Technique for Evaluation of Commingled Reservoir: A Case Study, SPE 109169, Asia Pacific Oil & Gas Conference and Exhibition, Jakarta, Indonesia, November 2007.
[0009] However, such gas chromatography based analyses use relatively complex equipment located in a laboratory in a location remote from the wellsite. Therefore the results are delayed and can be affected by changes in and possible contamination of the sample during transportation. Furthermore, complex gas chromatographic techniques are inherently prone to human operator errors.
[0010] Reyes, M V. Crude Oil Fingerprinting by the Total Scanning Fluorescence Technique , SPE 26943, 1993, Eastern Regional Conference & Exhibition 1993, discusses an application of total scanning fluorescence for crude oil fingerprinting, but does not discuss applying the techniques to the problem of production allocation. The technique relies on the detection of wide range of poly-aromatic hydrocarbon compounds (PAH) as well as the mono-ring aromatics.
[0011] Pasadakis, N., Chamilaki E., Varotsis N., Method measures commingled production, pipeline components , Oil & Gas Journal pp 46-47, Jan. 3, 2000 discusses the use Fourier Transform-Infrared Spectroscopy in identifying volumetric cuts in a three-oil mixture sample. FT-IR analyses use differences in the IR oil spectra in the region of about 3,000 cm −1 . Relative to other methods, analysis requires less time with the quantitative determination absolute error was found to be less than 2%. The analysis seems to have been performed in a lab, and there is no suggestion that the process can be performed real-time or at the wellsite.
[0012] Permanyer A., Rebufa C., Kister J., Reservoir compartmentalization assessment by using FTIR spectroscopy , Journal of Petroleum Science & Engineering vol. 58 pp 464-471, 2007 Permanyer et al (2007), discusses, on the other hand, the application of FT-IR spectroscopy for reservoir compartmentalization assessment and stress the complementary benefits that the techniques provide to conventional GC analysis.
SUMMARY
[0013] According to some embodiments, a method for real-time wellsite production allocation analysis is provided. The method includes making spectroscopic in-situ measurements in the vicinity of a wellsite of a produced fluid from one or more boreholes. The produced fluid includes in a co-mingled state, at least a first fluid component from a first production zone and a second fluid component from a second production zone. An allocation is estimated in real-time for at least the first fluid component in the produced fluid based at least in part on the spectroscopic in-situ measurements.
[0014] The in-situ measurements can be several types, for example: (1) absorption of electromagnetic radiation having wavelengths in the range of ultraviolet, visible and/or infrared light, (2) X-ray fluorescence spectroscopy measurements, (3) electromagnetic scattering spectroscopic measurements such as Raman spectroscopy measurements, (4) NMR spectroscopy measurements, and (5) terahertz time-domain spectroscopy measurements. According to some embodiments, a plurality of spectroscopic measurement techniques are performed and the method determines which of the techniques will be used in the estimation.
[0015] Data from the measurements can be corrected prior to the estimation. For example, techniques such as aligning signals, removing baseline, and removing offset can be carried out. The allocation estimation can include an error-minimization process, a constrained linear least-squares technique and/or a singular value decomposition technique. The first fluid and the second fluid can be produced from different boreholes, or the same borehole. The wellsite can be a marine wellsite or a land wellsite.
[0016] According to some embodiments, a system is also provided for real-time wellsite production allocation analysis.
[0017] As used herein the term “real-time” means performed within a time frame such that a user can take appropriate action so as to alleviate potential problems. In the context of production allocation estimates at the wellsite, “real-time” means a range from a few seconds to several hours, and up to about 1 day from the time the fluid is produced or a sample of the fluid is gathered at the wellsite.
[0018] As used herein the term “in-situ” in the context of measurements of a fluid means the measurement is made of the fluid in the same place or vicinity as the fluid is sampled. This is in contrast to transporting a sample to another location such as a laboratory where a measurement is made.
[0019] By providing real time production allocation analyses trough in-situ wellsite measurements, an increased ability to respond quickly to identified problems can be provided. For example, if it is discovered real time that one zone is shut down, then remedial action can be taken very quickly. Additionally, by providing real time production allocation analyses trough in-situ wellsite measurements problems associated with sample contamination during transportation to a remote laboratory can be alleviated.
[0020] Further features and advantages will become more readily apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The present disclosure is further described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of exemplary embodiments, in which like reference numerals represent similar parts throughout the several views of the drawings, and wherein:
[0022] FIG. 1 is a flow chart showing steps in the allocation method, according to embodiments;
[0023] FIGS. 2 a - 2 c show various components of and operational environments in which systems and methods for real-time wellsite production allocation, according to some embodiments;
[0024] FIG. 3 shows an example of optical spectra from three end-member oils and an associated commingled oil;
[0025] FIG. 4 shows a typical result of X-ray fluorescence spectroscopy analysis of an example oil, according to some embodiments;
[0026] FIG. 5 is a plot showing Raman spectra for a light hydrocarbon sample;
[0027] FIG. 6 shows NMR shift prints for different oil samples, according to some embodiments; and
[0028] FIG. 7 shows examples of Terahertz Domain Spectra.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] The following description provides exemplary embodiments only, and is not intended to limit the scope, applicability, or configuration of the disclosure. Rather, the following description of the exemplary embodiments will provide those skilled in the art with an enabling description for implementing one or more exemplary embodiments. It being understood that various changes may be made in the function and arrangement of elements without departing from the spirit and scope of the invention as set forth in the appended claims.
[0030] Specific details are given in the following description to provide a thorough understanding of the embodiments. However, it will be understood by one of ordinary skill in the art that the embodiments may be practiced without these specific details. For example, systems, processes, and other elements in the invention may be shown as components in block diagram form in order not to obscure the embodiments in unnecessary detail. In other instances, well-known processes, structures, and techniques may be shown without unnecessary detail in order to avoid obscuring the embodiments. Further, like reference numbers and designations in the various drawings indicated like elements.
[0031] Also, it is noted that individual embodiments may be described as a process which is depicted as a flowchart, a flow diagram, a data flow diagram, a structure diagram, or a block diagram. Although a flowchart may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be re-arranged. A process may be terminated when its operations are completed, but could have additional steps not discussed or included in a figure. Furthermore, not all operations in any particularly described process may occur in all embodiments. A process may correspond to a method, a function, a procedure, a subroutine, a subprogram, etc. When a process corresponds to a function, its termination corresponds to a return of the function to the calling function or the main function.
[0032] Furthermore, embodiments of the invention may be implemented, at least in part, either manually or automatically. Manual or automatic implementations may be executed, or at least assisted, through the use of machines, hardware, software, firmware, middleware, microcode, hardware description languages, or any combination thereof. When implemented in software, firmware, middleware or microcode, the program code or code segments to perform the necessary tasks may be stored in a machine readable medium. A processor(s) may perform the necessary tasks.
[0033] According to some embodiments, new techniques such as Near Infrared (NIR) Spectroscopy are used to analyze and differentiate oil samples. From the absorption spectra of both the pure end member and the commingled oil mixture, differentiating chemical component parameters are then selected and are used to quantify their relative contributions in a commingled oil mixture.
[0034] According to some embodiments, methods of back allocating commingled oil production use spectroscopic analysis to differentiate and back allocate commingled oil allocation. According to some embodiments, analysis techniques include: ultraviolet-visible-near infared (UV-Vis-NIR) spectroscopy, X-ray fluorescence spectroscopy, Raman spectroscopy, NMR spectroscopy, and terahertz spectroscopy.
[0035] FIG. 1 is a flow chart showing steps in the allocation method, according to embodiments. In step 110 , the samples are analyzed. Corresponding spectral analysis on the end-members and the commingled oil are collected.
[0036] In step 112 , the analytical results are interpreted. This interpretation leads to the selection of the data that are used. For example, in some cases the total signal is used. In other cases, only part of the signal is used so as to focus on the most differentiating part of the signal reflecting, for instance, a certain fraction of the oils. According to some embodiments, this step is also used to determine which of the available analytical techniques available is the most suitable for the particular application. According to some embodiments, a multivariate analysis technique such as principal component analysis (PCA) is used to differentiate the oils.
[0037] In step 114 , the data is corrected prior to treatment. Baseline removal, signal scale correction and alignment are examples of ways to limit errors/uncertainties, while making the data easily comparable. According to some embodiments, offsets are removed by adding a fictive end-member. According to some other embodiments, the derivative of the signal is used to enhance the features of the signal. According to some embodiments, no correction of the data is used for some applications.
[0038] In step 116 , calculations are performed using constrained linear least-squares, singular value decomposition or any error-minimization process. The system to solve is G·x=d, where G is the n-by-m-matrix constituted of end-members data, x is the n-vector with the proportion of each end-member, and d is the m-vector constituted of the data measured on the commingled oil. Because the system of linear equations is overdetermined (more equations than unknowns, i.e. m>n), different methods based on least-square method can be utilized to solve this system. According to one embodiment, singular value decomposition gives the pseudo-inverse of the matrix G. This method aims to find 3 square matrices U, S and V with G=U·S·V T (where G T is G transposed), so that x=V·S −1 ·U T ·d. According to another embodiment, the normal equations: (1) G T ·G·x=G T d x=(G T ·G) −1 ·G T d are inverted. According to some embodiments, the use of constraints (for example, non-negative, max=100%, sum of the contributions=100%) has been found to lead to a more reliable result.
[0039] FIGS. 2 a - 2 c show various components of and operational environments in which systems and methods for real-time wellsite production allocation, according to some embodiments. FIG. 2 a shows a marine wellsite 210 including a marine platform 214 that receives produced fluid from two wells 220 and 222 . Well 220 includes multiple lateral sections 224 and 226 that drain fluid from two production zones 202 and 204 respectively. Well 220 also drains fluid from production zone 206 . Well 222 drains a different area of production zone 204 . Wellsite 210 includes an in-situ measurement system 250 used to make spectroscopic measurements of fluid produced from wells 220 and 222 and calculate, in real time, production allocations for the produced fluids. End member samples are also preferably collected which can be used in the allocation estimates. According to some embodiments, the end members are sampled using known methods such as shutting in the well, or by downhole sampling.
[0040] FIG. 2 b is a schematic of an in-situ measurement system 250 used to make measurements of the produced fluid at the wellsite and to calculate, in real time, a production allocation, according to some embodiments. Measurement system 250 includes a central processing unit 244 , storage system 242 , spectroscopic measurement module 240 , a user display 246 and a user input system 248 . According to some embodiments, spectroscopic measurement module 240 includes one or more of the following spectroscopy systems: ultraviolet-visible-near infared (UV-Vis-NIR) spectroscopy, X-ray fluorescence spectroscopy, Raman spectroscopy, NMR spectroscopy, and terahertz spectroscopy.
[0041] FIG. 2 c shows a land-based wellsite 212 that receives produced fluid from a well 232 . Well 232 drains fluid from two production zones 208 and 209 . Wellsite 212 includes an in-situ measurement system 250 used to make spectroscopic measurements of fluid produced from well 232 and calculate, in real time, production allocations for the produced fluid.
[0042] Further detail on using Ultraviolet (UV)-Visible-Near Infrared (NIR) Spectroscopy will now be provided, according to some embodiments. This spectroscopy technique has been proven highly reliable in characterizing hydrocarbon fluids in oilfield settings. For example, optical spectroscopy methods are used in connection with the current Modular Dynamic Tester (MDT) tools from Schlumberger. Absorbance measurements on both commingled and pure end member oil samples (which can be collected either from well head or downhole sampling). The method relies on the fact that the NIR spectra of the commingled oils are a linear combination of the NIR spectra of the end-member. So, having the spectra of the end-member and the commingled oils allow to calculate easily the contribution of each end-member in the commingled production using a least-square method, singular value decomposition or a minimization process.
[0043] FIG. 3 shows an example of optical spectra from three end-member oils and an associated commingled oil. The spectra of the three end-member oils, Oil#1, Oil#2 and Oil#3 are shown with traces 310 , 312 and 314 respectively. The spectra of the associated commingled oil is shown with trace 316 . As can be seen from FIG. 3 , the spectra of the mixture fits between the three end-members' spectra. It has been found that results from the calculation using the whole spectra without the derivative gives an accurate result. For example, an allocation of 9.7 vol % of Oil#1, 60.4 vol % of Oil#2 and 29.9 vol % of Oil#3 was calculated using a least squares method, where the actual proportions where 10 vol %, 60 vol % and 30 vol %, respectively.
[0044] According to some embodiments, the techniques described in further detail below with respect to FIGS. 4-7 can also be used as an input to the process and replace the NIR spectra. According to some embodiments, if several spectroscopic techniques are available, the differentiation step of the process can also be used to determine the best analytical procedure to use depending on practical and economical aspects (differentiation of the oils but also applicability, accuracy, price, availability). Depending on the signal or the data used, the correction step may involve different techniques to align the signal, remove the baseline or any offset.
[0045] According to some embodiments X-ray fluorescence spectroscopy is used for making in-situ wellsite measurements on which real-time wellsite production allocation is based. X-ray fluorescence spectroscopy (XRF) is a widely used technique for nondestructive analysis of bulk samples. XRF can be used to rapidly identify most elements with an atomic number equal to or greater than Sodium. A crude oil usually contains Sulfide, Vanadium, Iron and Nickel in molecules. According to some embodiments, in situ wellsite XRF measurements are used to calculate fractions of elements such as Sulfide, Vanadium, Iron and Nickel. The fractions are then used for a production allocation. FIG. 4 shows a typical result of X-ray fluorescence spectroscopy analysis of an example oil, according to some embodiments. The XRF trace shows spectral lines 410 , 412 , 414 , 416 and 418 for Sulfur, Vanadium, Iron, Nickel, and Tungsten respectively. For further detail on the traces shown in FIG. 4 , see N. Ojeda, E. D. Greaves, J. Alvarado and L. Sajo-Bohus, Determination of V, Fe, Ni and S in Petroleum Crude Oil by Total Reflection X-ray Fluorescence, Spectrochimica Acta Vol 48B No. 2, pp 247-253 1993, and Energy Dispersive X-ray Spectroscopy (EDS), both of which are incorporated by reference herein. According to some embodiments, the XRF analysis is carried out in a similar manner to known GC data analysis techniques for variations on specific compound content. According to some embodiments, a field portable energy-dispersive x-ray analyzer is used due its relatively simple design and the ability to used miniature x-ray tubes or gamma sources.
[0046] According to some embodiments Raman spectroscopy is used for making in-situ wellsite measurements on which real-time wellsite production allocation based. Raman spectroscopy is commonly used in chemistry, since vibrational information is specific for the chemical bonds in molecules. It therefore provides a fingerprint by which the molecule can be identified. FIG. 5 is a plot showing Raman spectra for a light hydrocarbon sample. Plot 510 shows Raman data for a hydrocarbon sample. Similar to UV-Vis-NIR data, spectral features are unique for different oil samples and are used for back allocation, according to some embodiments. According to some embodiments, Raman microspectroscopy is used for in situ wellsite analysis for allocation. Raman spectroscopy offers some advantages for microscopic analysis. Since it is a scattering technique, specimens do not need to be fixed or sectioned.
[0047] According to some embodiments nuclear magnetic resonance (NMR) chemical shift analysis is used for making in-situ wellsite measurements on which real-time wellsite production allocation based. The chemical shift is of great importance for NMR spectroscopy, a technique to explore molecular properties by looking at nuclear magnetic resonance phenomena. Nuclear magnetic resonance spectroscopy analyzes the magnetic properties of certain atomic nuclei to determine different electronic local environments of hydrogen, carbon, or other atoms in an organic compound or other compound. This is used to help determine the structure of the compound. FIG. 6 shows NMR shift prints for different oil samples, according to some embodiments. 1H NMR spectra 610 , 612 and 614 are shown for three different oil samples Diesel #1, Biodiesel and Diesel #2, respectively. The spectra are shown both separately and superimposed. Similar to the other analyses described here, according to some embodiments, in situ wellsite NMR chemical shift analysis is employed to calculate production allocation. For further detail on NMR spectroscopy, see: Oliviera et, Talanta 69 (2006) 1278-1284 and Gnothe, J. Am. Oil Chem. Soc 78, 1025-1028, 2001, which is incorporated herein by reference.
[0048] According to some embodiments terahertz spectroscopy is used for making in-situ wellsite measurements on which real-time wellsite production allocation based. Terahertz time-domain spectroscopy (THz-TDS) is a spectroscopic technique where a special generation and detection scheme is used to probe material properties with short pulses of terahertz radiation. The generation and detection scheme is sensitive to the sample material's effect on both the amplitude and the phase of the terahertz radiation. In this respect, the technique can provide more information than conventional Fourier-transform spectroscopy that is only sensitive to the amplitude. FIG. 7 shows examples of Terahertz Domain Spectra. In particular, traces 710 , 712 and 714 are traces for petrol, linseed oil and black oil respectively. For further details of THz-TDS, see: Fukunaga K. Terahertz Spectral Database 2008—Journal of National Institute of Information and Communication Technology Vol. 55 No. 1, 2008, which is incorporated herein by reference.
[0049] Whereas many alterations and modifications of the present disclosure will no doubt become apparent to a person of ordinary skill in the art after having read the foregoing description, it is to be understood that the particular embodiments shown and described by way of illustration are in no way intended to be considered limiting. Further, the disclosure has been described with reference to particular preferred embodiments, but variations within the spirit and scope of the disclosure will occur to those skilled in the art. It is noted that the foregoing examples have been provided merely for the purpose of explanation and are in no way to be construed as limiting of the present disclosure. While the present disclosure has been described with reference to exemplary embodiments, it is understood that the words, which have been used herein, are words of description and illustration, rather than words of limitation. Changes may be made, within the purview of the appended claims, as presently stated and as amended, without departing from the scope and spirit of the present disclosure in its aspects. Although the present disclosure has been described herein with reference to particular means, materials and embodiments, the present disclosure is not intended to be limited to the particulars disclosed herein; rather, the present disclosure extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims. | Methods and related systems are described for real-time wellsite production allocation analysis. Spectroscopic in-situ measurements are made in the vicinity of a wellsite of a produced fluid from one or more boreholes. The produced fluid includes in a co-mingled state, at least a first fluid component from a first production zone and a second fluid component from a second production zone. An allocation is estimated in real-time for at least the first fluid component in the produced fluid based at least in part on the spectroscopic in-situ measurements. The in-situ measurements can be several types, for example: (1) absorption of electromagnetic radiation having wavelengths in the range of ultraviolet, visible and/or infrared light, (2) X-ray fluorescence spectroscopy measurements, (3) electromagnetic scattering spectroscopic measurements such as Raman spectroscopy measurements, (4) NMR spectroscopy measurements, and (5) terahertz time-domain spectroscopy measurements. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application contains some common subject matter with U.S. Provisional Application Serial No. 60/265,444. As to this common subject matter, Applicants claim benefit of the provisional patent application filed on Jan. 31, 2001, Serial No. 60/265,444.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Drilling rigs use blowout preventers (BOPs) to shut in a well during emergencies and for other purposes. The BOP operating system needs to be reliable in order to protect lives, the environment, and property. This invention relates to an improved BOP operating system and a quick dump valve. The quick dump valve includes a shuttle that has some structural similarity to shuttle valves used for control functions in prior art BOP operating systems. Specifically, the quick dump valve has some structural similarities to the Low Interflow Hydraulic Shuttle Valve which is the subject of a pending U.S. patent application Ser. No. 09/452,594 filed on Dec. 1, 1999 and a pending U.S. patent application Ser. No. 09/653,415 for a Pressure Biased Shuttle Valve filed on Sep. 1, 2000, both of which are incorporated herein by reference. Gilmore Valve Co. is the owner of these two pending U.S. Patent Applications, the present patent application for BOP Operating System with Quick Dump Valve and other U.S. patents for shuttle valves including U.S. Pat. Nos. 3,533,431 and 4,253,481. However, the present invention is structurally distinct from these prior art shuttle valves and it performs a different function as discussed below.
[0004] 2. Description of the Prior Art
[0005] Subsea wellhead systems are often relied upon during deep-water exploration for oil and natural gas. The subsea wellhead system includes a stack of BOPs. Annular BOPs are actuated on a routine basis to snub or otherwise control pressure during normal drilling operations. Other blowout preventers, such as blind rams, pipe rams, and shear rams will also be included in the stack on the subsea wellhead. When these types of rams are actuated, operations in the well cease in order to control pressure or some other anomaly. Blind rams, pipe rams, shear rams and annular preventers are periodically functioned and tested to make sure that they are operational.
[0006] BOPs are tested periodically to ensure that they will function in emergencies and in other situations. Prior art subsea BOP operating systems include control pods, the lower marine riser package (LMRP), the BOP stack and interconnecting hoses and pipes. From time to time it may be necessary to perform an emergency disconnect of the LMRP from the BOP stack, for example, if a drill ship drifts off station or if a storm approaches. If it is necessary to make an emergency disconnect of the LMRP from the BOP stack, it will be necessary to close the shear rams. During the closing sequence, hydraulic fluid is forced through pipes or hose, a shuttle valve and additional segments of pipes or hose before it finally reaches the directional control valve vent port on the control pod where it is vented to the ocean. This circuitous hydraulic vent path results in a high differential pressure, which decreases flow of control fluid through the close side of the operating system. The decreased flow consumes valuable seconds, and as such, increases the time required to close the shear rams and disconnect the LMRP from the BOP stack. In prior art BOP operating systems, pilot operated check valves or conventional sub-plate mounted (SPM) poppet valves were used to vent this fluid during the closing sequence. These prior art vent devices rely upon springs or pilot pressure to operate properly.
[0007] The present dump valve for use in the improved BOP operating system utilizes a ported shuttle that automatically shifts with the direction of hydraulic pressure to either expose or seal the vent port in the valve. The present dump valve has two positions—vent and open. It has several advantages over the prior art due to its location in the BOP operating system and its design. These advantages occur when the valve is in both the vent and the open positions as discussed below. The present dump valve is a much simpler design than the prior art pilot operated check valves and conventional SPM valves.
[0008] The present dump valve and improved BOP operating system are designed to reduce hydraulic shock and vibration, to reduce the incidence of hose collapse on both the close side and the open side of the system, to facilitate installation and maintenance, and to shorten the emergency disconnect sequence of the LMRP from the BOP stack. In some prior art systems, hydraulic shock and vibration would sometimes accompany the closing function.
[0009] In the improved BOP operating system the dump valve of the present invention is located at or near the open port of the BOP. During the closing sequence in the improved BOP operating system, the present dump valve is shifted to the vent position. In this position fluid is vented from the BOP operating system. When it is time to open the shear rams, fluid flow reverses through the dump valve and it moves to the open position. In the open position, the vent is closed allowing fluid to move through the open port into the BOP to open the rams.
[0010] Some BOP hoses may collapse in deep water when subjected to high velocity flows of hydraulic fluid resulting from functioning of the BOPs with large capacity operators. Hose collapse is, of course, undesirable. The present dump valve and the improved BOP operating system are designed to reduce flow velocities in the control system, and thereby reduce the incidence of BOP control hose collapse. In the improved BOP operating system, the dump valve is positioned at or near the open port on the BOP to vent fluid from the system during the closing sequence. Because the dump valve is located at or near the open port on the Ram's BOP, this high velocity fluid is vented and does not pass through the open side hose. The control hoses on the open side of the BOP will, therefore, be less prone to collapse because they are no longer exposed to the hydraulic shock and negative pressure waves caused by high velocity flow of fluid when the BOP rams are being closed.
[0011] When the rams are being opened, the dump valve also acts as a dampener to reduce the incidence of hose collapse on the close side of the operating system. In a preferred embodiment, when the rams are functioned open, fluid passing through the dump valve is restricted because the orifice through the dump valve is smaller than the inside diameter of the hose leading to and exiting from the dump valve. This flow restrictor will effectively slow down the velocity of the fluid entering the BOP rams. In turn, the velocity of the exhausting fluid from the close side will be reduced to a rate that reduces hydraulic shock and therefore reduces the incidence of hose collapse. In some prior art BOP operating systems, it may take as much as 20 seconds to close and open the rams. The improved BOP operating system with quick dump valve should allow the rams to close in approximately 5 to 15 seconds; however, it may take more than 30 seconds for the rams to open.
[0012] Maintenance on prior art BOP operating systems is sometimes lengthy and expensive. The present dump valve is smaller and lighter than conventional SPM valves or pilot operated check valves, which will facilitate valve installation reliability and maintenance.
[0013] The improved BOP operating system with quick dump valve should reduce the amount of time it takes to make an emergency disconnect of the LMRP from the BOP stack. In prior art BOP operating systems when it was necessary to close the rams, fluid was forced through a length of hydraulic hose, a shuttle valve and additional segments of tubing or hose before it finally reached the directional control valve vent port on the control pod. This circuitous hydraulic vent path on the close side of prior art operating systems results in a high differential pressure, which decreases flow of control fluid when the rams are being closed. The decreased flow consumes valuable seconds and, as such, increases the time required to close the rams and disconnect the LMRP from the BOP stack. Positioning the quick dump valve at or near the BOP Ram's open port will substantially shorten the hydraulic vent path and reduce the differential pressure. All of these features will reduce the amount of time required to close the BOP rams during an emergency and thus speed up the disconnect of the LMRP from the BOP stack.
SUMMARY OF THE INVENTION
[0014] The quick dump valve uses a ported shuttle design that shifts to either expose or seal off the vent port in the valve. When the BOP is being closed, the shuttle moves to the vent position allowing fluid to be vented from the improved operating system. This vent function which is located at or near the BOP prevents high velocity fluid from passing through the open side hose thus reducing the incidence of hydraulic shock, vibration and hose collapse.
[0015] When the BOP is being opened, the shuttle in the dump valve moves to the open position allowing fluid to pass through the dump valve and into the BOP. A flow restrictor is positioned in the shuttle, which acts as a dampener to reduce hydraulic shock, vibration and the incidence of hose collapse on the close side of the BOP rams. While the BOP is being opened, it is important that the shuttle achieve a good seal to prevent fluid from escaping to vent. The diameter on the supply side of the shuttle is larger than the diameter on the BOP side which results in more force being applied to the seals to prevent unwanted fluid from escaping to vent while the BOP is being opened.
[0016] In some situations, it is desirable to prevent fluid from flowing to supply when fluid is escaping to vent while the BOP is being opened. In the first alternative embodiment, a ball check valve, is positioned in the shuttle to block fluid flow from the BOP to supply when the dump valve is in the vent position. In the first alternative embodiment, the diameter on the supply side of the shuttle is larger than the diameter on the BOP side, which results in more force being applied to the seals to prevent unwanted fluid from escaping to vent while the BOP is being opened.
[0017] In the second alternative embodiment, a ball check valve is positioned in the shuttle to block fluid flow from the BOP to supply when the dump valve is in the vent position. In the second alternative embodiment, the diameter on the supply side of the shuttle is the same diameter as in the BOP side. The cracking pressure of the check valve results in the differential pressure and force required to energize the metal to metal face seal. Differential area was utilized to accomplish this in the alternative and first alternative embodiment.
[0018] In the third alternative embodiment, there is no internal check valve and the diameter on the supply side of the shuttle is the same diameter as on the BOP side. In the third alternative embodiment soft seals are used on both sides of the shuttle to achieve a seal. These seals may be located in either the shuttle or adapters.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] In order to more fully understand the aforementioned features, advantages and objects of the present invention, a more detailed description of the invention is provided in the appended drawings. It is noted, however, that the appended drawings illustrate only a typical embodiment of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments. Reference the appended drawings, wherein:
[0020] [0020]FIG. 1 is a hydraulic circuit showing the BOP rams in the closed position and the quick dump valve of the present invention in the vent position.
[0021] [0021]FIG. 2 is a hydraulic circuit showing the BOP rams in the open position and the dump valve of the present invention in the open position.
[0022] [0022]FIG. 3 is a perspective view of a preferred embodiment of the quick dump valve of the present invention.
[0023] [0023]FIG. 4 is a section view of the quick dump valve of FIG. 3 in the vent position with flow arrows showing the direction of fluid flow from the BOP through the dump valve and out the vent.
[0024] [0024]FIG. 5 is a section view of the dump valve of FIG. 3 in the open position with flow arrows showing the flow of fluid from supply through the dump valve through the BOP.
[0025] [0025]FIG. 6 is an enlargement of the metal to metal seal 6 shown in FIG. 5.
[0026] [0026]FIG. 7 is an alternative embodiment of the dump valve of the present invention including a ball check valve. This ball check valve eliminates all return flow through the supply side hydraulics during venting. The supply side of the shuttle has a larger diameter than the BOP side.
[0027] [0027]FIG. 8 is a second alternative embodiment of the dump valve of the present invention including a ball check valve. Both sides of the shuttle are the same diameter. The spring in the ball check valve creates a differential pressure across the shuttle and the force necessary to energize the metal seal.
[0028] [0028]FIG. 9 is a third alternative embodiment of the dump valve of the present invention having soft seals. Both sides of the shuttle have approximately the same diameter. Axial force is not required to energize these seals as in the previously described embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0029] The quick dump valve uses a ported shuttle design that shifts to either expose or seal off the vent port in the valve. When the BOP is being closed, the shuttle moves to the vent position, allowing fluid to be vented from the improved operating system. This vent function which is located at or near the BOP prevents high velocity fluid from passing through the open side hose, thus reducing the incidence of hydraulic shock, vibration and hose collapse.
[0030] Control pods, attached to the LMRP, direct hydraulic operating fluid to all the functions on the BOP and LMRP. The LMRP is positioned on the BOP stack. BOP control systems have two (2) redundant hydraulic systems commonly referred to in the industry as blue and yellow pods.
[0031] [0031]FIG. 1 is a hydraulic circuit diagram of a portion of the improved BOP operating system with the quick dump valve 10 positioned at or near the open port on the BOP. In FIG. 1, fluid flows from the yellow pod hydraulic supply through valves on the control pod through the shuttle valve generally identified by the numeral 12 through hoses 14 as identified by the flow arrow to the close port 16 in the BOP assembly 18 . This side of the operating system is referred to as the close side of the system because fluid flows into this side when the rams are functioned close. A piston 20 divides the BOP assembly 18 into a close chamber 22 and an open chamber 24 . A rod 26 extends from the piston 20 to the BOP rams.
[0032] The open chamber 24 connects to an open port 28 , which connects to a short conduit 30 , which connects to the quick dump valve 10 . Alternatively, the dump valve 10 can be directly connected to the open port 28 . Additional hoses 32 connect the dump valve 10 to one of three ports on the shuttle valve generally identified by the numeral 35 . The other two ports on the shuttle valve 35 connect to the blue pod and the yellow pod hydraulic supply as well known to those skilled in the art. When hydraulic fluid is directed from either the blue or yellow pods, the shuttle valve 35 seals off the path of the non-energized hydraulic system and routes the fluid to the BOP.
[0033] In order to open the rams as shown in FIG. 1, high pressure fluid exits from a pod, in this case the yellow pod, and moves through the shuttle valve 12 , the conduit 14 , the close port 16 and enters the close chamber 22 thus moving the piston 20 to the left-hand side of the BOP assembly 18 as shown in FIG. 1. As high-pressure fluid enters the close chamber 22 , fluid must exit the open chamber 24 . As the piston 20 moves to the closed position, the fluid in the open chamber 24 moves into the dump valve 10 , shifting it to the vent position (FIG. 4) thus venting the fluid to sea. During the closing process fluid is being vented through the dump valve 10 . After the BOP is closed, the pressure in the close chamber 24 equalizes and no further fluid is vented. However, the shuttle 36 in the dump valve 10 remains in the vent position until the BOP is opened. During vent flow the majority of the fluid exhausts through the vent port 44 of the dump valve 10 . A small portion of fluid, between 10 to 20%, flows through the flow restrictor passage 82 in the shuttle, and back through the shuttle valves 35 where it exhausts to the ocean (via components not shown in FIG. 1). Because the flow rate back through the shuttle valves is greatly reduced, energy which can trigger vibration or oscillation is also low. As an alternative configuration a check valve can be employed in the inside of the dump valve 10 to totally eliminate this flow.
[0034] The BOP assembly 18 operates with fluids that are flowing as fast as 320 gpm at pressures of 1500 to 3000 psi. These high pressures and high flow rates sometimes create hydraulic shock and vibration in the BOP operating system generally shown in FIG. 1. Prior art SPM's and pilot operated check valves are sometimes installed in “Tee” connections located near the BOP on both the opening and closing sides. These valves are actuated by external means to vent return flow to the ocean. This is similar to the function performed by the dump valve 10 , however, the dump valve 10 is a much simpler device containing fewer moving parts, and therefore improved reliability. Also due to the greater size of the prior art SPM's and pilot operated check valves, they must be mounted in the BOP frame or other structure which is a greater distance away than the location of the present dump valve 10 , increasing the resistance to vent flow. In the improved operating system of FIG. 1, the dump valve 10 is installed at the open port 28 or in close proximity thereto by conduit 30 . When the BOP is closed as shown in FIG. 1, the dump valve 10 is in the vent position allowing fluid from the close chamber 24 to vent from the operating system. This reduces hydraulic shock and vibration and the incident of hose collapse on the open side of the operating system. The improved BOP operating system of FIG. 1 with the quick dump valve 10 allows the BOP rams to be closed more quickly than most prior art systems because the fluid from the open chamber 24 is vented from the system at or near the open port 28 . Some prior art systems took up to 20 seconds to close. The present invention should be able to close in 5-15 seconds.
[0035] The dump valve 10 is smaller and lighter than conventional SPM or pilot operated check valves which should facilitate installation and maintenance on the improved BOP operating system. The dump valve 10 is a simpler more reliable design than prior art SPM and pilot operated check valves.
[0036] [0036]FIG. 2 is a partial hydraulic circuit diagram portion of the improved BOP operating system. In order to open the BOP rams, high pressure fluid flows from the blue pod hydraulic supply through the shuttle valve 35 through the piping and/or hose 32 and enters the dump valve 10 . The velocity of this fluid causes the dump valve to move from the vent position of FIG. 4 to the open position of FIG. 5. In the open position, fluid passes through a flow restrictor in the dump valve 10 to the open port 28 and into the open chamber 24 . This causes the piston 20 to move towards the right-hand side of the drawing, which retracts the rod 26 thus opening the BOP. As the piston 20 moves from the full closed position of FIG. 1 to the full open position, fluid in the closed chamber 22 moves through the close port 16 and the hose 14 on the close side of the BOP operating system. In order to dampen hydraulic shock, the present invention will take more than 30 seconds to open, but this is acceptable because the open function does not occur under emergency conditions.
[0037] [0037]FIG. 3 is a perspective view of the dump valve 10 , which is supported by brackets 38 and 40 . The dump valve 10 has a supply port 34 , which connects to the hose 32 on the open side of the operating system. A BOP port 42 connects to the hose 30 or directly to the open port 28 . A vent port 44 is connected to conduits, which are vented to sea.
[0038] [0038]FIG. 4 is a section view of the dump valve 10 in the vent position. In this position, fluid moves from the open chamber 24 , through the valve 10 and is vented to sea. When the shuttle 36 is in the vent position fluid flows through the dump valve 10 as shown by the flow arrows in the drawing. Fluid enters the dump valve 10 through the BOP port 42 and exits through the vent port 44 as shown by the flow arrows. The body 46 has a longitudinal bore that is threaded to receive the supply adapter 48 and the BOP adapter 50 . An O-ring 52 is positioned in channel 51 and between the body 46 and the BOP adapter 50 thus creating a seal between these two components. Another O-ring 54 is positioned between the supply adapter 48 and the body 46 to create a seal between these two components. The body also has a transverse bore which forms the vent port 44 and which connects to the longitudinal bore.
[0039] The shuttle 36 has a central radial collar 56 and opposing end portions 58 and 60 . The diameter, identified by the arrow A, of the end portion 58 , is larger than the diameter, identified by the arrow B, of the end portion 60 . This step in diameter produces greater area on the supply end 58 . When the shuttle 36 is in the open position shown in FIG. 5, and the BOP piston 20 has reached full travel stopping flow and equalizing the pressure across the shuttle, a difference in force is created by this greater area on the supply end holding the shuttle in the open position and effecting a metal to metal seal as shown in FIGS. 5 and 6. The area of the end portion 58 should be larger than the area of the end portion 60 to ensure a good seal. Applicants have determined that a good seal can be achieved if the area of end portion 58 is approximately 1.5 times greater than the area of the end portion 60 ; however other area ratios may be suitable, provided that a good seal is achieved when the valve 10 is in the open position as shown in FIGS. 5 and 6.
[0040] The end portion 58 has an O-ring groove 61 formed therein. An O-ring 62 and a first backup ring 64 and a second backup ring 66 are positioned in the O-ring groove 61 . The O-ring can be formed from conventional materials such as nitrile rubber provided that they will meet operational temperatures in the subsea environment. The backup rings are typically produced from polymers such as Delrin® or Teflon®.
[0041] The end portion 60 includes a plurality of apertures 68 , 70 , 72 , 74 and others not shown. These transverse apertures connect with a bore 76 to allow fluids to flow through the dump valve 10 to the vent port 44 as shown by the flow arrows in FIG. 4. Fluids flow from the open chamber 24 to the open port 28 , through the conduit 30 to the BOP port 42 through the bore 76 , and the plurality of apertures 68 , 70 , 72 and 74 to the vent port 44 and hence to sea.
[0042] A bore 80 is formed in the longitudinal axis of the end portion 58 of the shuttle 36 . A flow restrictor 82 allows fluid communication between the bore 80 and the bore 76 better seen in FIG. 5.
[0043] [0043]FIG. 5 is a section view of the dump valve 10 in the open position allowing fluid to flow through the dump valve 10 to the open chamber 24 of the BOP assembly 18 as shown by the flow arrows. Fluid enters the supply port 34 , passes through the bore 80 , the flow restrictor 82 , the bore 76 , the BOP port 42 and thereafter flows into the open chamber 24 in the BOP assembly 18 as better seen in FIG. 1. For a one inch dump valve, applicants have determined that a flow restrictor with an I.D. of from 0.156 to 0.375 inches is suitable. The 0.156 inch I.D. flow restrictor allows a flow rate of 20 gpm at 1500 psi differential pressure.
[0044] The shuttle 36 is typically located in one of two positions. The vent position is shown in FIG. 4 and the open position is shown in FIG. 5. When the shuttle is in the vent position of FIG. 4 the shoulder 55 abuts the supply adapter 48 . When the shuttle 36 is in the open position of FIG. 5, the end portion 58 of shuttle 36 is in sealing engagement with the supply adapter 48 and the end portion 60 of shuttle 36 is in sealing engagement with the BOP adapter 50 . Various types of seals could be used to accomplish a seal between the end portion 58 and the adapter 48 and the end portion 60 and the adapter 50 , including metal to metal seals or soft seals. It is important that the seals utilized withstand the high pressures and flow velocities encountered in this application. It is important that the shuttle 36 achieve a seal with the adapter 48 and adapter 50 when the shuttle is in the open position as shown in FIG. 5. Otherwise hydraulic fluid will bleed out the vent and slow down or thwart efforts to open the BOP rams. Likewise a good seal between the shuttle 36 and the adapter 48 and adapter 50 is important when the valve 10 is in the vent position.
[0045] [0045]FIG. 6 is an enlarged section view of the end portion 60 of the shuttle 36 and a portion of the BOP adapter 50 using metal to metal seals. Again, other types of seals may be suitable for this valve and the selection of metal to metal seals is a manufacturing choice. The shuttle 36 includes a circumfrential flange 56 with a shoulder 57 which is a part of end portion 60 . An outwardly tapered metal sealing surface 100 is formed on the shoulder 57 . Applicants believe that a taper of approximately 8° is optimum for this application. However, other tapers in the range of 5-15° may also be effective so long as they create a coining effect on the metal valve seat 102 of the supply adapter 50 . The only requirement for the angle of taper is to achieve coining and therefore sealing between the sealing surface 100 and the metal valve seat 102 . FIG. 6 shows the sealing surfaces after the dump valve 10 has been manufactured but before any coining has occurred.
[0046] The adapter 50 includes a chamfer 104 recessed behind the metal valve seat 102 to thereby create an obtuse metal point 106 that will contact the tapered metal sealing surface 100 on the flange 56 of the shuttle 36 . Coining occurs when the shuttle moves back and forth from the vent to the open positions. As the shuttle moves back and forth, the tapered metal sealing surface 100 impacts the point 106 and metal it displaced from the point 106 to the chamfer 104 . This displacement of metal is referred to as coining.
[0047] [0047]FIG. 6 shows the metal valve seat 102 and the metal sealing surface 100 on the end portion 60 of shuttle 36 before any coining has occurred. Applicant uses a chamfer with a 15° angle and a 0.015 inch radius. However, the exact size and depth of the chamfer are not particularly critical because this is merely a recess or space into which displaced metal will move due to progressive coining. A step back shoulder or other recess in lieu of the chamfer may also prove effective provided that there is room to receive the displaced metal from the point 106 such that it does not interfere with movement of the shuttle 36 .
[0048] After the shuttle 36 has moved back and forth on several occasions, the metal sealing surface 100 of the shuttle 36 impacts the point 106 of the metal valve seat 102 , and a portion of the metal in the point 106 is displaced into the chamfer 104 . A metal to metal seal is therefore achieved between the metal valve seat 102 and the outwardly tapered metal sealing surface 100 of the flange 56 on the shuttle 36 .
[0049] [0049]FIG. 7 is an alternative embodiment of the dump valve in the vent position. The valve 210 is constructed in a manner similar to the valve of FIG. 4 and includes a body 246 defining a vent port 244 , a BOP adapter 250 defining a BOP port 242 and a supply adapter 248 defining a supply port 234 . The shuttle 236 includes an end portion 258 and opposite end portion 260 . The shuttle 236 includes a bore 280 having a shoulder 294 . A ball check valve assembly 283 includes a ball 284 that is held in place against a valve seat 288 by spring 286 which rests against the shoulder 294 . The valve seat 288 threadably engages the shuttle at shuttle threads 292 and seat threads 290 .
[0050] When the valve 210 is in vent position, as is shown by the flow arrows in FIG. 7, the spring 286 holds the ball 284 against the valve seat 288 to prevent fluid flow to the supply port 234 . The end portion 258 has an O-ring groove 61 formed therein. An O-ring 62 is positioned in the O-ring groove 61 creating a seal between the adapter 248 and the shuttle 236 . Thus, when the valve 210 is in the vent position as shown, in FIG. 7 no fluid flows to supply because of the seal achieved by the O-ring 62 with adapter 248 and the ball check valve assembly 283 . However, when the valve 210 is in the open position, fluid pressure acting on the ball overcomes the spring force moving the ball away from the seal and allowing fluid to flow from supply to the BOP. The O-ring 62 makes a seal with adapter 248 to prevent fluid from escaping to vent when the valve is in the open position. The metal valve seat 102 and the metal sealing surface 100 on end portion 260 achieve a seal between the shuttle 236 and the adapter 250 , to likewise prevent fluid from escaping to vent when the valve is in the open position The diameter of the end portion 258 is larger than the diameter of end portion 260 . This step in diameter produces greater area on the supply end 258 . When the shuttle 236 is in the open position, and the BOP piston 20 has reached full travel stopping flow and equalizing the pressure across the shuttle, a difference in force is created by this greater area on the supply end portion 258 holding the shuttle in the open position. Applicants have determined that a metal to metal seal can be achieved if the area of end portion 258 is approximately 1.5 times greater than the area of the end portion 260 ; however, other area ratios maybe suitable, provided that a good seal is achieved when the valve is in the open position.
[0051] [0051]FIG. 8 illustrates a second alternative embodiment of the dump valve which includes the ball check assembly 283 , and including supply, vent and BOP ports of essentially the equal diameter. The body 346 defines the vent port 344 , and the adapters 350 and 394 define the BOP port 342 and the supply port 334 respectively. The ball check valve assembly 283 includes a ball 384 , a spring 386 and a valve seat 388 .
[0052] The metal valve seat 102 and the sealing surface 100 on the end portion 360 of shuttle 336 achieve a seal between the shuttle 336 and the adapter 350 , to prevent fluid from escaping to vent when the valve is in the open position.
[0053] The shuttle 336 has end portion 358 and opposite end portion 360 of approximately equal diameters. When in the open position, the spring 386 in the ball check valve results in the pressure on the supply side of the shuttle 336 to be greater than the pressure on the BOP side of the shuttle, resulting in a force pushing the shuttle 336 against the BOP adapter 350 , and effecting a seal between the tapered sealing surface 100 and the metal valve seat 102 .
[0054] [0054]FIG. 9 is a third alternative embodiment of the dump valve. The valve 410 is constructed in the same manner as the valve of FIGS. 3 - 5 , with the exception of the shuttle, the relative port diameters and the soft seal assembly. The shuttle 436 has end portion 458 and opposing end portion 460 . End portion 458 engages supply adapter 448 . End portion 460 engages BOP adapter 450 . Adapters 448 and 450 are of equal size and shape. In FIG. 9 the metal to metal seal illustrated in FIG. 6 is replaced by a soft seal created by O-ring 96 which is located in channel 98 of the shuttle 436 . Further, the diameters of the supply port 434 , vent port 444 and BOP port 442 are all the same diameter, which may be advantageous for particular applications. The type of seals employed do not require axial force to be energized as in the previous embodiments discussed.
[0055] The shuttle 436 has end portion 458 and opposing end portion 460 , both of which are of approximately equal diameter. Thus, the forces exerted by the fluid on the shuttle 436 are balanced when the shuttle 436 is in the vent position of FIG. 9 and the open position, not shown. As previously discussed, the type of seal is a matter of manufacturing convenience. The valve 410 uses two soft seals, i.e., the O-ring 96 and the O-ring 62 . As a matter of manufacturing choice, other types of seals could also be employed. A check valve could also be utilized in this concept if desired.
[0056] Having described the invention in detail, those skilled in the art will appreciate that modifications may be made of the invention without departing from its spirit and scope. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments described. Rather, it is intended that the scope of the invention be determined by the appended claims and their equivalents. | In some prior art Blowout Preventer (BOP) operating systems, high velocity fluid flows and low differential pressures induced vibration in the system. This vibration may result in collapse and failure of hydraulic hoses in the system. A quick dump valve has been added at or near the open port on the BOP assembly to reduce vibration and other problems. The dump valve has a vent position and an open position. Several alternative embodiments add a ball check valve assembly to the shuttle in the quick dump valve. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus for positioning a sensor in an operative location relative to a related part, and more particularly to a marine propulsion device including an internal combustion engine incorporating a crankshaft mounted timing ring, and a sensor operable to provide crankshaft angular position information to time the ignition spark of the internal combustion engine.
2. Description of the Prior Art
The prior art includes sensor devices and arrangements for positioning such sensors devices which are individually operable to time the spark sequence of an internal combustion engine. Examples of such sensor devices and positioning arrangements are shown in U.S. Pat. No. 4,406,272 to Kiess et al; U.S. Pat. No. 4,373,486 to Nicholas et al U.S. Pat. No. 4,508,092 to Kiess et al; and U.S. Pat. No. 4,635,353 and U.S. Pat. No. 4,677,946 to Tamange.
Marine propulsion devices such as stern drive units have employed an electronic ignition system including a sensor consisting of a molded electrical connector and sensing element assembly bonded to a housing and including three parallel probes. A magnet is bonded into the central probe and the outer probes act as Hall effect devices. The sensor provides crankshaft angular position information to an electronic control module that controls the spark sequence of the internal combustion engine. A crankshaft mounted timing ring, which has a plurality of vane segments and which further has common rotation with the crankshaft, activates the sensor. The sensor is mounted on the internal combustion engine such that the vane segments pass through a pair of spaces defined between the probes. The movement of the vane segments through the spaces defined by the probes has the effect of shunting the magnet flux fields generated by the probes and thereby generates a predetermined series of pulses at the electronic control module that is indicative of the firing order of the internal combustion engine.
SUMMARY OF THE INVENTION
The invention provides an apparatus for positioning a sensor relative to a rotatable timing ring included on an internal combustion engine, which apparatus includes a sensor, means for adjustably positioning the sensor on the internal combustion engine, the sensor positioning means being moveable relative to the sensor and to the timing ring, and means for fixing the sensor in an adjusted position on the internal combustion engine.
In one embodiment, the invention provides an internal combustion engine for a marine propulsion device having a flywheel housing, a crankshaft extending rotatably in the flywheel housing, a flywheel fixed on the crankshaft for common rotation with the crankshaft and positioned in the flywheel housing, a timing ring fixed on the crankshaft and having common rotation therewith, a base member moveably mounted on the flywheel housing a sensor fixed on the base member, and a means for adjustably positioning the sensor relative to the timing ring, the sensor positioning means being adapted to move to and from the timing ring.
In one embodiment the base member includes a means for fixing the sensor in an adjusted position on the flywheel housing of the internal combustion engine, the sensor fixing means including a flange fixed on the base member and having an elongated adjustment slot, and wherein the flywheel housing includes a threaded bore, and a screw threadably mates with the threaded bore and extends through the adjustment slot.
In one embodiment the base member includes a pair of bores, and the means for adjustably positioning the sensor relative to the timing ring includes a pair of shafts which are individually moveably housed in each of the bores, and wherein each of the shafts has a proximal and a distal end, and the distal ends include a longitudinally disposed slot which is adapted to receive the timing ring when the individual shafts are moved toward the timing ring.
In one embodiment the sensor positioning means includes a biasing means having an elongated main body with opposite ends, and wherein the opposite ends rest on the base and include an aperture, and wherein the individual shafts extend through each of the apertures, and wherein the proximal ends of each shaft is fixed on the opposite ends of a bar and the leaf spring acts upon the bar thereby positioning the shafts away from the timing ring.
In one embodiment, alignment of the individual shafts such that the timing ring is slideably received in the longitudinal slot formed in the distal end of each shaft thereby positions the electronic sensor in a proper operational attitude relative to the timing ring, and the base member is fixed in the adjusted position on the flywheel housing thereby securing the sensor in the proper operational attitude.
The invention also provides an internal combustion engine including a flywheel housing, a crankshaft extending rotatably in the flywheel housing, a flywheel fixed on the crankshaft, having common rotation therewith, and positioned in said flywheel housing, and a timing ring fixed on the crankshaft, positioned adjacent to the flywheel, and having common rotation with the crankshaft.
The invention also provides a marine propulsion device including an internal combustion engine having a flywheel housing, a crankshaft extending rotatably in the flywheel housing, a flywheel fixed on the crankshaft and having common rotation therewith, a timing ring fixed on the crankshaft, positioned adjacent to the flywheel, and having common rotation with the crankshaft, a base member moveably mounted on the flywheel housing, a sensor fixed on the base member and moveable relative to the timing ring, means on the base member for positioning the sensor relative to the timing ring, which sensor positioning means is moveable to and from the timing ring, and means for biasing the sensor positioning means from the timing ring.
Other features and advantages of the invention will become apparent to those skilled in the art upon reviewing the following detailed description, the drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation view of the present invention shown in typical operative configuration for use with a marine propulsion device.
FIG. 2 is somewhat enlarged, fragmentary, transverse vertical sectional view taken generally along line 2--2 of FIG. 1 and showing the internal portion of the flywheel housing.
FIG. 3 is a fragmentary, somewhat enlarged, longitudinal, vertical, sectional view of the present invention taken generally along line 3--3 of FIG. 2, and showing the position of the sensor on the flywheel housing, and the vane segments of the timing ring positioned between the probes of the sensor.
FIG. 4 is a somewhat enlarged, fragmentary, top plan view of present invention with some underlying surfaces shown in hidden lines.
FIG. 5 is a fragmentary, longitudinal sectional view of the apparatus of the present invention taken along line 5--5 of FIG. 4, and showing the alternative positions of the individual shafts in phantom lines.
FIG. 6 is a transverse, vertical sectional view of the apparatus of the subject invention taken along line 6--6 of FIG. 4, and showing the alternative positions of the individual shafts in phantom lines.
FIG. 7 is a fragmentary, side elevation of the apparatus of the subject invention taken from a position along line 7--7 of FIG. 4, and showing the relative positions of the probes with respect to the timing ring.
Before one embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details the of construction and the arrangements of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to the drawings, the apparatus for positioning a sensor of the present invention is generally indicated by the numeral 10 in FIG. 4. For illustrative convenience, the apparatus 10 as herein shown and described is depicted as it would be installed on, or retrofitted to, a marine propulsion device 11, which is illustrated as a stern drive unit 12 mounted on a boat 13. The boat is of common design and has a transom 14 through which a drive unit 15 extends. The drive unit 15 includes a rotatably moveable drive shaft 16 which is drivingly connected to a propeller 17. An internal combustion engine 20 is mounted in the boat and is drivingly connected to the drive unit in a fashion well understood by those skilled in the art. The internal combustion engine 20 has a flywheel housing 21 including a substantially rearwardly facing surface 22. As best illustrated by reference to FIG. 3, an opening 23 is formed in the rearwardly facing surface 22 and permits access to the inside of the flywheel housing.
A crankshaft 24 rotatably extends into the flywheel housing 21, and a flywheel 25 is fixed thereon and is adapted for common rotation therewith. The flywheel 25 has a main body 30 including a peripheral edge 31, and further has substantially forwardly and rearwardly facing surfaces 32 and 33, respectively. The main body includes a substantially centrally disposed passageway 34 through which the crankshaft passes, and a coupler assembly 35 is fixed on the flywheel 25 and has common rotation therewith. The coupler assembly is drivingly connected to the drive shaft 16 in a manner well understood in the art and therefore is not discussed in further detail herein.
A timing ring 40 has a main body 41 including a substantially centrally disposed passageway 42. The timing ring 40 is fixed on the crankshaft 24, and is disposed in a position immediately adjacent to the rearward surface 33 of the flywheel 25. This relationship is most clearly seen by reference to FIG. 3. The timing ring further has an arcuately shaped peripheral edge 43 which includes a first or inner timing vane segment 44 disposed in substantially right angular relation to the main body 41. A second or outer timing vane segment 45 is fixed on the main body 41 of the timing ring and is positioned in spaced relation to the first timing ring segment 44. A gap or space 46 is defined between the first and second timing vane segments.
As best illustrated by reference to FIGS. 3 and 4, there is also provided means for moveably mounting a sensor adapted to be adjustably fixed to the flywheel housing 21. While various arrangements can be used, in the specific construction illustrated, such means includes a base member 50 which has first and second ends 51 and 52, respectively, and top and bottom surfaces 53 and 54, respectively. The base member has a longitudinal axis which is generally indicated by the line 55 and which extends radially from the crankshaft 24. The base member 50 also has two flanges or bosses 56 which are positioned adjacent the second end, and which include respective elongated adjustment slots 60. The individual adjustment slots 60 are disposed in substantially parallel spaced relation to the longitudinal axis 55. Bushings 61 having substantially similar elongated shapes are respectively positioned in the adjustment slots, and screws 62 are respectively received in each adjustment slot. The screws 62 respectively threadably engage threaded bores (not shown) formed in the rearwardly facing surface of the flywheel housing 21. When in an untightened condition, the screws 62 permit movement of the base member 50 radially of the crankshaft, and along the longitudinal axis 55.
A pair of bores 63 and 64, respectively, are formed in the first end 51 of the base member 50 and are disposed in substantial registry with the opening 23 of the flywheel housing 21. An electronic sensor 70 is fixed on the base 50 and is moveable therewith. The sensor 70 includes a sensing element 71 and a lead frame assembly 72. A plurality of electric leads 73 are connected to the lead frame and are further connected to an electronic control module, not shown. The sensing element 71 further includes first, second and third probes 74, 75, and 76 respectively. The first and third probes carry Hall effect devices, (not shown) and the second probe carries a magnet (not shown). A gap 80 is defined between the first and second probes and a gap 80 is defined between the second and third probes. The first and second timing vane segments are respectively aligned for passage through the respective gaps 80 and in the manner as most clearly seen by reference to FIGS. 3 and 4.
Means are provided for adjustably locating or positioning the sensor 70 relative to the timing ring 40. While various arrangements can be used, in the specific construction illustrated, such means includes first and second shafts 81 and 82, respectively, which are moveably housed in respective bores 63 and 64 in the base member 50. The shafts have proximal and distal ends 83 and 84, and are reciprocally moveable both to and from the timing ring 40 a direction perpendicular to the axis 55 and in the manner as illustrated most clearly by reference to FIG. 5. The distal end 84 of each shaft has a longitudinally disposed slot 85 positioned in substantially parallel relation with respect to a tangent to the arc which is defined by the first timing vane segment 44. This relationship is seen in FIG. 4. The distal end 84 of each shaft also has a flared portion 90 which limits the movement of the shafts away from the timing ring by engaging the bottom surface 54 of the base member 50.
Connected on the proximal ends of each shaft is a bar 91 having first and second ends 92 and 93, respectively, and top and bottom surface 94 and 95, respectively.
Means are provided for biasing the shafts 81 and 82 away from the timing ring 40. While various arrangements can be used, in the specific construction illustrated, such means includes a leaf spring 100 having an elongated substantially arcuately shaped main body 101. The leaf spring 100 also has opposite first and second ends 102 and 103, respectively. Apertures 104 and 105 are respectively provided adjacent each end. As best illustrated by reference to FIGS. 5 and 6, the leaf spring 100 is operable to act upon the bar 91, thereby positioning the shafts in a retracted position 110, shown in full lines in FIG. 5. By exerting manual force on the bar 91 the force of the biasing spring 100 can be overcome and the shafts 81 and 82 can be moved toward the timing ring 40 and into an extended position 111 shown in phantom lines in FIGS. 5 and 6.
With this arrangement, the base member 50 may be adjustably positioned relative to the flywheel housing 21 such that the probes 74, 75, and 76 are operatively positioned relative to the first and second timing vane segments 44 and 45, respectively. More specifically, when the screws 62 are loosened, movement of the base member is permitted to afford radially adjusted location of the sensor 70 in an aligned position relative to the timing ring 40. In this regard, when the sensor 70 is properly located, the bar 91 is depressable to cause movement of the shafts 81 and 82 toward the timing ring 40 and into the extended position 111. By movably adjusting the base member 50 the individual shafts can be positioned such that the first timing vane segment 44 is slideably received in each of the longitudinally disposed slots 85. When the first timing vane segment is positioned in the slots 85, the individual probes 74, 75 and 76 are operatively positioned relative to the individual timing vane segments 44 and 45. The base member 50 is then secured to the flywheel housing by tightening the screws 62. The bar is thereafter released and the shafts 81 and 82 are returned to the retracted position 110 by the action of the leaf spring 100.
Various features of the invention are set forth in the following claims: | Disclosed herein is apparatus for positioning a sensor relative to a rotatable timing ring included on an internal combustion engine, which apparatus includes a sensor, a structure for adjustably positioning the sensor on the internal combustion engine and relative to the timing ring, which structure is movable relative to the sensor and to the timing ring, and additional structure for fixing the sensor in adjusted position on the internal combustion engine. | 5 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims the priority of German Application No. 199 05 668.4 filed Feb. 11, 1999, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates to a transfer needle for loop-forming machines making flat textile knitwear.
For making, for example, patterned knitwear, circular knitting machines with cylinder needles and dial needles may be used. Dependent on the pattern, individual loops are transferred from the cylinder needles to the dial needles and conversely. For this purpose special needles are used which have loop transfer elements and are designated as transfer needles.
German Patent No. 42 31 015 discloses transfer needles configured as compound needles which have a slide extending longitudinally along the needle shank and serve for opening and closing a hook (head) carried by the needle shank. A transfer spring secured to the side of the compound needle defines with the needle shank an intermediate space through which the hook and the shank of another needle may pass. The transfer spring is held only at one of its ends on the needle shank. For a suitable configuration of the intermediate space between the transfer spring and the needle shank the latter is provided with a recess which intersects the slide as well as the shank.
The intersecting faces of the slide and the shank each form guide faces which are to facilitate the penetration of another needle into the intermediate space.
German Patent No. 1,560,996 discloses a transfer needle which is configured as a latch needle rather than a compound needle. Accordingly, it has a solid needle shank without a slide element. To effect loop transfer, the latch needle has a laterally bent shank. That part of the shank which extends from the hook and which is designated as the main shank is of stepped structure having a high and a low portion. Starting from the low portion, a groove extends over the needle back to the high shank portion in which the groove is entirely open towards the side face of the needle.
A lateral bent portion of the shank is, however, in many instances undesirable.
German Patent No. 31 45 708 discloses a transfer needle for flat knitting machines. The needle has a transfer spring on its side for transferring the loops. The spring is a leaf spring and is affixed at one of its ends to the needle shank. The other, free end of the leaf spring forms, together with the needle shank, an intermediate space into which another needle may penetrate with its hook and shank. The leaf spring as well as the needle shank are, at their respective underside, provided with an oblique guide face which is intended to facilitate the penetration of another needle into the intermediate space between the transfer spring and the needle shank. The guide face provided on the shank is substantially planar and extends from the needle back to the outer side face of the needle.
Particularly the transfer spring of the transfer needle is exposed to substantial dynamic loads during operation. For the loop transfer first the hook and one part of the shank of another transfer needle enters the intermediate space in the vicinity of the free end of the transfer spring. This event may already cause the free end of the transfer spring to be pushed away laterally from the needle shank at which the transfer spring is secured. If such an occurrence takes place in a narrow needle guide channel where the transfer spring lies against the channel flanks, the transfer spring may undergo substantial local bending deformations which lead to high stresses. If such an occurrence causes breakage of the spring, the transfer needle becomes useless, and the knitting machine has to be stopped for servicing.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an improved transfer needle of the above-outlined type whose service life is lengthened.
This object and others to become apparent as the specification progresses, are accomplished by the invention, according to which, briefly stated, the transfer needle for loop forming machines includes an elongated needle shank having a needle back, an outer side face and a top face opposite the needle back; a transfer spring attached to the needle shank and defining an intermediate space therewith; and a lateral recess provided in the needle shank and forming part of the intermediate space. The recess is defined by a guide face extending from the needle back to the outer side face of the needle shank. The guide face includes a first length portion bordering the outer side face of the needle shank and extending toward the needle back; and a second length portion bordering the needle back and extending toward the outer side face of the needle shank. The first and second length portions of the guide face meet in an obtuse angle which is open toward the transfer spring.
Thus, the transfer needle according to the invention has at its side face a recess which is covered by a transfer spring. The transfer spring is, at one of its ends, connected with the needle shank and has a preferably pointed tongue which lies in a depression of the needle shank. The recess positively defines a guide face at the needle shank along which a penetrating hook of another needle may slide. The guide face extends along the recess from the needle back to the lateral needle face, while its angle formed with the needle back changes. Stated differently, the guide face has a first portion adjoining the needle back and a second portion adjoining the lateral needle face, and the two portions form an obtuse angle with one another, whereby the guide face is concave. This measure prevents an excessive weakening of the needle shank in the region of the recess. This measure also permits an enlargement of the depth of the recess compared to conventional configurations without causing an excessive weakening of the needle shank. Also, the displacement/time relationship concerning the excursion of the transfer spring may be positively affected, and a spring breakage is prevented which could otherwise occur as a result of dynamic loads on the transfer spring, particularly in the region of its free end. The service life or service expectancy of such a transfer needle is thus lengthened.
The transfer needle according to the invention may be configured such that the guide face forms, in vicinity of the needle back, a small angle with the principal direction of motion of a penetrating transfer needle. In this manner a penetrating transfer needle is relatively slowly deflected laterally and is relatively gradually accelerated. Thus, not only the transfer spring but also the penetrating transfer needle is gently handled.
Due to the particular configuration of the guide face, in the transfer needle according to the invention a smooth transition from the upper side (top face) of the needle to the outer side face thereof for forming the loop support edge is not affected. The depth of the penetration space, however, may be enlarged. The recess may be configured such that it terminates at the side face of the transfer needle. By virtue of this arrangement, in this region the loop supporting edge may configured without a profile change caused by the recess. This ensures that the loops glide gently and without damage over the loop supporting edge.
The concave shape of the guide face may be obtained in various ways. For example, the guide face may be at least partially arcuate in the longitudinal direction of the transfer needle. Additionally, the guide face may be at least partially arcuate or kinked at least once in a direction defined by the penetrating motion of another transfer needle. The curvature may be circular, parabolic or of any other shape. In any event, the recess may be deeper than it has been possible heretofore without adversely affecting the loop supporting edge or the stability of the loop forming region of the transfer needle. It has been found that the depression, compared to transfer needles having a linear guide face could be deepened by 0.1 mm at the height of the bottom edge of the transfer spring, corresponding at least to one-half of the thickness of the transfer spring. By making the depression deeper, the displacement/time relationship of the motion of the transfer needles and their parts during the loop transfer step is positively influenced in that the transfer spring bends to a lesser extent which means a relief of the transfer spring. Further, the introducing step is facilitated by the enlargement of the space between the transfer spring and the guide face; as a result, more space is provided for the penetrating transfer needle.
In the alternative, and in principle with the same effect, the guide face may have a kink line defined by two essentially planar surface regions.
The angle which the lower part of the guide face (in the vicinity of the needle back) forms with a line which is perpendicular to the needle back is preferably less than 20° (preferably 18°), and such an angle for the upper part of the guide face (which borders the lateral needle face) is preferably more than 20°. On the outer side face of the needle the angle is preferably substantially greater and amounts to, for example 25° or even more than 30°. The depth of the depression may so dimensioned that at the needle back it occupies more than one-half of the width of the transfer needle. At the height of the bottom edge of the transfer spring the depth of the depression is, however, preferably less than one-half of the shank thickness. At this height a kink line may be arranged at which the inclination of the guide face changes. In the alternative, a curved part of the guide face may start or may terminate at that location.
Advantageous geometrical conditions and advantageous conditions for the motion of the penetrating transfer needle are obtained when the depression on the needle back occupies more than one-half the width of the transfer needle. The transition of the guide face from a first angular orientation to a further angular orientation preferably occurs essentially at the height of the lower edge of the transfer spring.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified perspective view of one part of the transfer needle incorporating the invention.
FIG. 2 is a side elevational view of one part of the transfer needle shown in FIG. 1 .
FIG. 3 is a top plan view of one part of the needle shown in FIG. 2, also showing a channel side wall contacted by the transfer needle.
FIG. 4 is a sectional view taken along line IV—IV of FIG. 2 .
FIGS. 5 a , 6 a and 7 a are top plan views of a conventional transfer needle shown in different operational positions.
FIGS. 5 b , 6 b and 7 b are top plan views of a transfer needle according to the invention shown in the same operational positions as those illustrated in the respective FIGS. 5 a , 6 a and 7 a.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a transfer needle 1 including a shank 2 , a head 3 and the associated elements. The needle butt is not shown. The shank 2 is divided into a high length portion 4 and a low length portion 5 . Both length portions 4 and 5 extend upwardly from a common needle back 6 . The transition from the high length portion 4 of the shank 2 to its low length portion 5 is formed by a step 8 . On either side of the step 8 the shank 2 extends without a bend and linearly in the longitudinal direction L which coincides with the principal direction of motion of the transfer needle 1 .
In the needle shank 2 , in the zone of the transition between the length portions 4 and 5 , that is, approximately underneath the step 8 , a recess 11 is provided which serves for receiving the head 3 of another transfer needle 1 ′, as particularly well seen in FIG. 2 . The recess 11 constitutes a lateral opening in the shank 2 and thus extends from the needle back 6 to an outer needle side face 12 extending between the needle back 6 and the upper needle surface (top face) 7 . Between the outer side face 12 and the top face 7 of the needle a loop supporting edge 14 is formed which is spaced from the recess 11 .
The recess 11 is substantially covered by a transfer spring 15 which is a leaf spring having a linear, essentially rectangular mounting portion 16 held in a lateral depression 17 of the needle shank 2 , for example, by means of a plurality of embossments 18 . Starting from an end of the mounting portion 16 the transfer spring 15 is offset from the needle shank 2 , whereby a further length portion 19 of the transfer spring 15 extends parallel to and at a distance from the remaining needle shank 2 . In the corresponding zone adjacent the spring length portion 19 the shank 2 may have a slightly reduced thickness. Thus the shank 2 , starting from a location 21 situated at the start of the offset of the spring 15 , is slightly narrower than in the remaining shank regions.
The height of the length portion 19 of the transfer spring 15 is reduced in the length direction L of the shank 2 with a step 22 approximately at the same location where the height of the shank 2 is reduced. Such an arrangement is particularly well seen in FIG. 2 which illustrates the transfer needle 1 in side elevation. Starting from the step 22 the transfer spring 15 is further reduced so that eventually it ends approximately in a point at its terminus 23 . The bent configuration of the transfer spring 15 may be best observed in FIG. 3 : The transfer spring 15 extends, starting from the bend 24 , approximately parallel to the shank 2 ; the tapering portion with its end 23 is bent towards the shank 2 and lies under bias in a groove 25 provided in the shank 2 . Between the length portion 19 and an adjoining, tapering length portion 9 of the transfer spring 15 and the shank 2 thus an intermediate penetration chamber 27 is formed. Between the bend 24 of the transfer spring 15 and the step 22 of the needle shank 2 the transfer spring 15 has the planar, plate-like length portion 19 . The latter and/or the length portion 9 engages a flank F of a needle channel or may contact the flank F at least at one location of the spring 15 .
Opposite the recess 11 on the top face 7 of the shank 2 a cutout 28 is formed which extends into the adjoining lateral shank surface and which serves for guiding the loops lying on the shank 2 . Since the cutout 28 is situated opposite the recess 11 , a reduction of the cross section of the shank 2 is obtained. In order to maintain such a reduction to a possibly small value, the relatively larger recess 11 has a specific shape as shown in FIG. 4 .
The recess 11 is bordered towards the shank 2 by a guide face 29 which extends at the needle back 6 in an acute angle to the direction V (FIGS. 1 and 4) which, in turn, is oriented at 90° to the needle back 6 and is indicating approximately the direction in which a penetrating transfer needle 1 ′ (FIG. 3) is moved. The guide face 29 is concave relative to the lateral needle face 12 . The guide face 29 has a first surface region 31 which adjoins immediately the needle back 6 and a central surface region which is at least approximately planar. In the longitudinal direction L the recess 11 terminates in a preferably planar shape at both ends; the surface region 31 may be slightly arcuate.
Referring once again to FIG. 4, approximately at the same height as a linearly extending bottom edge 32 of the transfer spring 15 , the guide face 29 changes its angle of inclination. It changes at a kink line 33 , for example, into a planar second surface region 34 which is inclined at an angle larger than 25°, for example, 30° to the direction V. For illustrating the effect of this measure, a broken line 35 shows the course of a guide face which would result in case of an angle of 25°. It is seen that the recess is significantly smaller. The additionally obtained free space of the recess is designated at 30 . In contrast, a throughgoing arrangement of the guide face 29 at an angle of 18° would result in the guide face 29 reaching the loop supporting edge 14 . By subdividing the guide face 29 into two planar or curved surface regions 31 and 34 arranged at an obtuse angle to one another, the cross-sectional region of the shank 2 shown closely shaded in FIG. 4 ensures a stability of the shank 2 . The depth 30 of the recess 11 , measured at the bottom edge 32 of the transfer spring 15 , is significantly enlarged compared to a throughgoing guide surface having an angle of 25°. The increase of the depth of the recess 11 may be more than one-half of the thickness of the transfer spring 15 . The guide face 29 has an overall concave shape, which reduces the dynamic loads of the transfer spring 15 . The arrangement of such an overall concave shape may be explained with reference to FIG. 4 as follows: the earlier-noted broken straight line 35 may also be regarded as connecting an upper edge 29 a of the guide face 29 lying in the lateral needle face 12 and a lower edge 29 b lying in the needle back 6 . It is seen that the entire guide face 29 as viewed cross-sectionally in FIG. 4 is situated solely on one side of the broken line 35 and furthermore, as viewed between the edges 29 a and 29 b , the cross-sectionally viewed guide face 29 is throughout of concave configuration.
The second surface region 34 , as indicated with a line 36 in FIG. 4, may be planar, that is, it may be straight within the sectional plane. It may, however, also have a radius R, that is, it may be of arcuate shape. The radius of curvature may be constant. In the alternative, the radius of curvature may change as a function of the angle so that curvatures different from a circular arc may be obtained.
In the description which follows, the operation of the above-described transfer needle 1 will be set forth, particularly in conjunction with FIG. 2 .
For transferring loops which lie on the length portion 5 of the shank 2 , another transfer needle 1 ′ penetrates into the chamber 27 at which time the end 23 of the transfer spring 15 lies in the groove 25 of the shank 2 . FIGS. 5 a and 5 b compare a transfer needle 1 according to the invention (FIG. 5 b ) with a conventional transfer needle 1 a (FIG. 5 a ) at the beginning of the penetration by another transfer needle shown in section and designated at 1 ′ and 1 ′ a, respectively. Based on the deepening of the recess 11 because of the subdivision of the guide faces compared to the conventional transfer needle 1 a, the end 23 of the transfer spring 15 does not lift off the shank 2 of the transfer needle 1 , in contrast to the transfer needle 1 a.
Thus, the conditions are different in the transfer needle la according to the prior art as illustrated in FIGS. 5 a , 6 a and 7 a.
As seen in FIG. 5 a , at the beginning of the penetrating step the transfer spring 15 a of the conventional transfer needle la is lifted from the needle shank 2 a by the penetrating transfer needle 1 a ′. The transfer spring 15 a is pushed against the flank F of the needle channel in which the transfer needle 1 a runs. The support point onto which the transfer spring 15 a runs onto the flank F is designated at 40 . There is obtained a short leverage length of the outwardly moved portion of the transfer spring 15 a at the tapering portion 9 a of the transfer spring 1 a. This results in a high material stress which, as shown in FIG. 5 b , is avoided in the transfer needle 1 according to the invention.
The penetration step shown in FIG. 2 in side elevation first starts in the vicinity of the free end of the transfer spring 15 . Upon penetration, the penetrating transfer needle 1 ′ is moved in the direction of the obliquely upward directed arrow 41 . Accordingly, in the course of the penetrating step, the penetrating transfer needle 1 ′ or 1 a ′ moves away from the free end 23 of the respective transfer spring 15 or 15 a . As the penetrating step progresses, the transfer spring 15 of the transfer needle 1 according to the invention (FIG. 6 b ) is in engagement with the shank 2 as before, while the conventional transfer needle 1 a, as shown in FIG. 6 a , is lifted off the shank 2 as before.
Only as the penetrating step further progresses, as shown in FIGS. 7 a and 7 b , does the penetrating transfer needle 1 ′ advance into the penetrating chamber 27 to such an extent that it leaves the guide face 29 with its head and reaches the side face 12 of the transfer needle 1 . At the same time, the penetrating transfer needle 1 ′ has advanced to such an extent in the direction of the arrow 42 (FIG. 2) that it reaches a region of sufficient distance between the transfer spring 15 and the side face 12 to be able to move forward without causing an appreciable excursion of the transfer spring 15 . The penetrating step performed by the transfer needle 1 ′ is optimized to such an extent by virtue of the shape of the guide face 29 altered by the invention that the bending stress of the transfer spring 15 is reduced compared to the prior art and thus the service life of the needle is lengthened.
It will be understood that the above description of the present invention is susceptible to various modifications, changes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims. | A transfer needle for loop forming machines includes an elongated needle shank having a needle back, an outer side face and a top face opposite the needle back; a transfer spring attached to the needle shank and defining an intermediate space therewith; and a lateral recess provided in the needle shank and forming part of the intermediate space. The recess is defined by a guide face extending from the needle back to the outer side face of the needle shank. The guide face includes a first length portion bordering the outer side face of the needle shank and extending toward the needle back; and a second length portion bordering the needle back and extending toward the outer side face of the needle shank. The first and second length portions meet in an obtuse angle open toward the transfer spring. | 3 |
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 09/096,772, entitled “Logical Volume Mount Manager,” filed Jun. 12, 1998, which is hereby incorporated herein by reference in its entirety. Further, this application is related to co-assigned U.S. patent application Ser. No. 09/096,540, entitled “Persistent Names for Logical Volumes,” now U.S. Pat. No. 6,496,839, and U.S. patent application Ser. No. 09/097,061, entitled “Persistent Volume Mount Points,” now U.S. Pat. No. 6,119,131, both of which are hereby incorporated herein by reference by their entirety.
FIELD OF THE INVENTION
[0002] This invention relates generally to computer storage device configuration, and more particularly to managing logical volumes mounted in a computer system.
BACKGROUND OF THE INVENTION
[0003] Most operating systems identify a logical unit of mass storage through a “well-known” and system compatible name which defines an actual physical path to the logical unit, i.e., \device0\partition1\. The operating system then associates a user-friendly name, such as a drive letter, with the well-known name so that the data on the storage device can be easily accessible by higher layers of the operating system and user applications. The higher layers of the operating system and applications assume that the well-known names, and thus the associated user-friendly names, are persistent across boot sessions. In actuality, the names are persistent only as long as the physical configuration of the computer does not change. Persistence cannot be guaranteed because such operating systems assign the well-known names in the order in which the storage devices are detected when booting. When the physical locations of the storage devices change, these operating systems will assign the well-known names to different devices. Therefore, the consistency of name assignments across multiple boot sessions is not preserved under all circumstances, and the higher operating system layers and user applications will be unable to access the data on the devices without modification.
[0004] Furthermore, most operation systems assume that only the storage devices found during the boot process will be present during the boot session. Thus, new storage devices added after booting cannot be recognized. This limitation also means that a logical device unit will not be recognized if the underlying storage device is removed and then reinserted during a boot session.
[0005] Therefore, there is a need in the art for a operating system that tracks logical device units during and across boot sessions, and provides persistent names despite physical configuration changes.
SUMMARY OF THE INVENTION
[0006] The above-mentioned shortcomings, disadvantages and problems are addressed by the present invention, which will be understood by reading and studying the following specification.
[0007] A logical volume mount manager is responsible for identifying and tracking logical volumes created from a physical storage device by the operating system, and for determining a redirected name for a logical volume which is used by higher layers of the operating system and user applications. The mount manager builds and maintains a persistent data structure based on a unique volume identifier which identifies the logical volume. Optionally, the mount manager also creates an in-memory data structure as well. Each entry in the data structure(s) consists of the redirected name and the unique volume identifier for a logical volume so that the redirected name persists across boot sessions. Because the operating system addresses a logical volume through a non-persistent device name, the mount manager causes the operating system to create a symbolic link between the device name and the redirected name when the mount manager first identifies the logical volume during a boot session so that the higher layers of the operating system and user applications can access the logical volume through the persistent redirected name.
[0008] When the physical configuration of the computer changes, the device name changes but the unique volume identifier does not. The mount manager uses the unique volume identifier to locate the appropriate redirected name in its data structure(s) and causes a new symbolic link to be created with the new device name so that the symbolic link resolves the redirected name to the correct logical volume under all circumstances.
[0009] Because the mount manager identifies the logical volume through its unique volume identifier and does not rely on the devices being located in any particular order in the system, or being discovered in any particular order during the boot process, or being present only during the boot process, changes in the physical configuration of the computer between boots, or during a boot session, have no effect on the higher layers of the operating system and user applications which rely on the redirected name. Thus, the level of indirection provided by the mount manager and supporting data structures guarantees that the higher layers of the operating system and user applications will be able to access data on a logical volume for the life of the logical volume without modifications.
[0010] The present application describes computer systems, methods, and computer-readable media of varying scope. The mount manager is variously described as causing the processor of a computer to perform certain actions, as a series of steps executed from a computer-readable medium, and in terms of its interaction with objects and other system components in an object-based operating system. In addition to the aspects and advantages of the present invention described in this summary, further aspects and advantages of the invention will become apparent by reference to the drawings and by reading the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [0011]FIG. 1 shows a diagram of the hardware and operating environment in conjunction with which embodiments of the invention can be practiced;
[0012] [0012]FIG. 2A is a diagram illustrating a system-level overview of an exemplary embodiment of the invention;
[0013] [0013]FIGS. 2B and 2C illustrate mount manager data structures for use in the exemplary embodiment of the invention shown in FIG. 2A;
[0014] [0014]FIGS. 3A, 3B, 3 C and 3 D are flowcharts of method to be performed by a computer system according to an exemplary embodiment of the invention; and
[0015] [0015]FIG. 4 is a diagram illustrating a particular embodiment of the invention in a Microsoft Windows NT environment.
DETAILED DESCRIPTION OF THE INVENTION
[0016] In the following detailed description of exemplary embodiments of the invention, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration specific exemplary embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that logical, mechanical, electrical and other changes may be made without departing from the spirit or scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims.
[0017] The detailed description is divided into five sections. In the first section, the hardware and the operating environment in conjunction with which embodiments of the invention may be practiced are described. In the second section, a system level overview of the invention is presented. In the third section, methods for an exemplary embodiment of the invention are provided. In the fourth section, a particular Microsoft Windows NT 5.0 implementation of the invention is described. Finally, in the fifth section, a conclusion of the detailed description is provided.
Hardware and Operating Environment
[0018] [0018]FIG. 1 is a diagram of the hardware and operating environment in conjunction with which embodiments of the invention may be practiced. The description of FIG. 1 is intended to provide a brief, general description of suitable computer hardware and a suitable computing environment in conjunction with which the invention may be implemented. Although not required, the invention is described in the general context of computer-executable instructions, such as program modules, being executed by a computer, such as a personal computer. Generally, program modules include routines, programs, objects, components, data structures, etc., that perform particular tasks or implement particular abstract data types.
[0019] Moreover, those skilled in the art will appreciate that the invention may be practiced with other computer system configurations, including hand-held devices, multiprocessor systems, microprocessor-based or programmable consumer electronics, network PCs, minicomputers, mainframe computers, and the like. The invention may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote memory storage devices.
[0020] The exemplary hardware and operating environment of FIG. 1 for implementing the invention includes a general purpose computing device in the form of a computer 20 , including a processing unit 21 , a system memory 22 , and a system bus 23 that operatively couples various system components, including the system memory 22 , to the processing unit 21 . There may be only one or there may be more than one processing unit 21 , such that the processor of computer 20 comprises a single central-processing unit (CPU), or a plurality of processing units, commonly referred to as a parallel processing environment. The computer 20 may be a conventional computer, a distributed computer, or any other type of computer; the invention is not so limited.
[0021] The system bus 23 may be any of several types of bus structures including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. The system memory may also be referred to as simply the memory, and includes read only memory (ROM) 24 and random access memory (RAM) 25 . A basic input/output system (BIOS) 26 , containing the basic routines that help to transfer information between elements within the computer 20 , such as during start-up, is stored in ROM 24 . The computer 20 further includes a hard disk drive 27 for reading from and writing to a hard disk, not shown, a magnetic disk drive 28 for reading from or writing to a removable magnetic disk 29 , and an optical disk drive 30 for reading from or writing to a removable optical disk 31 such as a CD ROM or other optical media.
[0022] The hard disk drive 27 , magnetic disk drive 28 , and optical disk drive 30 are connected to the system bus 23 by a hard disk drive interface 32 , a magnetic disk drive interface 33 , and an optical disk drive interface 34 , respectively. The drives and their associated computer-readable media provide nonvolatile storage of computer-readable instructions, data structures, program modules and other data for the computer 20 . It should be appreciated by those skilled in the art that any type of computer-readable media which can store data that is accessible by a computer, such as magnetic cassettes, flash memory cards, digital video disks, Bernoulli cartridges, random access memories (RAMs), read only memories (ROMs), and the like, may be used in the exemplary operating environment.
[0023] A number of program modules may be stored on the hard disk, magnetic disk 29 , optical disk 31 , ROM 24 , or RAM 25 , including an operating system 35 , one or more application programs 36 , other program modules 37 , and program data 38 . A user may enter commands and information into the personal computer 20 through input devices such as a keyboard 40 and pointing device 42 . Other input devices (not shown) may include a microphone, joystick, game pad, satellite dish, scanner, or the like. These and other input devices are often connected to the processing unit 21 through a serial port interface 46 that is coupled to the system bus, but may be connected by other interfaces, such as a parallel port, game port, or a universal serial bus (USB). A monitor 47 or other type of display device is also connected to the system bus 23 via an interface, such as a video adapter 48 . In addition to the monitor, computers typically include other peripheral output devices (not shown), such as speakers and printers.
[0024] The computer 20 may operate in a networked environment using logical connections to one or more remote computers, such as remote computer 49 . These logical connections are achieved by a communication device coupled to or a part of the computer 20 , the local computer; the invention is not limited to a particular type of communications device. The remote computer 49 may be another computer, a server, a router, a network PC, a client, a peer device or other common network node, and typically includes many or all of the elements described above relative to the computer 20 , although only a memory storage device 50 has been illustrated in FIG. 1. The logical connections depicted in FIG. 1 include a local-area network (LAN) 51 and a wide-area network (WAN) 52 . Such networking environments are commonplace in offices, enterprise-wide computer networks, intranets and the Internet.
[0025] When used in a LAN-networking environment, the computer 20 is connected to the local network 51 through a network interface or adapter 53 , which is one type of communications device. When used in a WAN-networking environment, the computer 20 typically includes a modem 54 , a type of communications device, or any other type of communications device for establishing communications over the wide area network 52 , such as the Internet. The modem 54 , which may be internal or external, is connected to the system bus 23 via the serial port interface 46 . In a networked environment, program modules depicted relative to the personal computer 20 , or portions thereof, may be stored in the remote memory storage device. It is appreciated that the network connections shown are exemplary and other means of and communications devices for establishing a communications link between the computers may be used.
[0026] The hardware and operating environment in conjunction with which embodiments of the invention may be practiced has been described. The computer in conjunction with which embodiments of the invention may be practiced may be a conventional computer, a distributed computer, or any other type of computer; the invention is not so limited. Such a computer typically includes one or more processing units as its processor, and a computer-readable medium such as a memory. The computer may also include a communications device such as a network adapter or a modem, so that it is able to communicatively couple to other computers.
System Level Overview
[0027] A system level overview of the operation of an exemplary embodiment of the invention is described by reference to FIGS. 2 A-C. FIG. 2A shows one embodiment of a logical volume mounting subsystem 200 executing in a computer such as local computer 20 or remote computer 49 in FIG. 1. The physical media, such as hard disk drive 27 in local computer 20 , contains one or more logical volumes. The process of associating a logical volume with the appropriate underlying physical media is commonly referred to in the art as “mounting” the logical volume on the physical media. The logical volume must be mounted before the data on the physical media can be accessed. The logical volume mounting subsystem 200 shown in FIG. 2A comprises a mount manager 201 and a persistent mount manager data structure 203 , and is responsible for associating “redirected” names, used by the higher layers of the operating system and user applications, with mounted logical storage volumes 207 , 208 and 209 so that the data on the underlying physical devices can be accessed through the redirected names. In FIG. 2A, the redirected names are represented by drive letters, such as commonly used by personal computer applications. The redirected names are not limited to drive letters as will be readily apparent to one skilled in the art and described in more detail below in conjunction with FIGS. 2B and 2C.
[0028] The operating system 205 creates the logical volumes 207 - 209 from removable or fixed physical media devices, such as hard disk drive 27 . Each logical volume is identified by a unique volume identifier, such as 994 for logical volume 207 , which is stored on the physical device, or devices, that make up the logical volume, and which is guaranteed to be unique on the particular computer. Each logical volume is also assigned a device name, such as Vol1 for logical volume 207 , during the boot process. The device name can change across boot sessions but is unique for a particular boot session.
[0029] The mount manager data structure 203 is maintained by the operating system 205 with other configuration data so that it is persistent across boot sessions. The operating system 205 presents each logical volume 207 - 209 to the mount manager 201 in the order in which the operating system 205 locates each logical volume in the computer when the computer is booted. The mount manager 201 queries each logical volume 207 - 209 for its device name and unique volume identifier. The mount manager 201 searches the mount manager data structure 203 to find an entry that contains the unique volume identifier for the logical volume 207 - 209 .
[0030] As shown in FIG. 2A, the unique volume identifier 991 for logical volume 207 appears in entry 211 in the mount manager data structure 203 . Entry 211 also contains a redirected name (“C:”) for logical volume 207 . Therefore, the mount manager 201 informs the operating system 205 of the association between the redirected name, C:, and the device name, Vol1, for logical volume 207 . The operating system 205 creates a logical, symbolic link between the redirected name and the device name, and maintains that link in a symbolic link data structure 215 . Similarly, the mount manager 201 causes the operating system 205 to create symbolic links between the device names, Vol3 and Vol2, and the appropriate redirected names, E: and D: respectively, when logical volumes 208 , 209 are presented to it.
[0031] When a new logical volume is introduced into the system, the mount manager 201 creates an entry in the data structure 203 and a redirected name for the logical volume, and causes the operating system to create the corresponding symbolic link. The redirected name for the logical volume can stored on the physical device, or devices, that make up the logical volume so it can be recalled if queried.
[0032] Because the unique volume identifier 998 for logical volume 209 is associated with the redirected name D: in the persistent mount manager data structure 203 , logical volume 209 will be always be assigned the same redirected name even if the logical volume 209 is presented to the mount manager 201 after the logical volume 208 which is associated with redirected name E:. The order in which the logical volumes are presented is dependent upon the order in which they are detected by the operating system 205 so the order changes if the underlying physical devices are rearranged in the computer between boots. The device name of the logical volumes also change when the physical configuration changes. Because the mount manager data structure 203 depends on the unique volume identifiers rather than the device names to identify the logical volume, the mount manager data structure 203 ensures consistency between redirected names and logical volumes across boot sessions regardless of the underlying physical configuration of the computer or the order in which the devices are recognized as long as the logical volume is valid.
[0033] If a logical volume is permanently removed from the system, the operating system 205 notifies the mount manager 201 which deletes the corresponding entry from the data structure 203 and breaks the symbolic link. However, if the logical volume is only removed temporarily, as illustrated by logical volume 209 in FIG. 2A, the mount manager 201 only breaks the corresponding symbolic link.
[0034] As shown in phantom in FIG. 1, if the logical volume 209 is re-introduced in the same boot session, the device name, Vol4, is different because a device name is used only once during a boot session, but the mount manager 201 finds the entry 212 in the data structure 203 based on the unique volume identifier 998 . Because the entry is present, the mount manager requests that the operating system 205 re-establish the corresponding symbolic link between logical volume 209 and its redirected name D:.
[0035] Thus, the volume mounting subsystem 200 guarantees that symbolic links will always resolve to the correct logical volume, both during a boot session and across multiple boot sessions, during the life of the logical volume.
[0036] [0036]FIG. 2B illustrates an alternate embodiment of a mount manager data structure 221 in which the redirected name assigned to a logical volume is a mount manager identifier (“persistent mount name”) 222 , 223 , and 224 which is guaranteed to be unique across all computers. Certain logical volumes, illustrated by entries 228 and 229 , are also assigned an additional “user-friendly” redirected name, such as a drive letter. The alternate embodiment shown in FIG. 2B is particularly applicable in operating system environments in which the number of user-friendly names for logical volumes is limited because a logical volume without a user-friendly name can be addressed by its persistent mount name 223 and also benefits from the consistency provided by the redirected names of the present invention.
[0037] In an alternate embodiment of the logical volume mounting subsystem, the mount manager 201 copies the persistent mount manager data structure into memory so that the time required to mount logical volumes and to detect configuration changes during a boot session is decreased. The in-memory data structure is, by its nature, non-persistent across boot sessions and is recreated during the boot process.
[0038] One embodiment of an in-memory mount manager data structure 231 is shown in FIG. 2C. The in-memory mount manager data structure 231 has been created from the persistent mount manager data structure 221 illustrated in FIG. 2B but could also be created from the persistent mount manager data structure 203 shown in FIG. 2A.
[0039] Each entry 233 in the in-memory mount manager data structure 231 is composed of three fields: a redirected name field 235 , a unique volume identifier field 237 , and a device name field 239 . The redirected name field 235 and the unique volume identifier field 237 are copied from the persistent mount manager data structure 221 upon system boot. As each logical volume is presented to the mount manager 201 , the mount manager 201 stores the boot session device name in the appropriate device name field 239 in the in-memory mount manager data structure 231 .
[0040] When logical volume 209 is temporarily removed from the system, its device name, Vol2, is deleted from the appropriate entries 233 in the mount manager data structure 231 but the unique volume identifier 998 is maintained in the entries. Thus, when logical volume 209 is re-introduced into the system and assigned the new device name, Vol4, the mount manager 201 is able to identify it as a logical volume that it was previously present, update the data structure 231 appropriately, and re-establish the corresponding symbolic links.
[0041] In an alternate embodiment, the in-memory mount manager data structure is an identical copy of the persistent mount manager data structure without the device name field 239 .
[0042] The system level overview of the operation of an exemplary embodiment of the invention has been described in this section of the detailed description. A mount manager and supporting data structures enable consistent identification and addressing of logical volumes despite physical configuration changes for the life of the logical volumes. While the invention is not limited to any particular arrangement of data in the data structures, for sake of clarity exemplary embodiments of persistent and in-memory data structures have been illustrated and described.
Methods of an Exemplary Embodiment of the Invention
[0043] In the previous section, a system level overview of the operation of an exemplary embodiment of the invention was described. In this section, the particular methods performed by a computer executing an exemplary embodiment is described by reference to a series of flowcharts. The methods to be performed by a computer constitutes computer programs made up of computer-executable instructions. Describing the methods by reference to a flowchart enables one skilled in the art to develop such programs including such instructions to carry out the methods on suitable computers (the processor of the computers executing the instructions from computer-readable media). The methods are illustrated in FIGS. 3 A-D and are inclusive of the steps or acts required to be taken by the mount manager 201 operating in the environment shown in FIGS. 2 A-C.
[0044] Referring first to FIG. 3A, when the computer is booted, the mount manager 201 creates the in-memory data structure 231 from the persistent mount manager data structure 221 (step 301 ). Upon initial boot of the computer, the persistent mount manager data structure 221 contains only user-friendly redirected names as no logical volumes have yet been configured in the system. Upon subsequent boots, the persistent mount manager data structure 221 contains user-friendly names, persistent mount names, and unique volume identifiers for the logical volumes that were not known to be permanently deleted from the system when it was shut-down.
[0045] After initializing its in-memory data structure 231 , the mount manager 201 waits for notification from the operating system 205 that a logical volume has been detected in the computer (step 303 ). When the notification arrives, either during the boot process or during the boot session, the mount manager 201 queries the volume for its unique volume identifier and its boot session device name (step 305 ). The mount manager 201 uses the unique volume identifier to search the in-memory data structure 231 for a matching entry (step 307 ). If a matching entry is found (step 309 ), the mount manager 201 checks the entry to determine if any redirected name has been previously assigned to the volume (step 311 ).
[0046] If the entry contains a redirected name(s), the mount manager 201 updates the in-memory data structure 221 with the device name at step 315 , and causes the operating system 205 to create a symbolic link between the redirected name(s) and the boot session device name (step 317 ). Thus, the redirected name(s) used by the higher layers of the operating system 205 and user applications are preserved across boot sessions, even though the device names may change when the physical configuration of the computer is modified. In an alternate embodiment in which the in-memory data structure does not contain the device name field, the mount manager 201 skips step 315 , as both the in-memory and persistent data structures already contain the correct unique volume identifier and redirected name(s) (illustrated by a phantom logic flow path in FIG. 3A).
[0047] When a logical volume is re-introduced into the system, either during a boot or during a boot session, if the entry does not contain redirected name(s) (step 311 ) as discussed above, then the mount manager 201 queries the logical volume for its “desired” redirected name(s) (step 313 ) and updates the corresponding entries in the data structures 221 , 231 with the device names and/or redirected name(s) as appropriate. The mount manager 201 then requests the creation of the symbolic links (step 317 ).
[0048] If there is no existing data structure entry that matches the unique volume identifier (step 309 ), the mount manager 201 creates an entry for the logical volume (step 319 ) by inserting the unique volume identifier in an empty entry. The mount manager 201 creates a persistent mount name the new logical volume (step 313 ). If requested to do so by the operating system 205 , the mount manager 201 also assigns the next available user-friendly name to the new logical volume at step 313 . The mount manager 201 informs the logical volume of the assigned redirected name(s) so they can be stored for later use. The mount manager data structures 221 , 231 are updated with the redirected name(s) (step 315 ), and the corresponding symbolic links created (step 317 ).
[0049] The mount manager 201 is also notified by the operating system 205 when a logical volume is temporarily removed from the computer as shown in FIG. 3B. All symbolic links associated with the logical volume are retired (step 321 ). The mount manager 201 updates its data structures 221 , 231 by deleting the device name for the logical volume from all entries associated with the logical volume. The unique volume identifier is maintained in the entries to detect the re-introduction of the logical volume (refer to step 309 in FIG. 3A).
[0050] The mount manager 201 also provides for deleting the symbolic links and mount manager data structure entries associated with the logical volume as illustrated in FIG. 3C. When requested to do so by the operating system 205 , the mount manager 201 retired the corresponding symbolic links (step 327 ), and deletes the unique volume identifier, device name, and persistent mount name for the logical volume from all the appropriate entries in the mount manager data structures 221 , 231 (step 329 ). The operating system makes this request when a logical volume is permanently deleted from the system but the operating system can also make the request without deleting the logical volume. However, if the logical volume is being accessed by a higher-layer application, only the data structure entries are modified as described above (step 325 ). The symbolic link(s) are maintained so that the applications can continue to access the data on the logical volume.
[0051] [0051]FIG. 3D illustrates the query function of the mount manager 201 . The operating system 205 can query the mount manager 201 regarding a mounted logical volume by passing the symbolic link name, the unique volume identifier, or the boot session device name of a logical volume to the mount manager 201 at step 331 . The mount manager 201 searches its in-memory data structure, if present, or its persistent data structure (step 333 ) and returns the corresponding entry if one is found (step 337 ). If no entry matches the search criteria, the operating system 205 is so informed (step 339 ). If the device name is used as the search criteria and there is no in-memory data structure, or if the in-memory data structure does not contain the device name, the mount manager 201 uses the symbolic link to determine the redirected name in order to perform the search.
[0052] The methods performed by a mount manager of an exemplary embodiment of the invention have been described with reference to a series of flowcharts illustrated in FIGS. 3 A-C, including all the steps from 301 until 339 shown therein. In particular, the methods of associating redirected names with logical volumes, and the management of such associations have been described.
Microsoft Windows NT 5.0 Implementation
[0053] In this section of the detailed description, a particular implementation of the invention is described that executes as part of the Microsoft Windows NT 5.0 operating system kernel. In the implementation illustrated in FIG. 4, the mount manager 401 and four other kernel modules work together to provide a user with access to data stored on a physical storage device 411 (shown as a fixed hard disk): a plug and play manager 403 , an object manager 405 , a partition manager 407 , and at least one volume manager 409 . The mount manager 401 is not limited to use with only devices that adhere to the partition manager and volume manager architectures described below. The mount manager 401 will manage any device which registers with the plug and play manager 403 which has some mechanism for reporting a device name and a unique identifier that is persistent between boots. The partition manager 407 and the volume manager 409 are shown and described for the sake of clarity in understanding the invention.
[0054] As described above, the mount manager 401 is responsible for associating redirected names with unique volume identifiers for logical volumes so that higher layers of the operating system and user applications can easily access the data on the logical volume. In the NT 5.0 embodiment, the mount manager 401 persistent data structure is stored in the NT registry. Alternate embodiments in which the persistent data structure is stored in non-volatile memory, such as battery-backed RAM or flash memory, will be readily apparent to one skilled in the art and are contemplated as within the scope the invention. The mount manager 401 also builds an in-memory data structure from the persistent data structure to decrease the time required to react to configuration changes in the system. In FIG. 4, data structure 441 is representative of both the in-memory and persistent data structures.
[0055] Because NT 5.0 is an object-based operating system, every device, either physical, logical or virtual, within the system is represented by a device object. The objects are organized into a device hierarchy in a global namespace controlled by the object manager 405 . The object manager 405 is also responsible for creating and maintaining symbolic link objects which serve as aliases for named device objects. The mount manager redirected name is represented in the namespace by a symbolic link object which contains the non-persistent device name of the corresponding logical volume. Thus, an “Open” command operating on a redirected name symbolic link object is the same as an “Open” command on the logical volume device object having the device name contained in the symbolic link object.
[0056] The partition manager 407 is responsible for handling device objects associated with logical divisions, partitions 412 , 413 , 414 and 415 , of a physical device 411 . The partitions 412 - 415 are created when the physical device 411 is formatted. The partition 412 is the entire physical device 411 while the partitions 413 - 415 are sub-divisions of the physical device 411 . A device driver (not shown) for the physical device 411 “enumerates” corresponding partition device objects 421 , 422 , 423 , and 424 when the computer is booted. The partition manager 407 and at least one volume manager 409 cooperate to create logical volumes from the partitions 413 - 415 . The composition of a logical volume is defined when the physical device is formatted, and can comprise one or more partitions. Additionally, one partition can comprise more than one logical volume. A unique volume identifier for the logical volume is stored in a privileged section of the physical device, or devices, that contain the partitions making up the logical volume The volume manager, or the device driver in the case of a removable device, responsible for the volume device object creates the unique volume identifier.
[0057] When the partition manager 407 is initialized, it requests notification from the plug and play manager of all volume managers 409 registered in the system. As each volume manager 409 registers, the plug and play system notifies the partition manager 407 which maintains a list of the volume managers 409 ordered by their arrival in the system.
[0058] When the physical device 411 is detected by the plug and play manager 403 upon booting the system, the plug and play manager 403 determines the formatted characteristics of the physical device 411 . The plug and play manager 403 loads the appropriate device driver to handle I/O access to the device. The device driver enumerates the partition device objects 421 - 424 used to access the data. As each partition device object 422 - 424 not representative of the entire device is enumerated by the device driver, the partition manager 407 “captures” the partition device object 422 - 424 before the driver registers the object with the plug and play manager 403 . The partition manager 407 presents each partition device object 422 - 424 to the volume managers 409 in the order in which the volume managers 409 arrived in the system. Because each partition device object 424 - 424 is associated with at least one logical volume, the volume manager 409 responsible for the corresponding logical volume(s) accepts the device object.
[0059] When a volume manager 409 has received a sufficient number of partition device objects corresponding to a particular logical volume, the volume manager 409 assigns a device name to the logical volume and enumerates a volume device object 431 - 432 for the logical volume containing the device name and the unique volume identifier for the logical volume. In the NT 5.0 embodiment, the device name is guaranteed to be unique only during a boot session, while the unique volume identifier is guaranteed to be unique across boot sessions. A counted string is used as the unique volume identifier in the NT 5.0 environment but a fixed length string can be equally applicable in other operating system environments. The counted string is as long as necessary to uniquely identify the device in the computer across multiple boot sessions. The volume device object 431 - 432 is stored by the object manager 405 in the device hierarchy by its device name. The volume manager 409 informs the plug and play manager 403 of the creation of the volume device object 431 - 432 .
[0060] Each volume device object 431 - 432 is presented to the mount manager 401 by the plug and play manager 403 . The mount manager 401 queries the volume device object 431 - 432 for its device name and unique volume identifier. Because of the indeterminate length of the unique volume identifier, the volume device object returns a byte count along with the string.
[0061] The mount manager 401 scans its internal data structure 441 (in-memory or persistent) looking for a matching entry for the unique volume identifier of the volume device object 431 - 432 . If none is found, this particular logical volume is new to the system, so the mount manager 401 assigns it a unique persistent mount name, and creates an entry for the logical volume in the mount manager data structure(s) 441 . In the NT 5.0 embodiment, the persistent mount name is based on a 16-byte globally unique identifier (GUID) with following format:
[0062] \??\volume{GUID}\
[0063] where \??\ designates the entry point in the global namespace device hierarchy for logical volumes and is synonymous with \DosDevices\. The hexadecimal representation of GUID is xxxxxxxx-xxxx-xxxx-xxxx-xxxxxxxxxxxx. A GUID is comparable to the UUID (universally unique identifier) specified by the Open System Foundation. The persistent mount name is generated by a mount manager subroutine called “CreateNewVolumeName.” After a new entry is created, or if a matching entry is found, the mount manager 401 requests that the object manager 405 create a symbolic link object to represent the relationship between the device name and the persistent mount name for the logical volume.
[0064] In order to facilitate the assignment of user-friendly drive letters to logical volumes, the mount manager data structure(s) 441 contains an entry for each of the twenty-four drive letters assignable to fixed hard disks, i.e., \DosDevices\C:\-\DosDevices\Z:\. The entries are sorted in alphabetical order. Upon the initial boot of the computer, only the logical boot volume is assigned a drive letter (such as \DosDevices\C:\). When a drive letter is requested for a logical volume by the plug and play manager 403 during the initial boot process, the mount manager 401 assigns the next available drive letter by storing the unique volume identifier in the corresponding entry in the data structure(s) 441 . The mount manager 401 requests that the object manager 405 create a symbolic link object representing the association between the drive letter and the volume device name.
[0065] On subsequent boots, each logical device is assigned its previous drive letter if one is present in the data structure(s) 441 . If a new logical device is introduced into the system during the boot process, the plug and play manager 403 must request the assignment of a drive letter. On the other hand, a new logical volume that is introduced during a boot session is automatically assigned the next available drive letter.
[0066] The plug and play manager 403 also informs the mount manager 401 when a logical volume will be temporarily removed from the boot session. The mount manager 401 deletes the device names, if present, from the data structure(s) 441 . The mount manager 401 also causes the object manager 405 to retire the symbolic link objects relating the volume device name and the drive letter and/or persistent mount name.
[0067] If the logical volume is reintroduced into the system during the same boot session, the volume manager will assign a different device name because the device names are guaranteed not to be reused during a boot session, but the unique volume identifier will be the same. Because the mount manager 401 has not deleted the unique volume identifier from the entries in the data structure(s) 441 , the mount manager 401 recognizes the logical volume if it is reintroduced and uses the data structure entries to re-create the same symbolic link objects as before so that consistency can be maintained.
[0068] If the logical volume is permanently deleted, its unique volume identifier and persistent mount name are also removed from the data structure(s) 441 and any now-empty entries are freed.
[0069] The partitions comprising a logical volume can change without deleting the volume if the logical volume is a mirrored volume that has been broken or a striped set that has been rebuilt. Under such circumstances, the device name does not change, but the unique volume identifier associated with the logical volume does. The volume manager 409 so informs the mount manager 401 which updates the data structures to reflect the change in the unique volume identifier.
[0070] The mount manager 401 communicates with the logical volume device objects 431 - 432 through an application program interface (API) having six calls:
[0071] QueryDeviceName (pointer to device object);
[0072] QueryUniqueId (pointer to volume device object);
[0073] QueryDesiredName (pointer to volume device object);
[0074] QueryUniqueIdChangeNotify (pointer to volume device object);
[0075] LinkCreated (pointer to volume device object); and
[0076] LinkDeleted (pointer to volume device object),
[0077] where the pointer to a device object is passed to the mount manager 401 by the plug and play manager 403 .
[0078] The interface between the mount manager 401 and volume device objects is identified by a GUID called the “mounted_device_GUID.” Any device object that declares support for the mounted_device_GUID must implement at least QueryDeviceName and QueryUniqueId.
[0079] QueryDeviceName and QueryUniqueId return the device name and unique volume identifier for the specified volume device object. QueryDesiredName returns a recommended redirected name(s) for the mount manager 401 to use in the event that the mount manager data structure(s) 441 does not yet contain any entries for the specified volume device object. A physical device that supports QueryDesiredName usually stores the desired name(s) in the same privileged area of the physical device as the unique volume identifier.
[0080] The mount manager 401 uses QueryUniqueIdChangeNotify to determine if the unique volume identifier for the specified logical volume device object has changed. Such a change is usually due to a change in the location for the volume but other circumstances can also cause the unique volume identifier to change. The mount manager 401 then updates the unique volume identifier in the data structure entries associated with the device name.
[0081] LinkCreated and LinkDeleted are used by the mount manager 401 to inform the volume device object of the creation and deletion of the redirected names and the symbolic link objects that reference the volume device object. A physical device that supports LinkCreated and LinkDeleted can use the information to update any redirected name(s) it has internally stored.
[0082] The mount manager 401 also provides an API with the plug and play manager 403 for managing the association between unique volume identifiers and the redirected names:
[0083] QueryPoints (drive letter/*, unique volume identifier/*, device name/*);
[0084] DeletePoints (drive letter/*, unique volume identifier/*, device name/*);
[0085] DeletePointsDBOnly (drive letter/*, unique volume identifier/*, device name/*);
[0086] CreatePoint (drive letter, device name);
[0087] NextDriveLetter(device name);
[0088] AutoDriveLetter;
[0089] FindFirstVolume; and
[0090] FindNextVolume (persistent mount name).
[0091] QueryPoints is called by the plug and play manager 403 to retrieve the entry in the mount manager data structure 441 for a logical volume. The plug and play manager 403 specifies the drive letter, the unique volume identifier, or any device name associated with the logical volume as search criteria to be used by the mount manager 401 (* is a “wild card” that matches all entries).
[0092] DeletePoints causes the mount manager 401 to return the corresponding entries from the data structure 441 and then perform the deletion steps described above to delete all entries and symbolic link objects associated with the volume device object. If a drive letter for a logical volume is explicitly deleted, i.e., not as the result of a wildcard operation, then an indicator associated with the unique volume identifier is set to alert the mount manager 401 that the logical volume is not to be assigned a drive letter if it is re-introduced into the system. DeletePoints is used when a logical volume is permanently deleted from the system or to disassociate a logical volume from some or all of its existing redirected names even though the logical volume itself is still present in the system. DeletePointsDBOnly operates as does DeletePoints but does not delete the symbolic link object(s). DeletePointsDBOnly is used when a logical volume is not deleted or removed and a user application is currently accessing data on the logical volume.
[0093] CreatePoint causes the mount manager 401 to assign the specified drive letter to a logical volume which previously had its drive letter deleted through either DeletePoints or DeletePointsDBOnly.
[0094] In order to preserve the historical drive letter assignments across boot sessions, the mount manager 401 does not automatically assign a drive letter to a logical volume during the boot process unless the logical volume had previously been assigned a drive letter. Therefore, the plug and play manager 403 uses NextDriveLetter to request that the mount manager 401 assign a drive letter to the logical volume associated with the device name specified in the call. NextDriveLetter returns the current drive letter and an indication of whether a drive letter was assigned. A drive letter cannot be assigned if no drive letter is available or if the logical volume represented by the device name is already assigned a drive letter. The plug and play manager 403 can also use AutoDriveLetter once the historical assignments have been made to request the mount manager 401 assign drive letters to all subsequent logical volumes upon arrival.
[0095] Because the mount manager 401 does not necessarily assign a drive letter to a logical volume, the mount manager 401 provides two calls that enumerate the persistent mount names present in the system. The symbolic link objects can then be used to determine the device name of the associated logical volume. FindFirstVolume returns the persistent mount name found in the first entry in the mount manager data structure 441 . FindNextVolume returns the persistent mount name in the entry following the entry containing the specified persistent mount name.
[0096] Thus, the NT 5.0 mount manager and supporting data structures guarantee the same redirected name(s) will be associated with the same logical volume across any number of boots or reconfigurations as long as the logical volume itself remains valid. The persistence of the redirected names guarantees that I/O commands on a redirected name are resolved through the symbolic links to the current device name for the correct logical volume so that the higher layers of the operating system and user applications do not have to be modified when the underlying physical structure of the computer changes.
CONCLUSION
[0097] A logical volume mount manager and supporting data structures have been described. The logical volume mount manager creates persistent redirected names for logical volumes in a computer system to enable symbolic links between the redirected names, which are used by the higher layers of the operating system and user applications, and non-persistent device names that identify the logical volumes to the lower layers of the operating system during a single boot session. Because of the level of indirection provided by the mount manager, the symbolic links can be tom down and rebuilt to point to different device names for the same logical volumes when necessary without requiring modification of the higher levels of the operating system and user applications. Thus, the mount manager and supporting data structures guarantee configuration consistency across boot sessions of the computer and ensure that access through a redirected name is resolved through the symbolic link to the current device name for the correct logical volume.
[0098] Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations of the present invention.
[0099] The terminology used in this application with respect to is meant to include all operating system and programming environments capable of implementing the mount manager and supporting data structures as described above. Therefore, it is manifestly intended that this invention be limited only by the following claims and equivalents thereof. | A mount manager and supporting data structures enable automatic identification and re-establishment of logical volumes on non-removable storage devices in a computer system across multiple reboots and reconfigurations. The mount manager generates a redirected name for a new logical volume when a unique volume identifier is presented to the mount manager by the operating system. The mount manager stores the unique volume identifier and the associated redirected name in a persistent mount manager data structure The mount manager establishes a symbolic link between the persistent redirected name, which is used by higher layers of the operating system and user applications to address the logical volume, and a non-persistent device name used by the operating system. During the boot process, the mount manager uses the data structure entries identified by the unique volume identifiers of the arriving logical volumes to reconstruct the symbolic links so that references to the redirected name will resolve to the correct non-persistent device name. When the system undergoes physical reconfiguration, the mount manager associates an existing redirected name to a different non-persistent device name if the unique volume identifier is present in the data structure. In this fashion, logical volumes can be removed and restored in the computer without the knowledge of higher layers of the operating system and user applications. Optionally, the mount manager builds an in-memory data structure from the persistent data structure to increase the speed of the identification process. | 8 |
FIELD OF THE INVENTION
This invention concerns an image-guidance system for non-invasive irradiation treatment of patients.
BACKGROUND ART
Historically, the treatment of cranial lesions initially proceeded by way of surgical processes—gaining access to brain tissue by way of apertures created in the skull. Clearly, great accuracy was needed in such surgery, and the stereotactic frame was developed for this purpose by Lars Leksell in the late 1940s. This assisted surgeons by providing a precise frame of reference within which to operate. Typically, a stereotactic frame attaches to a patient via pins that extend through the soft anatomy under local anaesthesia and abut the bone to provide a frame of reference that is fixed relative to the rigid body that is the skull. Given that the brain tissue within the skull exhibits relatively little movement during normal movement of the human body, this allowed accurate positioning of surgical instruments relative to the brain tissue and its associated structures.
Leksell then sought to extend the ambit of intracranial surgery to areas that were difficult to reach via surgical methods, such as the base of the skull. To do so, he developed the Gamma Knife, a multi-source radiotherapy apparatus. This comprises 201 Co 60 sources mounted on a fixed support, usually hemispherical or cylindrical in form. The sources are distributed about the support, and each is collimated so as to produce a beam that is directed at a single defined point. Thus, the total dose at that point is provided by all the sources, whereas away from that point the total dose is at most that from one or only a small number of sources.
To proceed with treatment via a Gamma Knife, a stereotactic frame is affixed to the patient's bony anatomy in order to fix the position of the patient (and hence the lesion) relative to the device. The volume of lesion to be treated (henceforth referred to as the target) is localized using diagnostic imaging modalities such as computed tomography (CT) and magnetic resonance imaging (MRI) while the frame is in place, and the localization coordinates are then related to the frame. Treatment of the target is then achieved by careful positioning of the frame (with the patient affixed) with respect to the irradiation unit. The frame is therefore a longstanding and essential part of the treatment process for intracranial lesions.
SUMMARY OF THE INVENTION
The use of a stereotactic frame has two major weaknesses:
(i) the frame is invasive and cannot remain in place for long periods of time. It is therefore not readily usable for treatments that require multiple exposures over a prolonged time course (multiple days), usually referred to as fractionated treatment. This limits the type of lesion that can be treated to those that can be treated with a single dose.
(ii) the approach assumes a rigid transformation between the device and the relevant target together with the surrounding normal anatomy. This is a valid assumption in respect of lesions within the skull, but fails if applied to a wider area such as the neck and upper shoulder. This therefore also limits the type of lesion that can be treated, to those within the volume that can be treated as a rigid body.
This invention seeks to provide a volumetric-based x-ray image-guidance system for a multi-source irradiation unit, suitable for non-invasive irradiation treatment of conditions such as cancerous lesions in the brain, eye, head and neck regions, i.e. all the regions that are accessible to multi-source units and not necessarily just those that act as a rigid body with the skull. By relying on image-guidance for locational accuracy, the stereotactic frame can be made unnecessary. Some form of immobilisation of the patient's anatomy is likely to be needed; a stereotactic frame may be used for this purpose but need not be the sole choice. An alternative form of fixation may be suitable, such as the less invasive jaw clamp disclosed in WO96/036292A1.
Whilst such fixation methods may not offer the same positional reproducibility when a patient returns to the radiotherapy apparatus, this can be compensated for by the image-guidance system. In effect, the fixation system only needs to keep the patient still during treatment rather than provide a spatial frame of reference.
The incorporation of an imaging-guidance system into a multi-source irradiation routine would therefore allow for (i) non-invasive treatments that may be extended over longer periods, thus potentially increasing the biological effect of the treatment for certain lesions, (ii) non-invasive treatments that can be applied over a wider area, i.e. the head, neck and potentially the upper shoulder area, and (iii) more accurate localization of the target throughout the treatment process.
There is, of course, a problem in doing so. Specifically, the geometry of a Gamma Knife is not suited to the provision of an image guidance system. The array of sources around the patient and the associated shielding and collimation will obstruct any form of imaging that is presently available.
The present invention therefore provides a radiotherapeutic apparatus, comprising an array of therapeutic radiation sources, each in a fixed location and directed towards a common convergence point, an investigative radiation source and a detector therefor, moveable in synchrony to enable creation of a volumetric image of a region around an imaging point spaced from the common convergence point, and supported via a mount that is fixed relative to the common convergence point and articulations between the mount and the investigative source and detector so as to permit the movement thereof, and a patient support indexable between a first position, and a second position displaced from the first position by a displacement equivalent to that between the imaging point and the common convergence point.
In this way, the patient can be imaged whilst in place on the patient positioning system and then moved through a known displacement into the array of therapeutic sources. Positional accuracy is maintained since the displacement is known and therefore the location of the convergence point relative to the volumetric image is known. Smaller adjustments in order to bring one or more features in the volumetric image into register with the convergence point can be made via the patient support or otherwise.
The therapeutic radiation sources can be Co 60 sources, as these are well characterised and have proven reliability. Other sources could alternatively be employed.
The articulations are the part which allow the imaging system to be placed in front of the therapeutic system during an initial imaging step, and then moved away to allow access to the (usually) hemispherical or cylindrical therapeutic volume. These articulations preferably comprise a C-arm, on opposing ends of which are mounted the investigative source and the detector. The C-arm can be attached to the mount via a linkage or linkages that include a linear actuator, for example, to permit such movement in a space-efficient manner.
Alternatively, or in addition, the C-arm can be attached to the mount via a rotational joint. If the arm is attached via a rotation joint only, then it is preferred that the articulations further comprise an arm extending from the mount to the rotational joint, thereby spacing the rotational joint from the mount, and allowing the C-arm to be rotated so as to collect the data necessary for a volumetric image and to place the C-arm structure out of the way of the therapeutic volume.
Alternatively, the arm can be attached to the mount via a linear actuator. In this way, the linear actuator can be employed to clear the C-arm out of the way and the rotational joint employed to rotate the imaging system as required to generate a volumetric image. Thus, the linear actuator can be arranged to move the arm from a first position in which the arm is located between the patient support and the array of therapeutic sources, and a second position in which the arm is clear of the space between the patient support and the array of therapeutic sources.
In a further alternative, the arm can be attached to the mount via a further rotational joint. This can be arranged to move the arm from a first position in which the arm is located between the patient support and the array of therapeutic sources, and a second position in which the arm is clear of the space between the patient support and the array of therapeutic sources.
This invention therefore allows the volumetric image to be analysed to determine localization information in respect of the target site, and for the position of the patient support to be adjusted in dependence on the localization information to resolve discrepancies between specified and actual targeting locations. A suitable control means is preferably provided in order to do so.
The adjustment means can be arranged to adjust the position of the patient support in dependence on motion of the investigative source and detector. This can assist in accommodating the investigative system as they rotate around the patient support, while keeping the patient within the field of view of the investigative system. Generally, the investigative source and detector move in a rotational manner through an angle φ, in which case the adjustment means preferably moves the patient support in a linear manner by a distance proportional to k.sin(φ+α) where k and α are constants. Movement of the patient support towards the detector is preferred since this assists in keeping the patient in the useful field of view of the investigative system.
Accordingly, the present invention allows for an image-guided, non-invasive multi-source irradiation system comprising a multi-source irradiation subsystem comprising robotically driven radiation sources, capable of high-precision treatment of cranial and head-and-neck lesions; a volumetric x-ray imaging subsystem comprising one or more radiation detectors and x-ray tubes, capable of high-resolution (100 μm) imaging but is not limited to only include high-resolution imaging; a patient positioning subsystem; and a control system for communication of localization information between the subsystems.
Such a volumetric imaging subsystem can yield reconstructed images that have high geometric fidelity (relative and absolute) at resolutions approaching 100 μm at all points in the field-of-view. The image acquisition trajectory (rotations and translations) can be determined with performance consistent with the spatial resolution and the field of view.
Target localization information, as determined from these images, can be transferred or otherwise communicated via a suitable electronic means to the system's control system, and discrepancies between specified and actual targeting can be resolved through relative, compound movement of the sources, shielding, and the patient. This process is ideally active for positioning and monitoring of internal targets before, during, and after the irradiation process.
A secondary optical monitoring subsystem can be integrated with the unit, to provide high resolution temporal monitoring of the relative position of objects in the irradiation reference frame and the external surrogates of the patient's internal anatomy. Thus, the above-defined radiotherapeutic apparatus can further comprise an optical detector disposed to view a patient in the patient support.
The optical detector can be a video camera such as a stereoscopic video camera. It is preferably mounted on an arm secured to the patient support; the aim is to detect movement of the patient relative to the support and therefore mounting the optical detector on the patient support itself will simplify this considerably. The arm can be articulated, to aid ingress and egress of the patient.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the present invention will now be described by way of example, with reference to the accompanying figures in which;
FIG. 1 is an illustration of the control system;
FIG. 2 is a sketch of a C-arm x-ray imaging configuration with orbital rotation;
FIG. 3 is a sketch of the coordinate system for the entire unit, outlining possible bearing locations on which to mount the imaging subsystem;
FIG. 4 shows the C-arm of FIG. 1 in place on the unit;
FIG. 5 is a sketch of a C-arm x-ray imaging configuration with angular rotation and tilt angle;
FIG. 6 shows the C-arm of FIG. 5 in a rotated state;
FIGS. 7 a and 7 b are sketches of an x-ray-tube-detector system mounted on a linear rail, form the front and from the side respectively;
FIGS. 8 a , 8 b and 8 c show the system of FIGS. 7 a and 7 b affixed to the front of a radiation unit. FIG. 8 a shows the system in a parked or stowed state, FIG. 8 b shows the unit in an active or deployed state, and FIG. 8 c shows the unit in operation
FIG. 9 is a sketch of an x-ray-tube-detector system that can be parked or deployed using a rotational bearing affixed to the front of the radiation unit.
FIG. 10 shows the arrangement of the rotational bearing;
FIG. 11 is an isometric sketch of the two rotational bearings involved;
FIGS. 12 a to 12 d and 13 a to 13 d are renderings of the linear-rail-based x-ray system, in parked and various deployed positions.
FIGS. 14 a to 14 d , 15 a to 15 f , and 16 a to 16 e are views of various single-plane acquisition trajectories encompassing varying source-to-axis and detector distances, fixed versus moving object.
FIGS. 17 a to 17 d are 2-dimensional views of a two-source, 360-degree image acquisition geometry.
FIGS. 18 and 19 are sketches of the real-time optical monitoring system that can track markers placed on the patient and on the frame in 3D, for the side and the rear respectively.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The object of the present invention is to design a volumetric x-ray imaging system, that can be integrated with a multi-source gamma irradiation unit for on-line imaging and target localization.
The present invention achieves this object via an x-ray tube/detector subsystem mounted to the irradiation unit or a nearby structure and capable of fast rotation, acquisition of 2D images, and 3D image reconstruction. The detector preferably has a rectangular surface, of which the length and width define a cone-beam and fan-beam angle, respectively. Rotation of the device is performed around the z-axis, defined as the couch's long axis, with the long side of the detector (cone angle) parallel with the rotational plane. The volumetric imaging subsystem should be compact and made to adapt to the specifications of the multi-source irradiation unit, while maintaining a high-level of precision. Under these constraints, various embodiments of the imaging subsystem are possible.
The control structure of the entire system is sketched out in FIG. 1 , and overview of the integrated imaging guidance system. The control system handles data from the volumetric imaging and real-time monitoring subsystems to the irradiation subsystem based on the geometric and dosimetric objectives. Data flow is bi-directional: to and from the control system. Data from the volumetric imaging and real-time monitoring subsystems are fed into the control system, which then may update the patient position or source configuration with respect to the demands of the dosimetric and geometric objectives.
A first embodiment to be described is a C-arm system as shown in FIGS. 2 to 4 , with orbital rotation around the z-axis. Orbital rotation in this context refers to rotation in the direction of the C-arm circumference, as is apparent from FIGS. 3 and 4 . Given the constraints imposed by the nature of the C-arm, rotation of around 195 degrees is possible. Angular rotation in the context of this embodiment refers to rotation perpendicular to the direction of the C-arm circumference—i.e. about the z axis.
Thus, this embodiment employs a C-arm 10 supported on a mount 12 . The C-arm is part-circular in shape, and is supported on a linear actuator within the mount 12 . This allows the C-arm 10 to slide within the mount 12 so as to create the necessary rotation of the C-arm 10 through an angle θ. On either end of the C-arm 10 are a diagnostic source 14 and a two dimensional flat panel detector 16 . As the C-arm rotates, the source 14 and detector 16 sweep an arc of nominally 180°.
FIG. 3 shows the therapeutic radiation unit 18 . An array of Co 60 sources are arranged in a cylindrical array around a collimator (not shown). The collimator is cylindrical in nature and is a solid section of tungsten in which a plurality of collimator bores are formed, one or more for each source. The bores are angled so that each aims at a single common convergence point, meaning that the convergence point receives a very high dose, from effectively all sources. The sources can be moved away from their associated collimator bore or bores, to shut off the radiation source while the patient be being aligned, and then moved into place to apply the dose. An aperture 20 allows the head region of a patient to be placed within the radiation unit 18 to allow the application of a therapeutic dose. The mount 12 can be placed above the aperture as shown at 12 a or below the aperture 12 b , or otherwise. FIG. 4 shows the system in place, mounted below the aperture 20 at 12 b . A patient 22 is supported on the patient support 24 . The support has been positioned so as to place the head of the patient 22 in the arc of the C-arm 10 . Thus, by rotation of the C-arm 10 , a volumetric CT image of the patient can be created. The patient support can then be indexed to a further position in which the patient 22 projects in through the aperture 20 and their head is within the radiation unit for treatment.
Given that the movement of the patient has been entirely under the control of the patient support 24 , the displacement is known and the volumetric CT image can be correlated with the current position of the patient 22 . This allows fine adjustment of the patient position via the patient support 24 to place the target structures at the isocentre or convergence point of the radiation unit and allow treatment.
Depending on the circumference of the C-arm, the necessary orientation may be limited or prohibited by the positioning of the irradiation unit and/or the patient support 24 . A possible solution is to employ a tilt angle in the yz-plane, as shown in FIG. 3 . The C-arm 26 is this time mounted on a support arm 28 via a rotational joint 30 to permit rotation of the source 32 and detector 34 between the positions shown in FIGS. 5 and 6 , between which there is a 180° rotation. The support arm 28 positions the C-arm 26 forward of the radiation unit 18 and with the plane of view of the source 32 and detector 34 tilted forwards. Thus, rotation of this nature allows a CT image of the patient's head to be captured.
Due to the potentially limited angle of rotation in the orbital C-arm rotation case, and the constrained space in the angular C-arm rotation case, a further embodiment of the x-ray imaging system is shown in FIGS. 7 and 8 . In this variant, the x-ray tube (source) 100 and detector 102 are connected along a rotating gantry 104 , which is in turn mounted to a support arm 106 via a belt-driven rotational bearing 108 . The support arm 106 is mounted to the irradiation unit 110 via a linear bearing 112 allowing bodily horizontal movement of the support arm 106 . This allows the system to be parked or deployed as necessary.
Thus, as shown in FIGS. 7 a and 7 b , the cone beam emitted by the source 100 and detected by the detector 102 is able to cover the general volume of a patient's head 114 . Rotation of the gantry 104 around the bearing 108 then allows a number of such images to be collected and a volumetric CT image to be prepared.
Located in this position (relative to the patient), the gantry 104 , source 100 and detector 102 are ideally placed to acquire images of the patient but are also located so as to block access to the irradiation unit 110 . Therefore, the linear bearing 112 allows the entire sub-assembly to be bodily moved to one side so that it is located clear of the access aperture 116 of the irradiation unit 110 as shown in FIG. 8 a , allowing the patient on a patient support to be indexed forwards into the irradiation unit 110 by a known displacement. When needed, the linear bearing 112 can be operated to bring the sub-assembly into place in front of the access aperture 116 and acquire images.
FIG. 8 c shows that when in place in front of the access aperture 116 , the gantry 104 can rotate around the rotational bearing 108 in order to carry the source 100 and detector 102 around a circular path about the target volume.
FIGS. 9 to 11 depict sketches for an embodiment based on a rotational bearing. Again, the x-ray tube (source) 100 and detector 102 are connected along a rotating gantry 104 , which is in turn mounted to a support arm 106 via a belt-driven rotational bearing 108 . However, in this embodiment the support arm 106 is mounted to the irradiation unit 110 via a second rotational bearing 118 at its upper end, allowing bodily rotation of the support arm 106 about that upper end. This allows the system to be parked or deployed as necessary.
The beam geometry is of course the same as that shown in FIGS. 7 a and 7 b . Rotation of the gantry 104 around the bearing 108 again allows a number of x-ray images to be collected and a volumetric CT image to be prepared.
The gantry 104 , source 100 and detector 102 can be moved out of the way of the access aperture 116 by rotation of the second rotational bearing 118 which will rotate the entire sub-assembly so that it is located clear of the access aperture 116 of the irradiation unit 110 , as shown in FIG. 8 a . This then allows the patient on a patient support to be indexed forwards into the irradiation unit 110 by a known displacement. When needed, the further rotational bearing 118 can be operated to bring the sub-assembly into place in front of the access aperture 116 and acquire images.
FIG. 9 also shows that when in place in front of the access aperture 116 , the gantry 104 can rotate around the rotational bearing 108 by an angle θ in order to carry the source 100 and detector 102 around a circular path about the target volume.
FIG. 10 shows the arrangement of the two rotational bearings 108 , 118 on either end of the support arm 106 . Rotation about the further rotational bearing 118 transports the support arm 106 between the parked position illustrated in FIG. 10 and the deployed position 120 shown in dotted lines. A stop 122 is positioned on the irradiation unit 110 adjacent the support arm 106 when the latter is in the correct deployed position 120 , to provide a firm index point. This can be a rigid stop that simply prevents further movement of the support arm 106 , or it can also incorporate a detector for the arm 106 such as a proximity detector or a microswitch to provide feedback that the support arm 106 is in the correct position.
FIG. 11 shows how independent rotation of both rotational bearings can be easily provided for. A pair of concentric shafts 124 can be provided, the outer shaft passing through the further rotational bearing 118 to be attached to and drive the support arm 106 , and the inner shaft passing through the support arm 106 to drive an upper toothed wheel 126 located in front of the support arm 106 , mounted on the inner shaft concentric with the further rotational bearing 118 . This then drives a lower toothed wheel 128 mounted on a freely rotating shaft 130 at the lower end of the support arm 106 , via a belt or chain drive 132 connecting the two toothed wheels 126 , 128 . The gantry 104 is then mounted on the freely rotating shaft 130 .
In this way, both rotational bearings 108 , 118 can be controlled independently. The outer shaft 124 can be driven to rotate the support arm 106 and move the sub-assembly into or out of position, and the inner shaft 124 can be driven, once the sub-assembly is in place, in order to rotate the gantry 104 .
Of course, after 90° of rotation of the further rotational bearing 118 , the upper toothed wheel 126 will no longer be above the lower toothed wheel 128 but will be to one side thereof. Further rotation of the further rotational bearing 118 , if this is permitted, will place the lower toothed wheel 128 above the upper toothed wheel 126 . Nevertheless, the lower toothed wheel 128 will spend most of its time below the upper toothed wheel 126 and the names have been chosen for this reason; they are not intended to imply any form of permanent spatial relationship.
FIGS. 12 a to 12 d and 13 a to 13 d depict a computer rendering of a system according to the present invention using a linear rail, showing the system when parked and when deployed. FIGS. 12 a to 12 d show various rotations of the gantry arm, and FIGS. 13 a to 13 d show varying degrees of tilt. Dealing first with FIG. 12 , FIG. 12 a shows the system parked and FIG. 12 b shows the system deployed and at zero rotational angle. FIG. 12 c shows the system deployed at a small angle of rotation, and FIG. 12 d shows the maximum rotation angle allowed before the tube hits the couch.
Thus, FIG. 12 a illustrates a patient support 150 in front of a Gamma Knife irradiation apparatus of which the front panel 152 is shown, including an access aperture 154 through which a patient can be projected in order to receive a dose or doses. The patient support 150 includes a shoulder restraint 156 , shaped to fit a patient's shoulders. A patient is placed on the support 150 with their shoulders just behind the restraint 156 ; the apparatus is programmed so that the patient support can move as required but without allowing the restraint 156 to strike any other object. Given that we know the patient is behind the restraint 156 , this prevents the patient's shoulders from striking any objects during movement of the support 150 .
A linear actuator 158 is attached to the front of the irradiation unit 152 . This comprises a rail 160 that is fixed in place on the front panel 152 above and to one side of the aperture 154 , and a shuttle 162 that can be driven along the rail 160 in either direction. An arm 164 extends downwardly from the shuttle 162 and has a rotational bearing 165 at the same height as the isocentre of the irradiation unit. A gantry 166 is attached to the rotational bearing 165 , and is arranged in the general form of a C-arm gantry, i.e. with an investigative x-ray source 168 at one end and a flat panel detector 170 at the other. The source 168 and the flat panel detector 170 are mounted forward of the gantry 166 and with their axes generally parallel to the gantry 166 ; thus the detector 170 is located to receive the radiation emitted by the source 168 after attenuation by any matter in the open space between the two.
FIG. 12 a shows the apparatus in the parked position, i.e. with the shuttle 162 to one end of the rail 160 , away from the aperture 154 . FIG. 12 b shows the system after the shuttle is moved to a position along the rail that places the arm 164 directly in front of the aperture 154 and the rotational bearing 165 directly in front of the isocentre. The result of this is that the centre of rotation of the source 168 and detector 170 is now co-incident with the isocentre except for a longitudinal displacement. That displacement is however known, as it is fixed by the dimensions of the various components of the apparatus.
It will be noted that the arm 164 and the gantry 166 are dimensioned so that in the deployed position shown in FIG. 12 b with no rotation around the rotational bearing 165 , the detector 170 is just above the support 150 . Thus, from this position, the gantry 166 can be rotated around the rotational bearing 165 to rotate the source 168 and detector 170 around the patient acquiring x-ray images from a variety of directions as it does so. After a small rotation, the gantry reaches the position shown in FIG. 12 c . Eventually, the gantry reaches a maximum angle shown in FIG. 12 d at which the source 168 is about to strike the support 150 , shown in FIG. 12 d . In order to limit the necessary width of the investigative x-ray beam and thereby ensure its quality, the source 168 is mounted further from the rotational bearing 165 than the detector 170 . This maximises the distance between the source 168 and the patient, but means that a full 360° rotation is not possible. Thus, after rotation to the maximum position shown in FIG. 12 d , the gantry 166 can be rotated in the reverse direction until a corresponding maximum point in the other direction is reached.
The distance between the rotational bearing 165 and the detector 170 is of course limited by the height difference between the isocentre and the top of the support 150 , so that the detector 170 can clear the support 150 as shown in FIG. 12 b and noted above. In any case, so long as the detector 170 is below the patient, the precise distance is not as crucial. It is for this reason that (as shown in FIG. 12 a ) the device is parked with the detector at the bottom and the source at the top.
After images have been collected in this way, they can be passed to a suitable computing means to construct a volumetric CT image. The gantry 166 can be returned to the upright position shown in FIG. 12 b and the shuttle 162 moved along the rail 160 to park the apparatus as shown in FIG. 12 a . The apertures 154 is not clear, and the patient can be indexed forward by movement of the support 150 to place the patient's head and shoulders within the irradiation unit, by a displacement equal to that between the centre of rotation of the source 168 and detector 170 and the isocentre of the irradiation unit. The location in the patient that is at the centre of the volumetric CT image is therefore now at the isocentre; fine adjustments can be made via the patient support 150 to place the desired structures at the isocentre prior to delivering a dose. In this way, image-guided multi-source radiotherapy is achieved.
FIGS. 13 a to 13 d show a further embodiment demonstrating how a tilt angle can be incorporated. Each figure includes an isometric view and a view from the side. This embodiment employs a source 170 located at the lower end of the gantry 172 and a detector 174 at the upper end. The source 170 and detector 174 are located at nominally equal distances from the rotational bearing 176 on which the gantry 172 is mounted, to allow a 360° rotation of the gantry arm. Depending on the precise cone beam angle of the source, this may involve some sacrifice of field of view (or acceptance of a wider beam divergence) in return for a 360° rotation. This embodiment differs however from that of FIG. 13 in that the rotational bearing includes additional articulations to permit a forward tilt of the gantry 172 as illustrated, with the upper end of the gantry becoming further distant from the irradiation unit 178 and the lower end closer. This allows better clearance beneath the patient support 180 in that the effective centre of rotation of the source 170 and detector 174 is moved forwards relative to the lower end of the gantry arm 172 which does not therefore need to pass directly beneath the patient's head.
FIGS. 13 a to 13 d show various renderings of the system including a tilt angle. The specific angles are:
FIG.
Tilt angle
Rotation angle
13a
0°
0°
13b
10°
0°
13c
20°
0°
13d
20°
30°
The embodiment described above with respect to FIGS. 12 a to 12 d involved placing the centre of rotation of the imaging system comprising the source and detector in line with the isocentre of the irradiation system (albeit displaced therefrom) and generally at the centre of the object to the imaged. This is not essential, however. In terms of rotational trajectories, there are several proposed variants using a single x-ray source as illustrated in FIGS. 14 to 16 . The first variant, shown in FIGS. 14 a to 14 d , involves a simple rotation of the source 200 and detector 202 around a fixed isocentre 204 and a stationary object 206 located above a support 208 and generally corresponds to that of FIG. 12 . The source-to-axis distance (SAD) is 1000 mm while the axis-to-detector distance (ADD) is 200 mm. A fan angle of approximately 28° and a cone angle of approximately 37° will then suffice. As seen in the figure, 260° of rotation are permitted with this geometry, and the resulting magnification is approximately 1.2. FIGS. 14 a to 14 d show different angles of rotation φ as follows:
FIG.
φ
14a
50°
14b
90°
14c
135°
14d
180°
in which φ=0° is defined as the position in which the source is directly below the isocentre. Accordingly, in the parked position and in the position in which the imaging system is ready to move into the parked position, φ=180° as shown in FIG. 14 d . Thus, the system can rotate within the parameters 50°≦φ≦310°.
One single-source variant on the above arrangement involves simultaneous lateral shifting of the patient 206 to avoid patient-imaging system collision. The resulting magnification in these cases varies as a function of rotation angle. In the “tube over” design shown in FIGS. 15 a to 15 f , the source rotates over the patient through an angle of 280°. The SAD is 550 mm and the ADD 200 mm, whilst the cone angle is approximately 56° and the fan angle approximately 44°. As the source and detector rotate about a fixed axis, the object 204 being imaged is moved towards the detector in the x direction by manipulation of the support 208 as a function X shift =−40 sin(φ), so at an angle of 270° or 90° the maximum shift occurs (+/−40 mm). A generic form of this equation is of course x shift =k.sin(φ+α) where k and α are constants; k will depend on the scale of the apparatus and α will depend on the chosen orientation of φ=0°.
FIGS. 15 a to 15 f show different rotation angles as follows:
FIG.
φ
X shift
15a
42°
−26.8 mm
15b
60°
−34.6 mm
15c
90°
−40 mm
15d
120°
−34.6 mm
15e
150°
−20 mm
15f
180°
0 mm
from which it can be seen that shifting the object to be imaged allows it to remain largely within the cone beam despite the limitations of available space and the rotation of the beam.
In the “tube under” design ( FIGS. 16 a to 16 e ), the source rotates under the patient through a maximum angle of 240 degrees. To fit the source 200 beneath the patient 206 requires some adjustment of the imaging system geometry, and in this case the SAD is 310 mm, the ADD 310 mm, the cone angle approximately 66°, the fan angle approximately 52°, and the magnification factor 1.32 to 2.0. This permits up to 240° of rotation. As the source and detector rotate about a fixed axis, the object 206 being imaged again moves towards the detector in the x direction as a function x shift =610 sin(φ), so at an angle of 270° or 90° the maximum shift occurs (160 mm).
FIGS. 16 a to 16 e show different rotation angles as follows:
FIG.
φ
X shift
16a
60°
138.6 mm
16b
90°
160 mm
16c
120°
138.6 mm
16d
150°
80 mm
16e
180°
0 mm
from which it can again be seen that shifting the object to be imaged allows it to remain largely within the cone beam despite the limitations of available space and the rotation of the beam.
A two-source approach, as illustrated in FIG. 17 , allows for increased coverage of the imaged volume while using a compact source-to-detector setup which also facilitates a 360° rotation of the source and detector. Thus, a pair of side-by-side sources 200 a and 200 b each direct a divergent beam towards a single flat panel detector 202 . The detector 202 is generally aligned with the mid-point of the two sources 200 a , 200 b and the sources each emit a slightly asymmetrical cone beam that is wider in one direction towards the axis of the other source, so that each covers the whole of the area of the detector 202 . This allows a SAD of 290 mm and an ADD of 200 mm. The sources are spaced by 200 mm, and each is thus 100 mm from the central axis of the detector 202 . FIGS. 17 a to 17 d show this arrangement at various rotations as follows:
FIG.
φ
17a
0°
17b
45°
17c
90°
17d
180°
With this geometry, the greater degree of compactness achieved permits a 360° rotation.
The various aspects of the above embodiments can of course be combined. For example, the various rotational geometries described can also be applied with the source-detector axis tilted forward as illustrated in FIG. 5 , 6 or 13 . To maximize coverage of the imaged volume, this tilt angle can also be made to vary as a function of rotational angle. Further, the variable x-offset of FIGS. 15 and 16 can be combined with the dual source of FIG. 17 or otherwise.
The x-ray volumetric imaging subsystem, as described above, can be used for accurately localizing the position of internal anatomical structures. An optical monitoring subsystem can also be included for continuous, real-time 3D tracking of displacements during the entire treatment process, including the volumetric imaging. This will allow a continuous optical confirmation that the patient did not moved relative to the support between imaging and treatment. Markers can be placed on the patient and an immobilization frame, and their three-dimensional position automatically tracked by the optical system.
FIGS. 18 and 19 illustrate such a system. The camera 300 is mounted on a flexible arm 302 , which is in turn mounted to the treatment couch 304 . Thus, a constant and fixed frame-of-reference system is established between the camera 300 , patient 306 , and immobilization frame 308 as the couch is moved in and out of treatment or imaging positions. This subsystem provides increased confidence and accuracy of patient setup and immobilization. Visible markers 310 , 312 allow for simplification of the image analysis. As an alternative a fringe pattern can be projected onto the patient 306 , such as from a projector co-located with the camera 300 ; this will ensure that the viewed image changes dramatically if the patient 306 moves. Of course, it is possible to simply view the patient 306 and detect movement.
The camera 300 is stereoscopic to allow more accurate motion detection, and the support arm 302 is flexible via integral ball joints 314 to allow the camera to be moved out of the way during ingress and egress of the patient 306 .
Such a vision system could of course be employed with other radiation therapy and/or imaging systems.
It will of course be understood that many variations may be made to the above-described embodiment without departing from the scope of the present invention. For example, a linear actuator or linear guide could be attached to the roof of the treatment room, performing a linear or rotational movement. This would take the investigative source and detector to the common convergence point with very high repeatability before performing imaging. Thereafter, it could be moved back to allow the patient positioning system to perform the relative movement of the patient to the treatment focus point. Also, if space is limited it may be necessary to use a detector which is shorter along the long axis of the patient than might be required to image all the required parts of the patient. In this case, the patient would need to be moved between imaging, and a number of volumetric image sets combined to form an extended field of view. | A highly compact, high-performance volumetric imaging system is proposed, that is integrated with a multi-source Cobalt-60 gamma irradiator for high throughput, high accuracy and minimally invasive fractioned treatments of intracranial, orbital and head-and-neck targets. | 0 |
BACKGROUND OF INVENTION
An embodiment relates generally to autonomous parking a vehicle.
Parallel parking a vehicle between two vehicles is often a difficult task for a driver. Semi-autonomous parking systems are vehicle based systems designed to aid the driver in performing difficult parking maneuvers such as parallel parking. Such systems either guide the driver in steering the vehicle through its intended trajectory path or increase/decrease power steering efforts when the driver of the vehicle has deviated from the intended trajectory path. In such systems, the driver is required to control the steering efforts or make some adjustments to the steering wheel.
SUMMARY OF INVENTION
An advantage of an embodiment of the invention provides for an autonomous parallel parking system that smooths the profile of the parking trajectory based on arc circles and clothoids. The autonomous parallel parking system provides path planning for either a one cycle steering maneuver or a two cycle steering maneuver.
An embodiment contemplates a method of determining a vehicle path for autonomously parallel parking a vehicle in a space between a first object and a second object in response to an available parking distance between the first object and second object. A distance is remotely sensed between the first object and the second object. A determination is made whether the distance is sufficient to parallel park the vehicle between the first object and the second object based on a threshold. A first position to initiate a parallel parking maneuver is determined. A second position within the available parking space corresponding to an end position of the vehicle path is determined. A first arc shaped trajectory of travel is determined between the first position and an intermediate position, and a second arc shaped trajectory of travel is determined between the second position and the intermediate position. The first arc shaped trajectory is complementary to the second arc shaped trajectory for forming a clothoid which provides a smoothed rearward steering maneuver between the first position to the second position. A steering actuator is controlled to follow the determined vehicle path.
An embodiment contemplates an autonomous parking system for parallel parking a vehicle between a first object and a second object. A sensing device for detecting objects proximate to the driven vehicle, the sensing device provides signals configured for determining a space between the first object and the second object. A controller receives signals identifying the space between the first object and the second object. The controller autonomously controls steering of the vehicle for parallel parking the driven vehicle. The controller determines a first arc shaped trajectory of travel between a first position and an intermediate position. The first arc shaped trajectory is cooperatively formed from at least one clothoid and an arc circle. The controller determines a second arc shaped trajectory of travel between a second position and the intermediate position. The second arc shaped trajectory is cooperatively formed from at least one clothoid and an arc circle. The first arc shaped trajectory is complementary to the second arc shaped trajectory at the intermediate position for forming a smoothed transition rearward steering maneuver from the first position to the second position. The controller utilizes the smoothed transition rearward steering maneuver for autonomously parallel parking the vehicle driven vehicle.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a block diagram illustrating an autonomous parallel parking system according to an embodiment.
FIG. 2 is a geometric schematic illustrating vehicle path planning for applying a one cycle steering strategy maneuver according to an embodiment.
FIG. 3 is a geometric schematic of a vehicle according to an embodiment.
FIG. 4 is a graph of a road wheel angle as a function of distance traveled by a vehicle according to an embodiment.
FIG. 5 is a graph of a smoothed road wheel angle profile according to an embodiment.
FIG. 6 is a graphical representation of trajectory of the vehicle along a smoothed path profile according to an embodiment.
FIGS. 7-8 is a geometric schematic illustrating vehicle path planning for applying a two cycle steering strategy maneuver according to an embodiment.
FIG. 9 is a geometric schematic illustrating initial vehicle positioning relative to an available parking space according to an embodiment.
FIG. 10 is a diagram illustrating acceptable initial vehicle starting positions according to an embodiment.
DETAILED DESCRIPTION
There is shown in FIG. 1 an embodiment of an autonomous steering system 10 for parallel parking a vehicle. The autonomous steering system 10 includes a steering module 12 and a controller 14 for controlling steerable wheels 16 of the vehicle. The steering module 12 may be an electronic module or similar device that is capable of pivoting the steerable wheels 16 without a driver's steering demand via a steering wheel of the vehicle. The controller 14 provides control input signals to the steering module 12 , such as a conventional electronic power steering module, for controlling the pivoting of the steerable wheels during a parking maneuver. The controller 14 may be separate from the steering module 12 or may be integrated within the steering module 12 as a single unit.
The autonomous steering system 10 further includes a sensing device 18 for detecting objects proximate to the driven vehicle. The sensing device 18 detects the presence and non-presence of objects laterally from the vehicle for determining an available parking space between a first object and a second object. The sensing device 18 may include a radar-based sensing device, an ultrasonic-based sensing device, an imaging-based sensing device, or similar device capable of providing a signal characterizing the available space between the objects. The sensing device 18 is in communication with the controller 14 for providing signals to the controller 14 . The sensing device 18 may be capable of determining the distance between the respective objects and communicating the determined distance to the controller 14 , or the sensing device 18 may provide signals to the controller 14 to be used by the controller 14 to determine the distance of the spacing between the objects.
In response to the determined spacing between the first and second objects, controller 14 determines whether to apply a one cycle parking maneuver or a two cycle parking maneuver. The one cycle parking maneuver includes a single cycle steering strategy where the steerable wheels are pivoted in a first direction and then a counter direction for steering the vehicle to a parked position. No gear change is required in a one cycle parking maneuver.
The two cycle parking maneuver includes a two cycle steering strategy where the steerable wheels are pivoted in a first direction and then a counter direction (i.e., first steering maneuver). Thereafter, a gear change is performed (i.e., rearward to drive position) and a second steering maneuver is performed for steering the vehicle forward to a final park position. Determining whether the vehicle can be successfully parallel parked utilizing the two cycle steering strategy is modeled on a condition of whether the vehicle parked in the available parking space can leave the parking spot utilizing two steering maneuvers. That is, if the vehicle can leave the parking space utilizing only two steering maneuvers, then the vehicle can be parallel parked in the parking space utilizing only two steering maneuvers. A first steering maneuver includes the vehicle moving backward in the available parking space at a respective turning angle where a respective rear corner of the vehicle reaches a respective boundary (i.e., front of the first object). A second steering maneuver includes the vehicle moving forward where a respective front corner of the vehicle reaches a respective rear boundary of the second object (i.e., rear corner of the second object).
A routine for determining whether a vehicle can be parked in an available parking space utilizing either a single cycle steering strategy or a two cycle steering strategy is described in a application having a Ser. No. 12/107,130, filed on Apr. 22, 2008, which is incorporated by reference in its entirety. The routine determines a first minimum length for parking the vehicle using a single parallel parking maneuver and a second minimum length for parking the vehicle using a two cycle parallel parking maneuver based on the available parking space between the first object and second object.
For a one cycle parking strategy, as shown in FIG. 2 , the available parking space is bordered by two objects, specifically, two in-line parked vehicles with or without a curb. FIG. 3 illustrates the vehicle dimensions and vehicle region designations that will be used in conjunction with the each of the figures shown herein to explain the parallel parking strategies. Referring again to FIG. 2 , the available parking space with the curb has a respective length and width. The coordinate system (YAX) is used to show the relative position of the driven vehicle to the available parking space with the outer edge of object 2 being the origin (A). The coordinate system is oriented relative to curb. The x-axis of the coordinate system is parallel to the curb. The relative position of the driven vehicle to the available parking space is determined by the (1) relative angle of the vehicle centerline to the axis AX and (2) the vehicle position using the midpoint of the rear axle relative to (YAX) coordinate system.
Depending on the parking slot dimensions and orientation, the target position of the vehicle O(x 2 , y 2 ) can be defined. The objective is to bring the vehicle from its initial position O(x i , y i ) to the final position O(x 2 , y 2 ) To park the vehicle using the one cycle parking strategy, three steps are involved: (1) the vehicle is aligned using a shortest distance traveled (e.g. O(x i , y i ) to O(x 0 , y 0 )), (2) the vehicle is moved along the x-axis as far as possible until the location of the parallel parking maneuver is initiated (e.g. O(x 0 , y 0 ) to O(x 1 , y 1 )), and (3) parallel parking is performed from O(x 1 , y 1 ) to O(x 2 , y 2 )).
During the initial stage (i.e., step (1)) of the one cycle parking maneuver, depending on the location of the vehicle relative to the object, the vehicle is steered at a maximum possible angle until a heading (yaw) angle is brought to zero (i.e., O(x i , y i ) to O(x 0 , y 0 )). This gives the shortest possible arc length traversed by the midpoint of the rear axis of the vehicle. The location O(x 0 , y 0 ) as shown in FIG. 2 is the coordinate where the vehicle has a heading angle of zero. This coordinate is represented by the following:
x 0 =x i −R 1 sin φ,
y 0 =y i +R 1 (1−cos φ) if φ≦0 (1)
or
x 0 =x i −R 2 sin φ,
y 0 =y i −R 2 (1−cos φ) If φ>0 (2)
where R 1 is the radial distance from an initial turn center C i of an initial arc radius from O(x i , y i ) to O(x 0 , y 0 ) which is representative of the midpoint of the rear axle of the vehicle, R 2 is the radial distance from a first turn center C 1 of a first arc radius initiating at O(x i , y i ) to the midpoint of the rear axle of the vehicle, and φ angle of the first arc radius of the first turn center C 1 . This strategy can be modified if x 0 −x 1 is sufficiently large to accommodate smallest and smoothest possible road wheel angle profile.
In the second step (e.g., O(x 0 , y 0 ) to O(x 1 , y 1 )) the vehicle is moved along the x-axis with a road wheel angle of zero until the midpoint of the rear axle reaches a position O(x 1 , y 1 ). At position O(x 1 , y 1 ) the steering maneuver is initiated. The distance that the vehicle travels in a rearward direction along the x-axis is equal to x 0 −x 1 .
In the third step (e.g., O((x 1 , y 1 ) to O(x 2 , y 2 )) parallel parking is performed to park the vehicle at the final position. The shortest path of travel to park the vehicle from position O(x 1 , y 1 ) to position O(x 2 , y 2 ) consists of two arcs. The lateral distance in the (YAX) coordinate system between position O(x 1 , y 1 ) and position O(x 2 , y 2 ) is represented by the formula:
H=y 1 −y 2 >0 (3)
The angle of rotation ψ, as shown in FIG. 1 , is a function of H in the following geometric relation:
H = ( R 1 + R 2 ) ( 1 - cos ψ ) ,
ψ = arccos ( 1 - H R 1 + R 2 ) . ( 4 )
The longitudinal distance that the vehicle moves along the X-axis required for parallel parking is represented by the formula:
L≡x 1 −x 2 (5)
therefore,
L
=
(
R
1
+
R
2
)
1
-
(
1
-
H
R
1
+
R
2
)
2
.
(
6
)
Factors that must be taken into consideration when parking the vehicle includes the clearance between the vehicle and object 2 forward of the vehicle. Conditions for not interfering with the front object are as follows:
( R 2 +a 1 ) 2 +b 2 2 <x 2 2 +( y 2 +R 2 ) 2 (7)
x 1 >0 AND ( R 1 −a 1 ) 2 >x 1 2 +( y 1 −R 1 ) 2 . (8)
A portion of the vehicle that must clear the front object is the right front corner of the vehicle (B RF ) which must avoid hitting the front object as the vehicle travels rearward into the available parking space. An alternative condition may include x 1 <0 where the entire right hand side of the vehicle, and particular point G RHS , does not hit the front object.
A total distance traversed by the midpoint of the rear axle from O(x 1 , y 1 ) to O(x 2 , y 2 ) is equal to(R 1 +R 2 )ψ. FIG. 4 illustrates the road wheel angle as a function of distance traveled by the rear axle midpoint. Smoothing the road wheel angle (RWA) profile is needed since actuators such as an EPS or/and AFS cannot exactly follow a bang-bang command as shown in FIG. 4 due to the actuator limitations; however, smoothing of the RWA results in a longer distance traveled. Different functions can be used to smooth the transition between zero and maximum road wheel angle. One possible function makes the tangent of the road wheel angle a linear function of arc length (with some slope ξ), as shown in FIG. 5 . That is, the tangent of the road wheel angle is a piecewise linear function of arc length with the slope +/−ξ 1 . In this embodiment, the heading angle (yaw angle) changes quadratically with the arc length, and the trajectory is a clothoid. The durations of the maximums steering, s 1 and s 2 , are coordinated so that the net change of the yaw angle is zero. This relationship is represented by the following equation:
s 2 = tan δ 1 tan δ 2 s 1 + tan 2 δ 1 - tan 2 δ 2 ξ tan δ 2 ( 9 )
In changing s 1 and integrating equations of motion numerically, the final position of the midpoint of the rear axle (x 2 , y 2 ) can be obtained as a function of s 1 . In determining y 2 from the parking spot detection, one can determine s 1 from this relationship and store this relationship as a table lookup (see FIG. 5 where s 1 and s 2 are durations of full steer).
FIG. 6 illustrates a smoothed trajectory profile of the midpoint of the rear axle of the vehicle as it transitions through into the parking space. As shown in FIG. 6 , the trajectory is formed from a plurality of circle arcs and clothoids. The trajectory as a whole can be viewed as a first arc shaped trajectory 20 and a second arc shaped trajectory 22 that inversely mirror one another. The first arc shaped trajectory is complementary to the second arc shaped trajectory at an intermediate position 24 for forming a smoothed rearward steering maneuver from the first position where the parallel parking maneuver is initiated to a second position where the vehicle is either parked or the gears of the transmission are changed to a forward drive position.
In FIG. 6 , a first position 26 represents the starting position of the rearward parallel parking maneuver. A second position 28 represents an ending position for the rearward parallel parking maneuver. It should be understood that additional maneuvers may be added which include forward driving maneuvers within the available parking space to straighten the vehicle or even park the vehicle between two objects. The first arc shaped trajectory 20 includes an initial segment 30 (e.g., clothoid), a first segment 32 (e.g. circle arc) and a second segment 34 (e.g., clothoid). The second arc shaped trajectory 22 includes a first segment 36 (e.g. circle arc), a second segment 38 (e.g., clothoid), and an ending segment 40 (e.g., clothoid). The first segment 32 of the first arc shaped trajectory 20 and the first segment 36 of the second arc shaped trajectory 22 cooperatively form a clothoid that extends between the first arc-shaped trajectory 20 and the second arc-shaped trajectory 24 . The cooperative joining of each of the segments formed from arc circles and clothoids provide a smoothed transition into the available parking space.
The two cycle parking maneuver for the bang-bang control is illustrated in FIGS. 7-9 . The two cycle parking maneuver can best be explained by describing the path planning in reverse order (i.e., from the destination to the initial position). In FIG. 7 , K 1 ={O 1 , ψ=0} represents the final configuration of the vehicle inside the parking spot, where O 1 (x 1 , y 1 ) is the global coordinates of the vehicle and ψ 1 is the vehicle yaw angle. The coordinate system has a configuration relative to object 2 with its origin located at the left rear corner of object 2 . For simplicity purposes, assume the final yaw angle is zero. Let the vehicle move from configuration K 1 into K 2 where K 2 ={O 2 , ψ 2 } with a constant steer angle δ 1 such that the path curvature has a constant radius R 1 =R 1 (δ 1 ). The new position is represented by coordinates (x 2 , y 2 ) which can be determined by the following equations:
x 2 =x C 1 −R 1 sin ψ 2
y 2 =y C 1 +R 1 (1−cos ψ 2 ). (10)
The coordinates of the turn center C 1 is represented by coordinates (x C1 , y C1 ) which can be determined based on the following equations:
x C 1 =x 1
y C 1 =y 1 −R 1 . (11)
The turn angle ψ 2 may be determined by the following geometric condition:
( R 1 +a 1 )sin ψ 2 +b 1 cos ψ 2 =L+x 1 (12)
which represents the distance from O 1 to the left boundary of the parking spot (note that x 1 <0 as shown in FIG. 7 .) Utilizing trigonometric calculations, equation (12) is as follows:
ψ
2
=
arcsin
L
+
x
1
(
R
1
+
a
1
)
2
+
b
1
2
-
arcsin
b
1
(
R
1
+
a
1
)
2
+
b
1
2
(
13
)
FIG. 8 illustrates a next stage of the path planning, from position K 2 {O 2 , ψ 2 } to position K 3 {O 3 , ψ 3 }. The vehicle makes a turn while maintaining a constant radius R 2 where R 2 =R 2 (δ 2 ). The corresponding turn center C 2 for the turn has the following coordinates:
x C 2 =x C 1 −( R 1 +R 2 ) sin ψ 2
y C 2 =y C 1 +( R 1 +R 2 ) cos ψ 2 . (14)
Position K 3 is determined based on the condition that the right front corner of the vehicle is at the respective minimal distance d from the left rear corner of the object 2 . This respective condition can be represented by the following equation:
C 2 A=R 2 rf +d (15)
where C 2 A is the distance from the turn center to the origin of the coordinate system (XAY) located at the left rear corner of object 2 , and R 2 rf is the turning radius of the right front corner of the vehicle. Using Pythagorean's theorem, the respective distances may be solved for:
C 2 A =√{square root over ( x C 2 2 +y C 2 2 )} (16)
R 2 rf =√{square root over (( R 2 +a 1 ) 2 +b 2 2 )}. (17)
The vehicle coordinates when the at position K 3 are determined based on the following equations:
x 3 =x C 2 +R 2 sin ψ 3
y 3 =y C 2 −R 2 cos ψ 3 . (18)
Since R 2 rf is the maximum radius connecting the turn center C 2 and an arbitrary point of the vehicle boundary, d>0 is a sufficient condition for the vehicle to leave the parking spot without collision with object 2 . Based on the minimum spot length L min condition, the final position of the vehicle inside the parking spot is
K 1 ={O 1 (− b 2 ,−a 1 );0} (19)
If vehicle position K 3 is the position when the vehicle is at the minimum distance to object 2 (see FIG. 8 ), this represents a turning point for starting the right turn to bring the vehicle into position K 4 parallel to object 2 . Position K 4 is represented by the following vehicle configuration:
K 4 ={O 4 ( x 4 ,y 4 );0}. (20)
The turn center C 3 for the position K 4 has the following coordinates:
x C 3 =x C 2 +( R 2 +R 3 ) sin ψ 3 =x 4
y C 3 =y C 2 −( R 2 +R 3 ) cos ψ 3 =p+a 1 −R 3 (21)
where p is the distance between the vehicle and object 2 when the vehicle and object 2 are parallel to one another. Therefore, a turn angle ψ 3 as shown in FIG. 8 may be represented as follows:
ψ 3 = arccos y C 2 + R 3 - ( p + a 1 ) R 2 + R 3 ( 22 )
and
x 4 =x C 2 +√{square root over (( R 2 +R 3 ) 2 −( y C 2 +R 3 −p− 1) 2 )}{square root over (( R 2 +R 3 ) 2 −( y C 2 +R 3 −p− 1) 2 )}
y 4 =p+a 1 . (23)
The above equation (23) determines the position from which the vehicle should start its entrance into the available parking space. Note that all quantities given by the above equations (1) through (23) can be calculated before executing the path-planning algorithm.
To perform path planning and park the vehicle in the available parking space, the algorithm assumes that the vehicle's starting position is position K 4 for initiating the two cycle parking maneuver. The path from K 4 to the target position K 1 is simply the backward path from K 1 to K 4 . Therefore, the vehicle must be moved into position K 4 . It should be understood that there are multiple ways of transitioning the vehicle from a position K i to the position K 4 . FIG. 9 illustrates one of a plurality of methods for moving the vehicle from K i to position K 4 . The first step is to set the following conditions:
R 3 =R 1 =R rhs
R 2 =R lhs (24)
where R rhs is the minimal right turn radius and R lhs is the minimal left turn radius, respectively. Note that in general there are multiple ways of bringing the vehicle from its initial position K i into position K 4 . As shown in FIG. 9 , starting from K i , the vehicle makes a turn in a rearward direction until the vehicle becomes parallel to object 2 represented as position K 5 . The coordinate of the vehicle as represented by the position of the midpoint of the rear axle having the coordinate O 5 (x, y 5 ). Coordinate O 5 (x 5 , y 5 ) with a corresponding arc length is determined by the following equations:
x 5 =x i −R i sin ψ i
y 5 =y i −R i (1−cos ψ i )
ψ 5 =0
Δs=R i ψ i . (25)
The initial position K i can be arbitrary with some limits, but the turning radius must be such that at the end of the turn, the following condition must be satisfied:
y 5 =y 4 =p+a 1 . (26)
Moreover, there is also a constraint on x-coordinates such that
x 5 ≧x 4 . (27)
Substituting equation (26) into equation (25), produces the following:
R i = y i - ( p + a 1 ) 1 - cos ψ i . ( 28 )
A corresponding road steer angle δ can therefore be derived from Eq. (22) and (28):
δ = arctan w R i . ( 29 )
As stated earlier, the constraints shown in equations (26) and (27) place limitations on the initial positions from which it is possible to start the entire 2-cycle parking maneuver. By substituting the equation (25) into equation (27) and taking into account equation (28), the following result is derived:
x i α i ( ψ i ) + y i β i ( ψ i ) ≥ 1 ( 30 )
where
α i (ψ i )= x 4 −( p+a 1 )cot(ψ i /2)
β i (ψ i )=− x 4 tan(ψ i /2)+ p+a 1 . (31)
where x 4 is determined from equation (21).
Since a driver initiates the start of the two cycle parallel parking maneuver from the left side of object 2 , the condition R i ≧R lhs must be satisfied. Therefore, equation (28) also requires the following condition:
y i ≥ p + a 1 + 2 R lhs sin 2 ψ i 2 ≡ y i min ( ψ i ) ( 32 )
The inequalities as shown in equation (30) and equation (32) geometrically restrict the initial position K i to the sector area shown generally at 50 in FIG. 10 .
A second stage illustrates the vehicle moving from position K 5 to K 4 . In the second stage, the vehicle simply moves backward with a zero steer angle until the vehicle reaches O 4 (x 4 , y 4 ) position as shown in FIG. 9 . The corresponding path of travel is a straight line in the x-direction. The traveled distance and the steer angle are represented by the following formulas:
Δ s=x 5 −x 4
δ=0 (33)
where x 4 and x 5 must be determined in advance from equations (23) and (25), respectively.
A third stage illustrates the vehicle moving from position K 4 to K 3 . In the third stage, the vehicle makes a turn to move to position K 3 as shown in FIG. 8 . The vehicle configuration at position K 3 is represented by K 3 ={(x 3 , y 3 );ψ 3 }. A corresponding arc length and road steer angle from position K 4 to K 3 is represented by the following:
Δ s = R 3 ψ 3
δ = - arctan w R 3 ( 34 )
where ψ 3 and R 3 are determined by equation (22) and equation (24), respectively.
A fourth stage illustrates the vehicle moving from position K 3 to K 2 . In the fourth stage, as shown in FIG. 8 , the steer angle changes at the intermediate position K 3 from negative to positive. The vehicle continues its path of travel having a positive steer angle until a rear left corner reaches a minimal allowed distance to object 1 . The corresponding arc length and steer angle for the vehicle transitioning from K 3 to K 2 are represented by the following:
Δ s = R 2 ( ψ 3 - ψ 2 )
δ = arctan w R 2 ( 35 )
where ψ 2 and R 2 are determined from equation (4) and equation (24), respectively.
A fifth stage illustrates the vehicle moving from position K 2 to K 1 . In the fifth stage, as shown in FIG. 7 , the steer angle changes from positive to negative. The transmission gear is changed from a reverse gear position to drive gear position. The vehicle continues moving in a forward direction until the vehicle reaches position K 1 . The corresponding arc length and steer angle for the vehicle moving from K 2 to K 1 are represented by the following:
Δ s = R 1 ( ψ 2 - ψ 1 ) , ψ 1 = 0
δ = - arctan w R 1 ( 36 )
where ψ 2 and R 1 are determined from equation (12) and equation (24), respectively.
An optional stage may be included to better position the vehicle within the available parking space between object 1 and object 2 . The vehicle may be placed into the reverse gear position and the vehicle may be moved in a rearward direction with a zero steer angle to better position the vehicle. For example, the vehicle may sense the distance of object 1 rearward of the vehicle and the distance of object 2 forward of the vehicle. The vehicle is then parked evenly spaced between the first object and the second object.
For a smoothed control strategy, duration s 1 and position x 4 are table lookups for the y-coordinate of the final position.
While certain embodiments of the present invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention as defined by the following claims. | A method is provided for determining a vehicle path for autonomously parallel parking a vehicle in a space between a first object and a second object. A distance is remotely sensed between the first object and the second object. A determination is made whether the distance is sufficient to parallel park the vehicle between. A first position to initiate a parallel parking maneuver is determined. A second position within the available parking space corresponding to an end position of the vehicle path is determined. A first arc shaped trajectory of travel is determined between the first position and an intermediate position, and a second arc shaped trajectory of travel is determined between the second position and the intermediate position. The first arc shaped trajectory is complementary to the second arc shaped trajectory for forming a clothoid which provides a smoothed rearward steering maneuver between the first position to the second position. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation-in-Part (CiP) of, and claims benefit and priority to, U.S. patent application Ser. No. 14/939,188 filed Nov. 12, 2015 and titled “FIRE-TUBE BOILER CLEANER”, which itself claims benefit and priority to U.S. Provisional Patent Application No. 62/122,209 filed on Oct. 14, 2014, the entirety of each of which is hereby incorporated by reference herein.
BACKGROUND
[0002] Embodiments disclosed herein generally relate to pivoting tube brushes, such as may be utilized in tube cleaning operations. In some embodiments, a pivoting tube brush may be utilized in fire-tube boilers and provide solutions to the problem of cleaning the interior surface of fire-tubes with a lighter weight, easier to use machine.
[0003] The general construction of a fire-tube boiler is a tank of water penetrated by tubes that carry the hot flue gases from the boiler's combustion chamber. The tank is usually cylindrical for the most part (being the strongest practical shape for a pressurized container) and this cylindrical tank may be either horizontal or vertical. In a fire-tube boiler a large number of fire-tubes are arranged in a boiler drum for generating a large amount of steam (hot water) for its size as compared to flue boilers. Hot combustion gases pass through fire-tubes running through the sealed boiler drum containing water. The heat of the gases is transferred to the water through the walls of the tubes ultimately creating steam. The many small tubes offer far greater heating surface area for the same overall boiler volume. In operation, surface area heat transfer efficiency is diminished by buildup on the fire-tube interior surfaces by products of corrosion, oxidation, soot, and chemical reactions. Fire-tube boiler cleaning machines are available for tube cleaning, however, such machines are very heavy and hard to use in tight spaces or on elevated catwalks, platforms, or scaffolding. Machine weight is determined by the physics of pushing a rigid cleaning brush in a forward stroke down the full length of a tube by means of a steel tape. The steel tape needs to be thick and heavyweight to resist the significant compressive forces encountered in pushing the brush along the tube. Additionally, the machine needs sufficient mass (weight) to withstand the high loads developed on the brush forward stroke.
[0004] Some embodiments disclosed herein deal with the main problem of conventional fire-tube cleaners, i.e., the weight of the cleaner and component parts. Solutions disclosed herein provide a unique and brilliant way of substituting fire-tube boiler mass for the mass needed by conventional machines to withstand the high loads developed on the brush forward stroke. Embodiments disclosed herein generally, for example, take advantage of boiler mass by providing a machine for tube cleaning on reverse stroke.
SUMMARY
[0005] Pivoting and/or rotating tube brushes may be utilized to provide advantages in tube cleaning operations. Fire-tube cleaners according to embodiments described herein utilize lightweight, high strength components to propel a unique easy-push, clean on return stroke brush for tube cleaning. Brush design minimizes friction resistance on the forward stroke of the cleaning cycle, thereby substantially reducing compressive force on the tape pushing the brush and eliminating tendency of tape to collapse, buckle, or bind within a tube. On the return cleaning stroke the tape is in constant tension and can easily handle the forces involved. A preferred embodiment is designed for modern package boilers usually having tubes of maximum length of sixteen (16) feet and of outside diameter of two inches (2″) to two and one half inches (2½″).
[0006] An operator of the fire-tube cleaner according to some embodiments pre-sets the distance the tape and brush travel according to boiler tube length thereby allowing the operator to concentrate on machine and cleaning cycle. This feature eliminates operator need to concentrate on machine distance monitor to avoid cleaning brush slamming into the far side of the boiler damaging boiler cover, insulation, cleaning brush, etc.
[0007] The machine may also or alternatively include a distance monitor on both sides of the machine, a centrally located rear-mounted operating switch, and a main drive-train of motor, gearbox, clutch, and final drive located within the machine protecting the operator from moving parts and hot (e.g., one hundred and eighty degrees Fahrenheit (180° F.)) exposed drive motor. The machine allows for quick change of steel tape without the need for machine disassembly.
[0008] An easy-push, clean on return stroke brush reduces push force through fire-tubes. The brush may be mounted on a restricted movement swivel that allows the brush to fold over passing down the tube, and to setup and remain upright on the return stroke.
[0009] Specific examples are included in the following description for purposes of clarity, but various details can be changed within the scope of the present invention. While fire-tube cleaning is utilized as a primary non-limiting example of tube cleaning operations with a pivoting and/or rotating tube brushes, for example, other types of tubes and/or other types of cleaning machines may be utilized.
OBJECTS OF THE INVENTION
[0010] An object of the invention is to provide pivoting and/or rotating tube brush assemblies for use in various machines for cleaning tubes.
[0011] An object of the invention is to provide a machine for cleaning fire-tubes that cleans tubes on brush return stroke thereby to take advantage of boiler mass and reduce cleaning machine mass.
[0012] Another object of the invention is to provide a lightweight fire-tube cleaner with reduced resistance on brush push stroke and with tube cleaning occurring on the return stroke.
[0013] Another object of the invention is to provide a fire-tube cleaning machine with lightweight, high strength steel tape to propel brush down the tube.
[0014] Another object of the invention is to provide fire-tube cleaning machine with preset travel distance for tape selected according to fire-tube length.
[0015] Another object of the invention is to provide for tube cleaning machine with drive train located within the machine for operator protection.
[0016] Other and further objects of the invention will become apparent with an understanding of the following detailed description of the invention or upon employment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] An understanding of embodiments described herein and many of the attendant advantages thereof may be readily obtained by reference to the following detailed description when considered with the accompanying drawings, wherein:
[0018] FIG. 1 is a perspective view of a preferred embodiment of a fire-tube cleaner according to some embodiments;
[0019] FIG. 2 is a side elevation view of the fire-tube cleaner of FIG. 1 with first side cover plate removed to illustrate interior components;
[0020] FIG. 3 is a reverse side perspective view of the fire-tube cleaner of FIG. 1 and FIG. 2 with second side cover plate removed to illustrate interior components;
[0021] FIG. 4A is fragmentary side view of interior working components of a distance indicator;
[0022] FIG. 4B is a perspective view of interior working components of a distance indicator;
[0023] FIG. 5 is a front elevation view of the distance indicator cover shown in FIG. 1 and FIG. 4B ;
[0024] FIG. 6 is a fragmentary perspective view of a steel tape reel in open position for change of tape;
[0025] FIG. 7 is a fragmentary perspective view of a steel tape reel in closed position for tape operation in tube cleaning;
[0026] FIG. 8 is a perspective view of a pivoting tube brush assembly such as in a position for feeding into a tube on a forward stroke; and
[0027] FIG. 9 is a perspective view of a pivoting tube brush assembly such as in a position for cleaning a tube on a return stroke.
DETAILED DESCRIPTION
[0028] Referring to FIG. 1 , FIG. 2 , and FIG. 3 of the drawings, a fire-tube cleaning machine 10 includes housing 12 defined by confronting shell members 12 a - b defining an interior space 14 for placement of cleaner operating components 16 including drive-train 18 and tape reel 20 with drum drive gear 20 a. The housing further includes carry handle 12 c, cover plate 12 d for access to tape anchor 36 (also shown in FIG. 6 and FIG. 7 ), vacuum connection 12 e, and cleaner switch console 12 f. The shell members 12 a - b are secured to each other by suitable fasteners (not shown) at multiple locations 12 g.
[0029] A tape 22 and brush and/or brush assembly 24 may be housed in a deployment member in the form of a tape outlet barrel 26 that extends from the housing 12 for insertion into individual fire-tubes 28 so as to position tape 22 and brush assembly 24 at tube entry 28 a. The tape outlet barrel 26 serves as a vacuum conduit for carrying dislodged soot from each tube 28 to a vacuum source (not shown) at vacuum connection 12 e.
[0030] A distance indicator 30 (described in detail below) may be affixed to a side of housing 12 exterior for pre-setting distance of tape travel according to length of boiler fire-tubes 28 .
[0031] Layout of interior components according to some embodiments is shown in FIG. 2 and FIG. 3 including tape reel 20 with its drive gear 20 a and tape anchor 36 , and tape reel drive train 18 .
[0032] Drive train 18 may include, for example, an electric drive motor 18 a suitably powered with drive shaft 18 b rotating at one end a cooling fan 18 c, and worm gear box 18 d at other end. Output pinion 18 f is positioned between gear box 18 d and clutch 18 e. Out-put pinion 18 f is driven by worm gear (not shown; housed inside of the worm gear box 18 d ) to power drive chain or belt 18 g for turning tape reel 20 by its drive gear 20 a . Power switch 32 has forward, center, and reverse positions for directing rotation of the drive motor 18 a. Tape reel 20 is equipped with a reel stop 20 c for stopping the reel 20 (e.g., by a stop surface 20 cx engaging with a stop portion 20 x of the reel 20 , such as by the reel stop 20 c rotationally engaging therewith by rotating about a stop pivot 20 cy ) so tape holder or anchor 36 may be stopped/located at housing access panel 12 d (e.g., for access to allow tape changeover and/or maintenance or adjustment).
[0033] The distance indicator 30 on one or both sides of the housing 12 sets the distance of payout of tape 22 on brush forward stroke according to the length of fire-tubes 28 in a particular boiler (not shown). Referring to FIG. 4A , the distance indicator 30 has a first limit switch 30 i providing an “off” function for the drive motor 18 a at the end of a length of tape 22 paid out on forward stroke. The operator uses forward/reverse switch 32 on return stroke to pull tape 22 and brush assembly 24 in a cleaning pass through a fire-tube 28 . On return stroke the distance indicator 30 trips a second limit switch 30 j for providing an “off” function for drive motor 18 a. A distance adjustment control knob 30 m ( FIG. 1 ) is movable through an adjustment arc defined by an arced slot 30 k ( FIG. 1 and FIG. 4B ) in distance indicator 30 for setting payout distance of the tape 22 .
[0034] Reel drive gear or sprocket 20 a is fitted with distance indicator drive pinion 20 d for powering distance indicator 30 . Distance indicator 30 includes outer cover 30 a secured by a fastener such as a retaining bolt 30 b at socket 30 c formed in a housing shell member 12 a or 12 b with indicator sprocket gear 30 e ( FIG. 4B ) meshed with teeth of the distance indicator drive pinion 20 d. Inner web 30 f ( FIG. 4B ) of the indicator sprocket gear 30 e is provided with a movable forward actuator 30 g (also shown in FIG. 2 as engaged with first limit switch 30 i —although with the indicator sprocket gear 30 e is not shown in FIG. 2 ) and a stationary or fixed rearward actuator 30 h cooperating with the first or forward limit switch 30 i and with the second or rearward limit switch 30 j, which may for example, comprise micro-switches. Forward actuator 30 g comprises an arcuate bar at a first fixed radius R 1 from sprocket center 30 b - 1 (e.g., coincident with a center axis of the retaining bolt 30 b ), the bar being slidable along the arced slot 30 k formed in the sprocket web 30 f. The forward actuator fixed radius R 1 is equal to a distance between the sprocket center 30 b - 1 and a contact surface of the first limit switch 30 i. Forward actuator 30 g and forward limit switch 30 i cooperate (e.g., as depicted in FIG. 2 ) to stop tape 22 and brush assembly 24 forward movement into the fire-tube 28 . Rearward actuator 30 h is affixed to circular rib 30 n (and/or comprises a raised portion of the circular rib 30 n ) positioned on inner web 30 f at a second fixed radius R 2 from sprocket center 30 b - 1 . The second fixed radius R 2 is equal to a distance between the sprocket center 30 b - 1 and the rearward limit switch 30 j.
[0035] FIG. 1 and FIG. 5 show distance indicator cover 30 a with slot 30 k and indicator knob 30 m. The distance travelled forward into a tube by tape 22 and brush assembly 24 in a tube cleaning pass is selected by moving knob 30 m (and accordingly the attached/cooperative forward actuator 30 g ) along slot 30 k. As shown in FIG. 5 , indicator cover 30 a has indicia “I” arranged along its circumference with a portion of indicia “I”, i.e., labels representing numbers/settings seven (7) through sixteen (16), arranged alongside slot 30 k . The indicia “I” correlates to tube length, and by positioning knob 30 m adjacent a specific value representing a desired/known tube length, the operator thus selects distance cleaning brush assembly 24 travels on forward stroke. The knob 30 m has a threaded connection (not shown) with forward actuator 30 g for tightening forward actuator 30 g in selected position in the slot 30 k. In operation, rearward actuator 30 h stops tape movement when sprocket 20 a (e.g., via engagement of the distance indicator drive pinion 20 d ) brings the rearward actuator 30 h into contact with the rearward limit switch 30 j, as occurs when the tape 22 and brush assembly 24 are withdrawn from a tube 28 . Forward movement of tape 22 and brush assembly 24 in another tube 28 occurs with forward actuation of operating switch 32 by machine operator. Forward movement of tape 22 and brush assembly 24 continues for a pre-selected distance corresponding to the dialed-in position of forward actuator 30 g. Forward movement of tape 22 and brush assembly 24 stops when movable forward actuator 30 g trips the forward limit switch 30 i. At this point operator uses main switch 32 to reverse tape 22 and brush assembly 24 movement drawing them rearward in a cleaning pass through a tube 28 .
[0036] FIG. 6 and FIG. 7 show tape reel or drum 20 for forward unwinding and reverse rewinding of tape 22 for cleaner operation. Tape 22 may comprise a stainless steel band having strength and stiffness capable of pushing tube cleaning brush assembly 24 described herein through the length of a fire-tube 28 , of pulling the brush assembly 24 back through the tube 28 in a cleaning stroke, and having a suitable level of pliability to coil about the tape reel 20 . While typical fire-tube cleaning tape (not shown) must be designed of a sufficient width and thickness to provide approximately two hundred (200) pounds of push force, for example, the tape 22 in accordance with embodiments herein may generally be about half the width and thinner than typical tape, such that the tape 22 of the fire-tube cleaning machine 10 described herein may be designed and configured to maintain structural integrity upon an application of approximately one hundred (100) pounds of push-force. In such a manner, for example, the tape 2 may be approximately one half the weight of typical tapes, significantly reducing the overall wright of the fire-tube cleaning machine 10 as compared to previous cleaning machines for fire-tubes.
[0037] In some embodiments, on reverse stroke the reel stop 20 c positions tape notches 22 a adjacent access panel 12 d. Tape 22 has end notches 22 a for engagement with a movable anchor 36 fitted to the reel 20 . A spring loaded platform 36 a positions anchor pins 36 b in engagement with notches 22 a for securing tape 22 to reel 20 . Platform 36 a is lowered to disengage pins 36 b from notches 22 a when tape 22 is replaced. Spring 36 c urges platform 36 a and pins 36 b into normal position of anchoring pins 36 b to tape notches 22 a . Cover plate 12 d ( FIG. 1 and FIG. 3 ) provides access to platform 36 a and tape notches 22 a so that tape 22 can be changed without dismantling the cleaner housing 12 . Rollers 34 remove binding friction on the tape 22 when outward bound into a tube 28 .
[0038] FIG. 8 and FIG. 9 illustrate a brush assembly 24 comprising a cleaning brush 24 a and a brush head 24 b. Cleaning brush 24 a, in some embodiments, is attached to an elongate forcing element such as a tape 22 (e.g., disposed along an axis X-X′) by means of brush head 24 b. According to some embodiments, the tape 22 may instead comprise a cable or other means (not shown; e.g., a rope, tube, shaft, magnet, vacuum, and/or motor) for pulling and/or pushing the brush 24 a through a tube (not shown; e.g., the tube 28 of FIG. 1 ). In some embodiments, the brush head 24 b may comprise an elongate block 24 c with center recess 24 d for insertion and securing tape end 22 b (or for insertion and/or securing of another terminal component of a different forcing element such as an end of a cable or shaft) to the block 24 c using suitable fasteners 24 e . According to some embodiments, block end 24 f comprises a plurality of spaced arms 24 g - h (e.g., two (2) spaced arms 24 g - h as depicted) defining between them a socket 24 i for receiving cleaning brush subassembly of brush 24 a and brush post 24 j. Brush post 24 j may, for example, be nested within socket 24 i and secured to arms 24 g - h by pivot pin 24 k for pivotal movement of brush 24 a and brush post 24 j from horizontal to vertical positions of FIG. 8 and FIG. 9 , respectively. Brush subassembly may, for example, have a normal position (e.g., a first orientation) for forward stroke, as shown in FIG. 8 , and may set up and/or transition to a vertical position (e.g., a second orientation; e.g., disposed at ninety degrees (90°) from the first orientation) when tape 22 is in reverse stroke pulling brush 24 a through a tube 28 (or in the case the brush 24 a is otherwise pulled via application of force).
[0039] The brush 24 a itself may be mounted by securing bolt or fastener 24 m on brush post 24 j for optional and/or selective fixed placement or free-wheeling rotation about brush axis X-X′. The brush 24 a may comprise or be coupled to, for example, a bushing or bearing (not separately labeled or specifically depicted) through which the fastener 24 m passes, permitting the brush 24 a to rotate about the fastener 24 m. According to some embodiments, such as in the case that the brush 24 a is passed (e.g., via force applied by a forcing element such as the tape 22 or a cable or shaft) through an “enhanced” tube having internal rifling, grooves (e.g., helical), or other raised or depressed internal features, the passing of the brush 24 a over or through such features may impart rotational movement to the brush 24 a (e.g., about the fastener 24 m ). According to some embodiments, the brush 24 a may alternatively be fixedly coupled via the fastener 24 m (e.g., the fastener 24 m may engage with threads (not shown) of the brush 24 a ) and rotation of the brush 24 a may be imparted by a rotation of the forcing element. The forcing element (such as a flexible drive shaft) may, for example, impart both longitudinal (e.g., with respect to the axis X-X′) and rotational force to the brush 24 a . The brush 24 a may, for example, be powered by a tube cleaning system with a rotating brush such as depicted and described in and with respect to FIG. 1 of co-pending U.S. patent application Ser. No. 14/830,774 filed on Aug. 20, 2015 and titled “SYSTEM AND METHODS FOR TABLETIZED TUBE CLEANING”, the tube cleaning mechanics, systems, and concepts of which are hereby incorporated by reference herein.
[0040] In some embodiments, the term “vertical” may be descriptive of (and/or specifically defined as) the brush 24 a being oriented such that a centerline of the fastener 24 m (not separately labeled) is oriented along the X-X′ axis. According to some embodiments, the term “horizontal” may be descriptive of (and/or specifically defined as) the brush 24 a being oriented such that the centerline of the fastener 24 m (not separately labeled) is oriented perpendicular to the X-X′ axis. While the terms “horizontal” and “vertical” are utilized for ease of illustration to describe the change in orientation of the brush subassembly (e.g., the brush 24 a, brush post 24 j, and/or fastener 24 m ) with respect to a generally horizontally-oriented tube, the first and second orientations may deviate from true horizontal and/or vertical depending upon the orientation of the tube being cleaned. In the case that a vertically-oriented tube is cleaned, for example, the first or forward stroke orientation of the brush 24 a may be substantially vertical (i.e., the brush 24 a being inserted side-long into the tube such that the centerline of the fastener 24 m is perpendicular to the axis of the tube), while the second or reverse stroke orientation may be substantially horizontal vertical (i.e., the brush 24 a being removed from the tube in a pivoted and engaging orientation such that the centerline of the fastener 24 m is parallel to the axis of the tube).
[0041] According to some embodiments, the brush 24 a comprises cleaning strips or blades 24 n of suitable material extending radially from brush axis X-X′. The brush strips 24 n may be pitched at an angle to brush axis X-X′ to promote rotation and cleaning action of the brush 24 a as it travels in reverse stroke through a fire-tube 28 . In some embodiments, the brush 24 a may comprise an annular body defining a central hole (not visible in FIG. 8 or FIG. 9 ) for accepting the fastener 24 m. According to some embodiments, the blades 24 n may emanate radially from the annular body, defining a disc-shaped brush 24 a (as depicted). According to some embodiments, other blade and/or brush shapes may be employed while retaining the pivoting functionality of the brush assembly 24 .
[0042] In some embodiments, the underside of the brush head 24 b defines a recess 24 p to accommodate positioning of the brush 24 a horizontally ( FIG. 8 ). The tape 22 and brush assembly 24 are in position of FIG. 8 on forward stroke for pushing brush 24 a through, e.g., a fire-tube 28 , to initiate cleaning operation. For a reverse stroke or cleaning pass, the tape 22 (and/or other forcing element) pulls brush 24 a back through a tube. In this cleaning pass, the brush 24 a pivots to vertical ( FIG. 9 ) with brush tips (tips of the blades 24 n ; not separately labeled) engaging interior tube surface (not shown) while rotating and scrubbing soot and other dirt and contaminants (not shown) from the tube. In some embodiments, a vacuum source (not shown) secured to machine vacuum connection 12 e draws scrubbed material (not shown) from fire-tube 28 through machine barrel 26 .
[0043] In use of the fire-tube cleaning machine 10 , an operator sets distance indicator 30 according to fire-tube length for a particular boiler (not shown). With brush assembly 24 in position of FIG. 8 , operator advances the brush assembly 24 in a forward stroke by reeling out the tape 22 the set distance. Diametrically opposed edges of brush blades 24 n slip along interior fire-tube surface with minimum resistance. Here the chief requirement of the machine 10 is for a tape 22 of sufficient strength to push against this minimum resistance. The need for a massive conventional machine to support a forward stroke cleaning pass is eliminated. For cleaning the fire-tube 28 , the tape 22 is pulled through reverse stroke with brush assembly 24 setting up to position of FIG. 9 with entire complement of blade tips scrubbing tube interior. On the reverse pass, the boiler (not shown) provides mass and cleaning machine 10 provides lightweight, high strength structure for pulling brush 24 a back through each tube 28 . In some embodiments, other devices comprising tubes to be cleaned may provide similar mass for setting the pivoting brush 24 a up for the reverse or cleaning stroke as described.
[0044] Various changes may be made to the structure embodying the principles of the embodiments described herein without deviating from the scope of the overall invention. The foregoing embodiments are set forth in an illustrative and not in a limiting sense. The foregoing description has particular reference to cleaning boiler fire-tubes, however, it is understood that the cleaning machine described herein may be used for a wide variety of tube cleaning applications.
[0045] The present disclosure provides, to one of ordinary skill in the art, an enabling description of several embodiments and/or inventions. Some of these embodiments and/or inventions may not be claimed in the present application, but may nevertheless be claimed in one or more continuing applications that claim the benefit of priority of the present application. Applicants intend to file additional applications to pursue patents for subject matter that has been disclosed and enabled but not claimed in the present application. | Pivoting brush heads and associated machines in which cleaning of interior tube surfaces occurs by a forward non-cleaning pass of a pivoting brush head through a tube followed by a reverse cleaning pass where the pivoting brush head engages and cleans the interior surface. The pivoting brush head has a first position for the forward pass producing minimum engagement of interior tube surfaces, and a second position for the reverse pass of full cleaning engagement with the interior tube surfaces. | 5 |
BACKGROUND OF THE INVENTION
In one aspect, the invention relates to the separation of the components of a gas stream. In another aspect, the invention relates to the separation of a high purity stream of hydrogen gas from a gas stream. In still another aspect, the invention relates to the separation and recycling of a high purity hydrogen stream from and to a hydroretort.
"Hydroretorting" is retorting which is conducted in the presence of added hydrogen. Retorting is one method by which carbonaceous material, especially oil shale, can be upgraded to more valuable predominantly liquid hydrocarbon products. It has been found that conducting the retorting of certain oil shales in the presence of added hydrogen provides increased yield and product quality.
To promote the thermal efficiency of the retorting process, it is desirable to combust residual carbon from the retorted shale using oxygen containing gas to provide the heat for driving the retorting process. Leakage of combustion products from the combustion zone to the retorting zone results in combustion products being recovered from the retorting zone. The presence of combustion products such as carbon monoxide causes problems in the purification and recycling of hydrogen to the retort.
Hydrogen recovery is more important in a hydroretorting process than is common for many hydrogen purifiers because the hydroretorting process is a large consumer of hydrogen. Any loss of hydrogen must be made up by converting hydrocarbon retort product to hydrogen and carbon dioxide, an expensive process.
OBJECTS OF THE INVENTION
It is an object of this invention to provide an apparatus and process which result in high hydrogen recovery of high purity from a hydrogen containing gas stream.
It is another object of this invention to provide an apparatus and process for hydrogen recovery which requires no external refrigerant.
It is yet another object of this invention to provide a process for the recovery and recycle of hydrogen to and from a hydroretort which is simple and easily controlled.
It is another object of this invention to provide an apparatus and process for the production of two compositionally different substitute natural gas streams, a low pressure low BTU fuel gas stream and a relatively high pressure high BTU stream suitable for process use, e.g., reforming.
SUMMARY OF THE INVENTION
In one aspect, there is provided a process for providing a high purity hydrogen stream. An off-gas from a hydroretort means containing predominantly hydrogen and small amounts of methane and ethane and carbon monoxide is introduced into a separation means to separate the off-gas stream into a hydrogen first stream, a low BTU gas second stream containing carbon monoxide and a high BTU predominantly hydrocarbon third stream containing predominantly C 1 to C 4 hydrocarbons and a small amount of carbon monoxide. The third gas stream is fed from the separation means to a reformer means to provide the makeup hydrogen for the hydroretort. By separating out the carbon monoxide from the feed to the reformer process equilibrium can be shifted to favor hydrogen production.
In another aspect of the invention, hydrogen for a hydroretort can be provided from a dry, relatively low purity hydrogen gas first stream by cooling the first stream by indirect heat exchange in addition to cooling the first stream by expansion. With sufficient cooling the first stream is divided into a gaseous second stream which is hydrogen enriched and a liquid third stream which is hydrogen depleted. The expansion supplies the first portion of the cooling required to divide the first stream. The second stream is passed into indirect heat exchange relationship with the first stream to provide a second portion of the cooling required to divide the first stream. The third stream is passed into an indirect heat exchange relationship with the first stream to provide a third portion of the cooling required to divide the first stream. By the indirect heat exchange, the third stream is heated sufficiently to be divided into a gaseous fourth stream and a liquid fifth stream. The fourth stream is then passed through a second expander for cooling and the cooled fourth stream is then passed into indirect heat exchange relationship with the first stream to provide a fourth portion of the cooling required to separate the first stream. The fifth stream is passed into indirect heat exchange relationship with the first stream to provide a fifth portion of cooling required to divide the first stream. Where the first stream has issued from a hydroretort and is at a sufficiently high pressure, no external refrigeration is required in accordance with the invention.
In yet another aspect of the invention, there is provided an apparatus comprising a hydroretort means for producing an effluent off-gas containing carbon monoxide and hydrogen. A separation means is provided for separating the effluent off-gas into: (a) a high purity hydrogen gas stream; (b) a low BTU gas stream; and (c) a high BTU gas stream. A first conduit connects the hydroretort means with the separation means. A second conduit means connects the separation means and the hydroretort for passing the high purity hydrogen gas stream back to the hydroretort. A reformer is provided for converting the high BTU gas stream into a predominantly hydrogen stream. A third conduit means connects the separation means with the reformer for feeding the high BTU gas stream from the separation means to the reformer. A fourth conduit means connects the reformer with the hydroretort for passing hydrogen from the reformer to the hydroretort.
In yet another aspect of the present invention, an apparatus for separating the components of a gas stream comprises a means for passing two fluids in indirect heat exchange relationship and a first expander means for reducing the pressure on a fluid. A first conduit means connects the means for passing two fluids in indirect heat exchange relationship with the first expander means. A first vessel provides a means for phase separating a liquid and a gas. A second conduit means connects the first expander with the first vessel. A third conduit means connects an upper portion of the first vessel with the means for passing the two fluids in indirect heat exchange relationship. A second vessel provides a means for phase separating a liquid and a gas. A fourth conduit means connects the lower portion of the first vessel with a second vessel and passes through the means for passing two fluids in indirect heat exchange relationship. A fifth conduit means is connected to a lower portion of the second vessel and passes through a portion of the means for passing two fluids in indirect heat exchange relationship. A second expander is provided for reducing the pressure on a fluid. A sixth conduit means connects an upper portion of the second vessel with a second expander and a seventh conduit means is connected to the second expander and passes through a portion of the means for passing two fluids in indirect heat exchange relationship.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE schematically illustrates certain features of one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with certain aspects of the present invention, an apparatus 2 comprises a means 4 for carrying out a hydroretorting process; a means 6 for separating components from a gas stream; and a means 8 for reforming hydrocarbons to provide hydrogen make-up for the hydroretort. A conduit means 10 connects the retort means 4 with the separation means 6. The separation means 6 divides the contents of the conduit means 10 into a high purity hydrogen gas stream 12, a low BTU gas stream 14 and a high BTU gas stream 16. A conduit means 18 can be provided to connect the separation means 6 with the hydroretort 4 for passing the high purity hydrogen gas stream to the hydroretort. A conduit means 20 can be provided to connect the separation means 6 with the reformer means 8 for feeding the high BTU gas stream to the reformer means 8. A conduit means 22 can be provided for connecting the reformer means 8 with the hydroretort 4 for passing hydrogen from the reformer means 8 to the hydroretort means 4.
Preferably, the hydroretort 4 is a unit which receives a stream of crushed oil shale 24 and pyrolyzes the received oil shale at a temperature in the range of from about 800° to about 1200° F. in the presence of added hydrogen to produce, after suitable cooling and separation, a liquid shale oil stream 26. More preferably, the pyrolysis zone is maintained in the range of 850°-950° F. The pressure in the oil hydroretort 4 generally ranges from about 250 to about 2500 psig and the hydrogen partial pressure ranges from about 20 to about 2000 psig. More preferably, total pressure is between 500 and 1500 psig and hydrogen pressure is between 500 and 1000 psig. Preferably, the oil shale is of the type commonly found in the Eastern United States known as Devonian oil shale because there is greater economic incentive to hydroretort Devonian oil shale than shale, for example, from the Green River formation although the present invention is also applicable to Green River and oil shales from other sources as well. Residual carbon remaining on the oil shale after pyrolysis is combusted in the hydroretort 4 by combusting the residual carbon with a stream 28 of oxygen containing gas such as oxygen. A spent shale stream 30 is withdrawn from the hydroretort 4. Flue gas is withdrawn via line 32. The line 10 withdraws a gaseous effluent from the hydroretorting unit 4 which contains predominantly hydrogen and small amounts of methane and ethane and carbon monoxide.
The reformer 8 can use catalytic steam reforming, non-catalytic steam reforming, etc., but preferably uses the well known partial oxidation process for making synthesis gas which includes hydrogen, carbon monoxide, carbon dioxide and water vapor resulting from the reaction of steam, oxygen and a suitable hydrocarbon. The hydrocarbon is introduced via the line 20. Steam can be introduced into the zone 8 via a line 34. Oxygen can be introduced into the zone 8 via a line 36. After separation procedures, the hydrogen is withdrawn from the reformer via the line 22. The carbon dioxide, carbon monoxide and water vapor are withdrawn via the line 38. The hydrogen carried by the line 22 can be combined with the hydrogen carried by the line 18 and introduced into the hydroretort 4 via a line 40. Where the hydrogen introduced into the hydroretort 4 by the line 40 is of high purity, the hydrogen partial pressure in the retort can be maintained nearer that of the total retort pressure.
In accordance with another aspect of the present invention the separator means 6 is formed in the following manner. The separator 6 comprises a means 42 for passing fluids, i.e., two or more, in indirect heat exchange relationship. A first expander means 44 is provided for reducing the pressure on a fluid. A first conduit means 46 connects the means 42 with the means 44. A first vessel 48 provides a means for the phase separation of a liquid and a gas. A second conduit means 50 connects the expander means 44 with a vessel 48. A conduit means 52 connects an upper portion of the vessel 48 with the means 42 for passing the two fluids in indirect heat exchange relationship. A second vessel 54 provides a means for phase separating a liquid and a gas. A conduit means 56 connects a lower portion of the vessel 48 with the vessel 54. A pump 58 can be disposed in the conduit means 56 to cause fluid flow from the vessel 48 to the vessel 54. A level controller 60 can be coupled to the vessel 48 and a valve 62 disposed in the line 56 for controlling the liquid level in the vessel 48. The conduit means 56 passes through the means 42 for passing two fluids in indirect heat exchange relationship. A conduit means 64 is connected to a lower portion of the vessel 54 and also passes through a portion of the means 42 for passing two fluids in indirect heat exchange relationship. Preferably, the conduit means 64 provides the stream 16. If desired, a level controller 66 can be coupled to the vessel 54 and a valve 68 positioned in line 64 to provide for control of liquid level in the vessel 54. A second expander means 70 is provided for reducing the pressure on a fluid. A conduit means 72 connects an upper porition of the second vessel 54 with the expander 70. A conduit means 74 leads from the expander 70 and passes through a portion of the means 42 for passing two fluids in indirect heat exchange relationship. A pressure controller 76 can be coupled to the line 72 and the expander 70 to control the degree of expansion by the expander 70.
In a preferred embodiment of the invention the means 42 for passing two fluids in indirect heat exchange relationship comprises a first heat exchanger 78, a second heat exchanger 80, and a third heat exchanger 82. Exchangers 78, 80 and 82 may be plate-type cryogenic aluminum alloy exchangers. A conduit means 84 passes through the first heat exchanger 78, the second heat exchanger 80 and the third heat exchanger 82 and connects the conduit means 10 with the conduit means 46. The conduit means 52 connected to the upper portion of the vessel 48 passes in a countercurrent fashion with respect to the contents of the conduit 84 through the third heat exchanger 82, the second heat exchanger 80, and the first heat exchanger 78. The conduit means 56 connected to the lower portion of the vessel 48 passes through the third heat exchanger 82 and the second heat exchanger 80 countercurrently to the contents of the conduit 84. The conduit means 74 passes through the second heat exchanger 80 and the first heat exchanger 78 countercurrently to the contents of the conduit means 84. The conduit means 64 leading from the lower portion of the second vessel 54 passes through the first heat exchanger 78 countercurrently to the contents of the conduit means 84.
In a further preferred embodiment of the invention, a portion of the energy given up by the expanders 44 and 70 can be recaptured with the following apparatus. A compressor 86 is suitably connected through the expander 44 such as by a shaft 88. The conduit means 52, after passing through the third heat exchanger 82, the second heat exchanger 80, and the first heat exchanger 78 connects to the compressor 86. A second compressor 90 is connected to the expander 70 by suitable means such as by shaft 92. The conduit means 74, after passing through the second heat exchanger 80 and the first heat exchanger 78 is connected to the compressor 90. The stream 14 preferably issues from the compressor 90 and results from the compression of the contents of the conduit means 74. As required, an exhaust conduit 94 from the compressor 86 carries the compressed contents from the line 52 to compressor 96 having an external drive 98 for further compression to form the stream 12.
According to certain other aspects of the invention, there is provided a process as follows. An off-gas from a hydroretort means is provided which contains predominantly hydrogen and smaller amounts of methane and ethane and carbon monoxide and inerts, e.g. N 2 . The stream should have a low water and CO 2 content to facilitate processing, hence may require dehydration and CO 2 removal by conventional means not shown. Such a stream is carried by the conduit means 10. The off-gas stream is introduced into a separation means which is connected to the hydroretort means to separate the off-gas stream into a high purity hydrogen first stream, a low BTU gas second stream containing carbon monoxide, and a high BTU predominantly hydrocarbon third stream containing predominantly C 1 to C 4 hydrocarbons and a small amount of carbon monoxide. The means 42 can constitute a suitable separation means. The stream 12 can carry the high purity hydrogen stream. The stream 14 can correspond to the low BTU gas stream. The stream 16 can carry high BTU gas. The high BTU gas stream is fed from the separation means to a reformer means connected thereto to be reformed into hydrogen to provide makeup hydrogen for the hydroretort. A suitable reformer is represented by the zone 8 for example. The reformer 8 can be coupled to the hydroretort by the lines 22 and 40 for example. Suitable off-gas streams from the hydroretort will generally contain carbon monoxide in the range of from about 1 to about 10 percent by volume, usually from about 2 to 8 percent by volume. The high purity hydrogen stream will generally contain in the range from 90 to 100 percent by volume hydrogen, usually in the range from about 95 to about 99.8 percent by volume hydrogen. By low BTU gas stream is meant a gas stream having a BTU value in the range of from about 80 to about 800 British thermal units per standard cubic foot, BTU/SCF (lower heating value). The BTU value of this stream will generally be reduced by carbon monoxide and hydrogen. Usually the low BTU gas stream in the present invention will contain carbon monoxide in the range of from about 10 to about 50 volume percent, usually in the range of from 20 to 40 volume percent. It will also contain most of the inert gases, if present. The high BTU gas stream in accordance with the present invention will generally have a BTU value in excess of 800 BTU/SCF. Such a gas stream will contain predominantly hydrocarbons. Usually, the high BTU gas stream will contain from 95 to 99 volume percent hydrocarbon and only minor amounts of carbon monoxide and/or hydrogen, such as from 1 to about 5 percent by volume carbon monoxide.
In a still further aspect of the present invention, there is provided a process for separating components from a dehydrated, low purity hydrogen gas first stream. The first stream is cooled in a suitable means to provide a high purity hydrogen-containing gas phase and a carbon monoxide enriched hydrogen-lean liquid phase. An expander can be incorporated into the means for cooling the first stream for reducing the pressure of the first stream and further cooling it to a temperature sufficiently low to divide the first stream into a gaseous second stream containing a higher concentration of molecular hydrogen than the first stream and a liquid third stream containing a lower concentration of molecular hydrogen than the first stream. The expansion supplies the first portion of the cooling required to divide the first stream into the second stream and the third stream. The streams are divided in suitable means for separating the high purity hydrogen gas stream from the CO rich liquid stream such as a vessel in which phase separation can occur.
The second stream is passed in an indirect heat exchange relationship with the first stream to provide a second portion of the cooling required to divide the first stream into the second stream and the third stream.
The third stream is passed into indirect heat exchange relationship with the first stream to provide a third portion of the cooling required to divide the first stream into the second stream and the third stream. The third stream thereby becomes heated sufficiently so that it can be divided into a gaseous low BTU fourth stream and a liquid high BTU fifth stream in a means for separating the third stream into a low BTU gas stream and a high BTU liquid stream such as a vessel in which phase separation can occur. Preferably, the third stream is passed in countercurrent indirect heat exchange relationship with the first stream. The low BTU gas fourth stream can be conveyed to an expander via suitable conduit means so as to be reduced in pressure and cooled. The low BTU gas fourth stream can then be passed into indirect heat exchange relationship with the first gas stream to provide a fourth portion of the cooling required to separate the first gas stream into the second stream and third stream. Preferably, the fourth stream is passed into indirect countercurrent heat exchange relationship with the first stream. The fifth stream is passed into indirect heat exchange relationship with the first stream to provide a fifth portion of the cooling required to separate the first stream into the second stream and the third stream. Preferably, the fifth passes countercurrently through the means for cooling the first gas stream and can be introduced into the reformer means to be converted therein from a high BTU liquid stream into a high purity hydrogen stream which can then be fed to a hydroretort. In a preferred embodiment the first stream is cooled by indirect heat exchange in a first zone, a second zone, and a third zone. The second portion of the cooling is provided in the first zone, the second zone, and third zone. The third portion of cooling is provided in the second zone and the third zone. The fourth portion of cooling is provided in the first zone and in the second zone. The fifth portion of cooling is provided in the first zone.
Generally speaking, the first stream will contain in excess of 90 percent by volume hydrogen and moderate amounts of C 1 through C 4 hydrocarbon and carbon monoxide. The second stream will preferably contain in excess of 95 percent of the hydrogen contained in the first stream and will usually have a hydrogen concentation in excess of 95 volume percent. The fourth stream will usually contain in excess of 50% by volume of C 1 hydrocarbon and significant amounts of carbon monoxide such as in the range of 10-50% by volume. The fifth stream will usually contain in excess of 95% by volume C 1 through C 3 hydrocarbons and a small amount of carbon monoxide such as in the range of 0.1 to 5 volume %.
Where the first stream is from a hydroretort, it will usually be at a pressure in the range of from about 250 to about 2500 pounds per square inch, and frequently be at a temperature in the range of from about 50 to about 250° F. The stream will contain relatively pure hydrogen such as hydrogen at a concentration within the range from about 90 to 99 percent by volume. Minor amounts of other materials will usually be present in the first stream, such as from 1 to about 10 percent by volume carbon monoxide and from 1 to about 10 percent by volume C 1 hydrocarbon.
To further recover energy given off by expansion of the first gas stream, the second stream can be compressed in a compressor powered by the expander after the second stream is passed through an indirect heat exchange relationship with a first stream. Similarly, the fourth stream can be compressed utilizing the energy given off by the expander after passage through indirect heat exchange relationship with first stream.
The invention is illustrated by the following example:
Calculated Example
Table I below shows the material balance for the separation process illustrated in FIG. 1.
TABLE I______________________________________Mols/HrComponent Feed (10) H.sub.2 (12) Low BTU (14) High BTU (16)______________________________________H.sub.2 191,412 191,402 10 0CO 7,040 5,404 1,445 191C.sub.1 5,647 214 3,530 1,903C.sub.2.sup.= 131 0 26 105C.sub.2 1,555 1 183 1,371C.sub.3.sup.= 411 0 10 401C.sub.3 586 0 12 574C.sub.4.sup.= 272 0 2 270NC.sub.4 404 0 2 402Total 207,458 197,021 5,220 5,217______________________________________
Table II below calculated temperatures and pressures for the noted streams of the Figure.
TABLE II______________________________________Stream °F. Psia Stream °F. Psia______________________________________101 100 650 112 81 375102 -91 646 113 -325 300103 -192 643 114 -322 385104 -298 640 115 -203 382105 -325 300 116 -103 380106 -325 300 117 -103 380107 -203 297 118 -203 50108 -103 294 119 -103 45109 81 290 120 81 40110 131 360 121 184 85111 312 715 122 -103 380______________________________________ | A cryogenic hydrogen purification system is disclosed which produces low and high BTU substitute natural gas byproduct from a feed stream containing substantial carbon monoxide concentration. The required process cooling is provided by a pair of gas expanders. The purified hydrogen stream can be recycled to a hydroretort. The low BTU substitute natural gas stream contains most of the carbon monoxide. The high BTU natural gas stream forms suitable feed for a hydrogen plant. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invenation
[0002] The present invention relates to a shield assembly for a computer enclosure and a pressing machine for making the shield assembly, and particularly to a shield assembly for ready attaching to a computer enclosure and a pressing machine for pressing the shield assembly together.
[0003] 2. Related Art
[0004] A support bracket in a computer enclosure often defines a number of cavities for accommodating data storage devices therein. A front panel of the computer enclosure accordingly defines a number of openings for insertion of the data storage devices. A number of metal shields is attached in the openings of the front panel, to prevent electromagnetic radiation generated by the computer from coming out of the computer. Such metal shields are commonly integral with the front panel. When a data storage device is required to be installed, a metal shield is removed from the front panel using a tool.
[0005] However, removing this kind of metal shield from the front panel with a tool is unduly inconvenient. Furthermore, the metal shield cannot be reused. Thus when a data storage device is removed from the support bracket, the opening of the front panel cannot be covered back over again with the shield. This allows electromagnetic radiation to come out of the computer, or necessitates use of a replacement shield.
[0006] It is strongly desired to provide a shield assembly for a computer enclosure which overcomes the above problems encountered in the related art.
SUMMARY OF THE INVENTION
[0007] Accordingly, an object of the present invention is to provide a shield assembly for covering an opening defined in a computer enclosure, to prevent electromagnetic radiation from coming out of the computer.
[0008] Another object of the present invention is to provide a pressing machine which can readily make the shield assembly.
[0009] To achieve the above-mentioned objects, a shield assembly of the present invention comprises a plastic member and a metal member attached on the plastic member. The plastic member forms a tab with a projection and a plurality of cross protrusions. The metal member has a gap for extension of the tab therethrough, an inclined plate defining an aperture for engaging with the projection to prevent the metal member from moving relative to the plastic member in a vertical direction, and a plurality of cross cuts for engaging with the cross protrusions to prevent the metal member from moving relative to the plastic member in a horizontal direction.
[0010] The pressing machine for combining the metal member and the plastic member of the shield assembly together comprises a workbench, a cylinder, a guide device, a pressing device and a coupling bar connected between the cylinder and the pressing device. The workbench comprises a position board defining a plurality of channels for receiving the corresponding plastic members thereon. The pressing device comprises a pair of pressing blocks and a pressing bar between the pressing blocks. Each pressing block defines a plurality of cross indentions for receiving the protrusions of the plastic members. This allows the metal member to be downwardly pressed, thereby causing the cross cuts of the metal member to engage with the cross protrusions of the plastic member. The pressing bar comprises a plurality of pressing feet for downwardly pressing the inclined plates of the metal members, to allow the inclined plates to engage with the projections of the plastic member in the apertures thereof.
[0011] Other objects, advantages and novel features of the present invention will be drawn from the following detailed description of preferred embodiments of the present invention with reference to the attached drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] [0012]FIG. 1 is an assembled view of a shield assembly in accordance with the present invention;
[0013] [0013]FIG. 2 is an enlarged view of the circled portion II of FIG. 1;
[0014] [0014]FIG. 3 is a perspective view of a pressing machine for combining the shield assembly of FIG. 1;
[0015] [0015]FIG. 4 is a perspective view of a base of a guide device of the pressing machine of FIG. 3;
[0016] [0016]FIG. 5 is a perspective view of a pressing block of FIG. 3;
[0017] [0017]FIG. 6 is a bottom planar view of FIG. 5; and
[0018] [0018]FIG. 7 is a perspective view of a pressing bar of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Referring to FIGS. 1 and 2, a shield assembly 12 in accordance with the present invention comprises a plastic member 14 and a metal member 16 attached on an inner side of the plastic member 14 .
[0020] The plastic member 14 is rectangular. A tab 22 extends upwardly from a central portion of the inner side of the plastic member 14 . A projection 24 is formed on one side wall of the tab 22 . Four cross protrusions 20 respectively extend upwardly from the inner side of the plastic member 14 , two on each side of the tab 22 . A pair of spaced fasteners 26 extends upwardly from one end of the inner side of the plastic member 14 . A pair of hooks 28 extends upwardly from the other end of the inner side of the plastic member 14 , opposite to the fasteners 26 . Four cross cuts 34 are defined in the metal member 16 for receiving the four cross protrusions 20 of the plastic member 14 , to prevent the metal member 16 from moving relative to the plastic member 14 in a horizontal direction. A gap 38 is defined in a central portion of the metal member 16 , for extension of the tab 22 of the plastic member 14 therethrough. An inclined plate 40 extends from an edge of the metal member 16 , adjacent the gap 38 . An aperture 42 is defined in a free end of the inclined plate 40 for receiving the projection 24 of the plastic member 14 , to prevent the metal member 16 from moving relative to the plastic member 14 in a vertical direction. A pair of first arms 48 extends from one end of the metal member 16 . A first cutout 46 is defined between the pair of first arms 48 . Each first arm 48 defines a cutaway 50 in a free end thereof, for extension of the corresponding fastener 26 of the plastic member 14 therethrough. A pair of second arms 58 extends from the other end of the metal member 16 . A second cutout 56 is defined between the pair of second arms 58 . Each second arm 58 defines a hole 59 therein, for extension of the corresponding hook 28 of the plastic member 14 therethrough.
[0021] In use, the shield assembly 12 is embedded in an opening defined in a front panel of a computer enclosure (not shown). The fasteners 26 and the hooks 28 of the shield assembly 12 are respectively engaged with the computer enclosure. The first and second arms 48 , 58 are resiliently retained against the enclosure such that the metal member 16 covers the opening. Thus electromagnetic radiation is prevented from coming out of the opening.
[0022] Referring to FIG. 3, a pressing machine 10 combines corresponding metal members 16 and plastic members 14 together to form shield assemblies 12 of the present invention. The pressing machine 10 comprises a cylinder 54 , a workbench 60 , a guide device 100 , a pressing device 200 , and a coupling bar 205 connected between the cylinder 54 and the pressing device 200 .
[0023] The workbench 60 comprises four side walls 62 and a top wall 64 disposed on the four side walls 62 . A mounting board 66 is secured on the top wall 64 . A position board 68 is mounted on the mounted board 66 . A plurality of channels 70 is defined in a top surface of the position board 68 , for receiving the plastic members 14 of the shield assemblies 12 . Three through holes 72 are defined in a front portion of the top wall 64 of the workbench 60 , for mounting three buttons 74 therein. A pair of support plates 76 is secured on a rear portion of the top wall 64 , opposite to the buttons 74 . A vertical plate 78 is connected between side walls of the pair of the support plates 76 , forming a space (not labeled) for receiving a control circuit (not shown) therein.
[0024] Referring also to FIG. 4, the guide device 100 comprises a base 110 , a pair of guide bushings 112 , and a pair of guide posts 114 . A recess 116 is defined in a central portion of a top surface of the base 110 , forming a pair of shoulders 124 on opposite sides of the recess 116 . A passageway 118 is defined in the base 110 , below the recess 116 . Four first shoulder holes 120 are defined in the base 110 , below the recess 116 and around the passageway 118 . Each shoulder 124 forms a connecting portion 126 extending upwardly from one end thereof. A second shoulder hole 130 is defined in each shoulder 124 . Each connecting portion 126 defines a screw hole 128 , for extension of a bolt (not shown) therethrough to engage with the vertical plate 78 and thereby secure the base 110 on the workbench 60 .
[0025] The cylinder 54 is secured on the base 110 with a chassis (not labeled) thereof received in the recess 116 . Four screws 122 are extended through the shoulder holes 120 of the base 110 to engage with threaded holes (not labeled) defined in the cylinder 54 . The guide bushings 112 interferentially engage with the base 110 in the second shoulder holes 130 . The guide posts 114 respectively extend through the corresponding guide bushings 112 .
[0026] Referring also to FIGS. 5 - 7 , the pressing device 200 comprises a connecting plate 210 , a bottom plate 212 , a pair of pressing blocks 220 , and a pressing bar 222 . The connecting plate 210 is secured on a top surface of the bottom plate 212 . The guide posts 114 of the guide device 100 are secured on opposite sides of the connecting plate 210 . The pressing bar 222 is secured under a central portion of a bottom surface of the bottom plate 212 . The pair of pressing blocks 220 is respectively secured under the bottom surface of the bottom plate 212 , on opposite sides of the pressing bar 222 . Each pressing block 220 defines a longitudinal groove 224 in a center of a bottom surface thereof. A plurality of spaced slots 226 is defined in the bottom surface of the pressing block 220 , perpendicular to the longitudinal groove 224 , thereby forming a plurality of cross indentions 228 . A pair of stanchions 230 is formed on opposite sides of the bottom surface of the pressing block 220 . The pressing bar 222 forms a plurality of press feet 232 , corresponding to the channels 70 of the position board 68 .
[0027] In operation, the plastic members 14 of the shield assembly 12 are respectively placed on the channels 70 of the position board 68 . The corresponding metal members 16 are placed on the plastic members 14 , with the cross cuts 34 of the metal members 16 above the corresponding cross protrusions 20 of the plastic member 14 . The fasteners 26 of the plastic members 14 respectively extend through the corresponding cutaways 50 of the metal members 16 , and the hooks 28 of the plastic members 14 extend through the corresponding holes 60 of the metal members 16 . The power supply button of the buttons 74 is then turned on. The coupling bar 205 is pushed downwardly by air pressure of the cylinder 54 . The pressing device 200 is accordingly downwardly moved. The cross indentions 228 of the pressing block 220 respectively receive the corresponding cross protrusions 20 of the plastic member 14 therein, and the bottom surface of the pressing block 220 downwardly presses the metal members 16 near the cross openings 340 of the metal members 16 . The press feet 232 of the pressing bar 222 respectively downwardly press the inclined plates 40 of the metal members 16 , thereby causing the inclined plates 40 to downwardly snap on the corresponding projections 24 . The coupling bar 205 continues to move downwardly until the stanchions 230 of the pressing block 220 abut the position board 68 of the workbench 60 . At this time, the cross protrusions 20 of the plastic members 14 are completely received in the cross cuts 34 of the metal members 16 , and the apertures 42 of the metal member 16 engage with the projections 24 of the plastic member 16 .
[0028] It is understood that the invention may be embodied in other forms without departing from the spirit thereof. Thus, the present examples and embodiments are to be considered in all respects as illustrative and not restrictive, and the invention is not to be limited to the details given herein. | A pressing machine ( 10 ) for combining metal members ( 16 ) and plastic members ( 14 ) of shield assembles ( 12 ) includes a workbench ( 60 ), a cylinder ( 54 ), a guide device ( 100 ), and a pressing device ( 200 ). The workbench defines channels ( 70 ) for receiving the corresponding plastic members thereon. The pressing device includes two pressing blocks ( 220 ) defining cross indentions ( 228 ) for receiving protrusions formed in the plastic members to allow the metal members to be downwardly pressed thereby causing the cross cuts defined in the metal member to engage with the cross protrusions of the plastic member, and a pressing bar ( 222 ) forming pressing feet ( 232 ) for downwardly pressing inclined plates ( 40 ) formed in the metal members to allow apertures ( 42 ) defined in the inclined plates to engage with projections ( 24 ) formed in the tabs ( 22 ) of the plastic members. | 8 |
This application is a continuation of U.S. patent application Ser. No. 11/015,508, filed Dec. 16, 2004, now U.S. Pat. No. 7,381,824, which claims the benefit of U.S. Patent Application No. 60/532,725, filed Dec. 23, 2003, all of which are hereby incorporated by reference.
FIELD OF THE INVENTION
This invention relates to novel quinoline analogs and derivatives thereof, including pharmaceutically acceptable derivatives, such as salts, and solvates. The compounds of the present invention inhibit the activity of receptor kinases such as VEGFR and PDGRF that are required for cell growth and differentiation and angiogenesis. Particularly, the compounds in this invention inhibit VEGFR/KDR and therefore are useful for treatment of diseases and conditions that are associated with VEGFR/KDR activity, e.g., cancer and ophthalmic diseases such as age-related macular degeneration. This invention also relates to a method of using such compounds in the treatment of hyperproliferative diseases in mammals, especially humans, and to pharmaceutical compositions containing such compounds.
BACKGROUND OF THE INVENTION
A cell may become cancerous by virtue of the transformation of a portion of its DNA into an oncogene (i.e., a gene that upon activation leads to the formation of malignant tumor cells). Many oncogenes encode proteins that are aberrant tyrosine kinases capable of causing cell transformation. Alternatively, the overexpression of a normal proto-oncogenic tyrosine kinase may also result in proliferative disorders, sometimes resulting in a malignant phenotype.
Receptor tyrosine kinases are large enzymes that span the cell membrane and possess an extracellular binding domain for growth factors, a transmembrane domain, and an intracellular portion that functions as a kinase to phosphorylate a specific tyrosine residue in proteins and hence to influence cell proliferation. Tyrosine kinases may be classified as growth factor receptor (e.g. EGFR, PDGFR, FGFR and erbB2) or non-receptor (e.g. c-src and bcr-abl) kinases. Such kinases may be aberrantly expressed in common human cancers such as breast cancer, gastrointestinal cancers such as colon, rectal or stomach cancer, leukemia, and ovarian, bronchial or pancreatic cancer. Aberrant erbB2 activity has been implicated in breast, ovarian, non-small cell lung, pancreatic, gastric and colon cancers. Studies indicate that epidermal growth factor receptor (EGFR) is mutated or overexpressed in many human cancers such as brain, lung, squamous cell, bladder, gastric, breast, head and neck, oesophageal, gynecological and thyroid cancers. Thus, inhibitors of receptor tyrosine kinases may be useful as selective inhibitors of the growth of mammalian cancer cells.
EGFR inhibitors may be useful in the treatment of pancreatitis and kidney disease (such as proliferative glomerulonephritis and diabetes-induced renal disease), and may reduce successful blastocyte implantation and therefore may be useful as a contraceptive. See PCT international application publication number WO 95/19970 (published Jul. 27, 1995), hereby incorporated by reference in its entirety.
Polypeptide growth factors, such as vascular endothelial growth factor (VEGF) having a high affinity to the human kinase insert-domain-containing receptor (KDR) or the murine fetal liver kinase 1 (FLK-1) receptor have been associated with the proliferation of endothelial cells and more particularly vasculogenesis and angiogenesis. See PCT international application publication number WO 95/21613 (published Aug. 17, 1995), hereby incorporated by reference in its entirety. Agents that are capable of binding to or modulating the KDR/FLK-1 receptor may be used to treat disorders related to vasculogenesis or angiogenesis, such as diabetes, diabetic retinopathy, age related macular degeneration, hemangioma, glioma, melanoma, Kaposi's sarcoma and ovarian, breast, lung, pancreatic, prostate, colon and epidermoid cancer.
Compounds and methods that reportedly can be used to treat hyperproliferative diseases are disclosed in the following patents and applications: PCT international patent application publication number WO 00/38665 (published Jul. 6, 2001), PCT international patent application publication number WO 97/49688 (published Dec. 31, 1997), PCT international patent application publication number WO 98/23613 (published Jun. 4, 1998), U.S. patent application Ser. No. 09/502,129 (filed Feb. 10, 2000), U.S. patent application Ser. No. 08/953,078 (filed Oct. 17, 1997), U.S. Pat. No. 6,071,935 issued Jun. 6, 2000, PCT international patent application publication number WO 96/30347 (published Oct. 3, 1996), PCT international patent application publication number WO 96/40142 (published Dec. 19, 1996), PCT international patent application publication number WO 97/13771 (published Apr. 17, 1997), PCT international patent application publication number WO 95/23141 (published Aug. 31, 1995), PCT international patent application publication number WO 03/006059 (published Jan. 23, 2003), PCT international patent application publication number WO 03/035047 (published May 1, 2003), PCT international patent application publication number WO 02/064170 (published Aug. 22, 2002), PCT international patent application publication number WO 02/41882 (published May 30, 2002), PCT international patent application publication number WO 02/30453 (published Apr. 18, 2002), PCT international patent application publication number WO 01/85796 (published Nov. 15, 2001), PCT international patent application publication number WO 01/74360 (published Oct. 11, 2001), PCT international patent application publication number WO 01/74296 (published Oct. 11, 2001), PCT international patent application publication number WO 01/70268 (published Sep. 27, 2001), European patent application publication number EP 1086705 (published Mar. 28, 2001), and PCT international patent application publication number WO 98/51344 (published Nov. 19, 1998). The foregoing patent and applications are each incorporated herein by reference in their entirety.
SUMMARY OF THE INVENTION
Described herein are compounds capable of modulating the activity of receptor kinases such as VEGFR and PDGRF and methods for utilizing such modulation in the treatment of cancer and other proliferative disorders. Also described are compounds that mediate and/or inhibit the activity of protein kinases, and pharmaceutical compositions containing such compounds. Also described are therapeutic or prophylactic use of such compounds and compositions, and methods of treating cancer as well as other diseases associated with unwanted angiogenesis and/or cellular proliferation, by administering effective amounts of such compounds.
In one aspect are novel quinoline compounds. In another aspect provided are compounds that modulate the activity of receptor kinases such as KDR/VEGFR2 kinase in vitro and/or in vivo. According to a further aspect, provided are compounds that can selectively modulate the activity of receptor kinases such as KDR/VEGFR2 kinase. In yet another aspect, provided are pharmaceutical compositions of such VEGFR2-modulating compounds, including pharmaceutically acceptable salts thereof. According to yet another aspect, provided are syntheses schemes for the preparation of such VEGFR2-modulating compounds, and pharmaceutically acceptable salts thereof. In yet another aspect, methods are provided for modulating KDR/VEGFR2 kinase which comprise contacting the VEGFR2-modulating compounds, or pharmaceutically acceptable salts thereof, described herein, with KDR/VEGFR2 kinase. In yet another aspect, provided are methods for treating patients comprising administering a therapeutically effective amount of a VEGFR2-modulating compound, or a pharmaceutically acceptable salt thereof. In yet another aspect, are combination therapies involving administration of an anti-neoplastic agent and an effective amount of a VEGFR2-modulating compound, or a pharmaceutically acceptable salt thereof.
In one aspect are compounds of Formula (I):
wherein
the ------ in Formula (I) indicates an optional bond;
is selected from the group consisting of
the ------ line indicates an optional bond;
X 1 is a bond or —C(O)NH—;
X 2 is O, S, or NR 9 where ----- is not a bond, or X 2 is N or CH where ----- is a bond;
R 9 is H or —CH 3 ;
R 1a and R 1b are selected from the group consisting of H, —(CR 10 R 11 ) j CN, —(CR 10 R 11 ) j —(C 3 -C 8 )cycloalkyl, —(CR 10 R 11 ) j —(C 5 -C 8 )cycloalkenyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, —(CR 10 R 11 ) j -aryl, —(CR 10 R 11 ) j -heterocyclyl, and (C 1 -C 8 )alkyl, and wherein the C atoms of R 1a and R 1b can be optionally substituted with 1-3 independently selected R 12 groups;
R 2a and R 2b are selected from the group consisting of H, —CH 3 , —CF 3 , —CN, —CH 2 CH 3 , —OCH 3 , and
—OCF 3 ;
R 3 and R 8 are independently F;
X 3 is O or NH;
X 5 is C where ----- in Formula (I) is a bond, or, where ----- in Formula (I) is not a bond, is CH or N;
R 4 and R 7 are independently selected from H, halogen, —CH 3 , and CF 3 ;
R 5 and R 6 are independently selected from the group consisting of H, halogen, —CF 3 , —N 3 , —NO 2 ,
—OH —NH 2 , —OCF 3 , —X 4 (CR 10 R 11 ) j CN, —X 4 (CR 10 R 11 ) j —(C 3 -C 8 ) cycloalkyl, —X 4 (CR 10 R 11 )—(C 5 -C 8 ) cycloalkenyl,
—X 4 (C 2 -C 6 ) alkenyl, —X 4 (C 2 -C 6 )alkynyl, —X 4 (CR 10 R 11 ) j -aryl, —X 4 (CR 10 R 11 ) j -heterocyclyl, heterocyclyl, and
—X 4 (C 1 -C 8 )alkyl, and wherein the C and N atoms of R 5 and R 6 can be optionally substituted with 1 to 3 independently selected R 13 groups, or wherein R 5 and R 6 taken together may form a cyclic moiety selected from the group consisting of a 4-10 membered carbocyclyl and a 4-12 membered heterocyclyl which is optionally substituted with 1 to 3 independently selected R 13 groups;
X 4 is selected from the group consisting of a bond, O, NH, —C(O)—, —NHC(O)—, —OC(O)—, —C(O)O—,
—C(O)NH—, and S;
each R 10 and R 11 are independently selected from the group consisting of H, F, and (C 1 -C 6 )alkyl, or R 10 and R 11 taken together may form a carbocyclyl, or two R 10 groups attached to adjacent carbon atoms may be selected together to form a carbocyclyl;
each R 12 and R 13 are independently selected from the group consisting of halogen, cyano, nitro, tetrazolyl, guanidino, amidino, methylguanidino, azido, —C(O)R 14 —C(O), —CF 3 , —CF 2 CF 3 , —CH(CF 3 ) 2 ,
—C(OH)(CF 3 ) 2 , —OCF 3 , —OCF 2 H, —OCF 2 CF 3 , —OC(O)NH 2 , —OC(O)NHR 14 , —OC(O)NR 14 R 15 , —NHC(O)R 14
—NHC(O)NH 2 , —NHC(O)NHR 14 —NHC(O)NR 14 R 15 , —C(O)OH, —C(O)OR 14 —C(O)NH 2 , —C(O)NHR 14 , —C(O)NR 14 R 15 , —P(O) 3 H 2 , —P(O) 3 (R 14 ) 2 , —S(O) 3 H, —S(O) m R 14 , —R 14 —OR 14 , —OH, —NH 2 , —NH, —NHR 14 —NR 14
—NR 14 R 15 , —C(═NH)NH 2 , —C(═NOH)NH 2 , —N-morpholino, (C 2 -C 6 )alkyl, where any of the C atoms can be optionally substituted with an O atom, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 2 -C 6 )haloalkenyl, (C 2 -C 6 )haloalkynyl, (C 1 -C 6 )haloalkoxy, —(CR 16 R 17 ) r NH 2 , —(CR 16 R 17 ) r NHR 14 , —CNR 14 R 15 , (CR 16 R 17 ) r NR 14 R 15 and —S(O) m (CF 2 ) q CF 3 ;
or any two R 12 or any two R 13 groups attached to adjacent carbon atoms may be selected together to be —O[C(R 16 )(R 17 )] r O— or —O[C(R 16 )(R 17 )] r+1 —; or any two R 12 or any two R 13 groups attached to the same or adjacent carbon atoms may be selected together to form a carbocyclyl or heterocyclyl;
each R 14 and R 15 are independently selected from the group consisting of (C 1 -C 12 ) alkyl, (C 3 -C 8 ) cycloalkyl, (C 6 -C 14 ) aryl, 4-12 membered heterocyclyl, —(CR 10 R 11 ) j —(C 6 -C 10 ) aryl, and —(CR 10 R 11 ) j -(4-12 membered heterocyclyl);
each R 16 and R 17 are independently selected from the group consisting of hydrogen, (C 1 -C 12 ) alkyl, (C 6 -C 14 ) aryl, 4-12 membered heterocyclyl, —(CR 10 R 11 ) j —(C 6 -C 10 ) aryl, and —(CR 10 R 11 ) j -(4-12 membered heterocyclyl);
and wherein any of the above-mentioned substituents comprising a CH 3 (methyl), CH 2 (methylene), or CH (methine) group which is not attached to a halogen, SO or SO 2 group or to a N, O or S atom optionally bears on said group a substituent selected from the group consisting of hydroxy, halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy and —N[(C 1 -C 4 )alkyl][(C 1 -C 4 )alkyl];
and wherein j is 0, 1, 2, or 3 and when j is 2 or 3, each CR 10 R 11 unit may be the same or different;
and wherein n is 0, 1, 2, or 3, and m is 0, 1 or 2;
and wherein q is an integer from 0 to 5, and r is an integer from 1 to 4;
or a pharmaceutically acceptable solvate or pharmaceutically acceptable salt thereof.
In one embodiment are compounds having the structure of Formula (I), wherein
wherein R 1a , R 2a , X 2 and X 3 are as defined in connection with Formula (I). In further embodiments provided are compounds where (a) n and m are both 0; (b) X 4 is O; (c) R 4 and R 7 are both H; (d) R 2a is CH 3 ; (e) R 4 and R 7 are both H, R 2a is CH 3 , and n and m are both 0 (and further, wherein X 2 is either O or S); (f) X 2 is either O or S; or (g) R 4 , R 5 , and R 7 are all H. Where R 4 , R 5 and R 7 are H, an alternative embodiment is directed to compounds wherein R 2a is CH 3 , n and m are both 0, and X 2 is either O or S; this embodiment may further include compounds, wherein (1) R 6 is —X 4 (CR 10 R 11 ) j -heterocyclyl, and X 4 is a bond or O or (2) R 6 is —X 4 (C 1 -C 8 )alkyl, and X 4 is a bond or O
In another embodiment provided are compounds having the structure of Formula (I), wherein
wherein R 1a , R 2a and X 2 are as defined in connection with Formula (I) and j is 0. In a further embodiment of such compounds, R 1a is selected from the group consisting of —(C 3 -C 8 )cycloalkyl, -aryl, -heterocyclyl, and (C 1 -C 8 )alkyl all of which may be optionally substituted with 1 to 3 independently selected R 12 groups.
In another embodiment are compounds having the structure of Formula (I), wherein
wherein X 1 , R 1b , R 2b and R 9 are as defined in connection with Formula (I).
In a further embodiment are compounds in which X 3 is NH. In yet further embodiments are such compounds in which (a) X 1 is —C(O)NH—; (b) R 2b is —CH 3 ; or (c) R 2b is CH 3 and n and m are both 0. Where R 2b is CH 3 and n and m are both O, another embodiment is directed to compounds in which X 1 is —C(O)NH—. This embodiment may further include compounds where (1) R 6 is —X 4 (CR 10 R 11 ) j -heterocycle, and X 4 is a bond or O; or (2) R 6 is —X 4 (C 1 -C 8 )alkyl, and X 4 is a bond or O.
In another embodiment are compounds having the structure of Formula (I) selected from the following group consisting of:
5-[(7-chloroquinazolini-4-yl)amino]-N,2-dimethyl-1H-indole-1-carboxamide, 6-[(7-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, N-2-dimethyl-6-[(7-pyridin-4-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, N-2-dimethyl-6-[(7-pyridin-3-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, N-2-dimethyl-6-[(7-pyridin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, N-2-dimethyl-6-[(7-pyridin-4-ylquinolin-4-yl]oxy]-1-benzothiophene-3-carboxamide, N-2-dimethyl-5-[(7-pyridin-4-ylquinolin-4-yl]amino]-1H-indole-1-carboxamide, N,2-dimethyl-5-[(7-pyridin-3-ylquinolin-4-yl)amino]-1H-indole-1-carboxamide, 6-{[7-(2-furyl)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide, N-2-dimethyl-6-[(7-pyridin-3-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide, 6-[(7-{[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]carbonyl}quinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, 6-[(7-{[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]carbonyl}quinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide, N,2-dimethyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide, N,2-dimethyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, 6-[(7-bromoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, 6-[(7-bromoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide, 6-[(6-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide, 6-[(6-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, N,2-dimethyl-6-[(6-pyridin-4-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, 6-[(6-methoxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide, 6-[(6-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide, N,2-dimethyl-6-({6-[2-(1-methylpyrrolidinyl-2-yl)ethoxy]quinolin-4-yl}oxy)-1-benzothiophene-3-carboxamide, 6-[(7-methoxyquinoline-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, 6-[(7-hydroxyquinoline-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide, N,2-dimethyl-6-{(7-1,3-thiazol-2-yl)quinolin-4-yl)oxy}-1-benzofuran-3-carboxamide, N,2-dimethyl-6-[(7-pyridin-2-yl)quinolin-4-yl)oxy}-1-benzothiaphene-3-carboxamide, N,2-dimethyl-5-[(7-pyridin-2-yl)quinolin-4-yl)amino]-1H-indole-1-carboxamide, N,2-dimethyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N,2-dimethyl-6-{[7-(pyridin-2-ylmethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N,2-dimethyl-6-{[7-(thiazol-2-ylmethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N,2-dimethyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N,2-dimethyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, 6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-N,2-dimethyl-1-benzofuran-3-carboxamide, N-butyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-pyridin-2-yl-1-benzofuran-3-carboxamide, N-butyl-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, 6-{[7-(allyloxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide, N-isopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-butyl-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-butyl-2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-butyl-6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide, N-butyl-2-methyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-cyclopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-[2-(dimethylamino)ethyl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, [(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-propyl-1-benzothiophene-3-carboxamide, N-[3-(dimethylamino)propyl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-cyclohexyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-cyclopentyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-3-ylmethyl)-1-benzothiophene-3-carboxamide, 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-N-propyl-1-benzothiophene-3-carboxamide, N-[2-(dimethylamino)ethyl]-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-cyclopentyl-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-[3-(dimethylamino)propyl]-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-3-ylmethyl)-1-benzothiophene-3-carboxamide, N,2-dimethyl-6-{[7-(trifluoromethyl)quinolin-4-yl]oxy}-1-benzothiophene-3-carboxamide, N,2-dimethyl-6-{[7-(trifluoromethyl)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzothiophene-3-carboxamide, N-cyclopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-2-ylmethyl)-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-benzofuran-3-carboxylic acid (3-dimethylamino-propyl)-amide, N-(3-hydroxypropyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-(5-hydroxy-1H-pyrazol-3-yl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, 6-[(7-hydroxyquinolin-4-yl)oxy]-N-isopropyl-2-methyl-1-benzofuran-3-carboxamide, 6-[(7-hydroxyquinolin-4-yl)oxy]-N-isopropyl-2-methyl-1-benzothiophene-3-carboxamide, N-isopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, [(7-methoxyquinolin-4-yl)oxy]-N,1,2-trimethyl-1H-indole-3-carboxamide, N-isopropyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-butyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-N,1,2-trimethyl-1H-indole-3-carboxamide, N,1,2-trimethyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide, N,1,2-trimethyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide, N-(2-hydroxypropyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-(2-hydroxybutyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N-(3-hydroxybutyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide, N,1,2-trimethyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide, 6-{[7-(1,3-dioxolan-2-ylmethoxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[(2R)-tetrahydrofuran-2-ylmethyl]-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[(2S)-tetrahydrofuran-2-ylmethyl]-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[ethoxy-ethyl]-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[2-methoxy-1-methyl-ethyl]-1-benzofuran-3-carboxamide, N-(2-methoxyethyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-({7-[2-(methylamino)ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-({7-[2-(diethylamino)ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-({7-[2-hydroxy-ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide, 6-{[7-(2-bromoethoxy)quinolin-4-yl]oxy}-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{7-[2-(4-ethyl-piperazin-1-yl)-ethoxy]quinolin-4-yloxy}-1-benzofuran-3-carboxamide, N-cyclopropyl-6-({7-[2-(isopropylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-6-({7-[2-(cyclopropylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-6-[(7-{2-[(2-methoxy-1-methylethyl)amino]ethoxy}quinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, 6-({7-[2-(tert-butylamino)ethoxy]quinolin-4-yl}oxy)-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, 6-({7-[2-(cyclobutylamino)ethoxy]quinolin-4-yl}oxy)-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide, 6-{[7-(benzyloxy)quinolin-4-yl]oxy}-N-(4,6-dimethylpyridin-2-yl)-2-methyl-1-benzofuran-3-carboxamide, N-(4,6-dimethylpyridin-2-yl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-(4,6-dimethylpyridin-2-yl)-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(2-piperazin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, N-cyclopropyl-6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide, 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-{6-[(3-methylbutyl)amino]pyridin-3-yl}-1-benzofuran-3-carboxamide, 7-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide, N,2-dimethyl-7-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}imidazo[1,2-α]pyridine-3-carboxamide, N,2-dimethyl-6-({7-[(2-oxo-1,3-dioxolan-4-yl)methoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide, N-(2-methyl-1H-indol-5-yl)-7-(trifluoromethyl)quinoline-4-amine, 8-chloro-N-(2-methyl-1H-indol-5-yl)quinolin-4-amine, N-(2-methyl-1H-indol-5-yl)quinolin-4-amine, 6-hydroxy-N,2-dimethyl-1-benzofuran-3-carboxamide, N,2-dimethyl-6-[(6-pyridin-4-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide, N-cyclopropyl-6-({7-[2-(ethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(6-morpholin-4-ylpyridin-3-yl)-1-benzofuran-3-carboxamide, 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzofuran-3-carboxamide, N-cyclopropyl-2-methyl-6-{[7-(2-piperazin-1-ylethoxy)quinolin-4-yl]oxy}-1 benzofuran-3-carboxamide, 6-{[7-(2,3-dihydroxypropoxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide, N-[5-(aminomethyl)pyridin-2-yl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, N-[6-(aminomethyl)pyridin-3-yl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide, 4-{[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}butanoic acid, {[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}acetic acid, N-(4,6-dimethylpyridin-2-yl)-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide, methyl 2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxylate, 6-({7-[2-hydroxy-3-(methylamino)propoxy]quinolin-4-yl}oxy)-N,2-dimethyl-1-benzofuran-3-carboxamide, and methyl 4-{[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}butanoate,
or a pharmaceutically acceptable solvate or pharmaceutically acceptable salt thereof.
In another embodiment are compounds having the structure of Formula (I) selected from the group consisting of:
or a pharmaceutically acceptable solvate or pharmaceutically acceptable salt thereof.
In another embodiment are methods for producing a compound having the structure of Formula (I), wherein
comprising (a) treating a carboxylic acid having the formula
with an activating agent; and
(b) contacting the corresponding product with H 2 NR 1a . In a further embodiment of such methods, the activating agent is selected from the group consisting of thionyl chloride, oxalyl chloride, and O-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HATU).
In another embodiment are methods for producing a compound having the structure of Formula (I), wherein
comprising treating a quinoline compound having the formula
with a compound having the formula
in the presence of an acid. In a further embodiment of such methods, X 3 is NH and said acid is HCl.
In another embodiment are methods for producing a compound having the structure of Formula (I), wherein
comprising treating a quinoline compound having the formula
with a compound having the formula
in the presence of a base.
Patients that can be treated with the compounds of formula (I), and pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, according to the methods of this invention include, for example, patients that have been diagnosed as having psoriasis, benign prostatic hypertrophy (BPH), lung cancer, eye cancer, bone cancer, pancreatic cancer, skin cancer, cancer of the head and neck, cutaneous or intraocular melanoma, uterine cancer, ovarian cancer, rectal cancer, cancer of the anal region, stomach cancer, colon cancer, breast cancer, gynecologic tumors (e.g., uterine sarcomas, carcinoma of the fallopian tubes, carcinoma of the endometrium, carcinoma of the cervix, carcinoma of the vagina or carcinoma of the vulva), Hodgkin's disease, cancer of the esophagus, cancer of the small intestine, cancer of the endocrine system (e.g., cancer of the thyroid, parathyroid or adrenal glands), sarcomas of soft tissues, cancer of the urethra, cancer of the penis, prostate cancer, chronic or acute leukemia, solid tumors of childhood, lymphocytic lymphomas, cancer of the bladder, cancer of the kidney or ureter (e.g., renal cell carcinoma, carcinoma of the renal pelvis), or neoplasms of the central nervous system (e.g., primary CNS lymphoma, spinal axis tumors, brain stem gliomas or pituitary adenomas).
The invention also relates to a pharmaceutical composition for the treatment of a hyperproliferative disorder in a mammal which comprises a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, and a pharmaceutically acceptable carrier. In one embodiment, said pharmaceutical composition is for the treatment of cancer such as brain, lung, ophthalmic, squamous cell, bladder, gastric, pancreatic, breast, head, neck, renal, kidney, ovarian, prostate, colorectal, oesophageal, gynecological or thyroid cancer. In another embodiment, said pharmaceutical composition is for the treatment of a non-cancerous hyperproliferative disorder such as benign hyperplasia of the skin (e.g., psoriasis) or prostate (e.g., benign prostatic hypertrophy (BPH)).
The invention also relates to a pharmaceutical composition for the treatment of pancreatitis or kidney disease (including proliferative glomerulonephritis and diabetes-induced renal disease) in a mammal which comprises a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, and a pharmaceutically acceptable carrier.
The invention also relates to a pharmaceutical composition for the prevention of blastocyte implantation in a mammal which comprises a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, and a pharmaceutically acceptable carrier.
The invention also relates to a pharmaceutical composition for treating a disease related to vasculogenesis or angiogenesis in a mammal which comprises a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, and a pharmaceutically acceptable carrier. In one embodiment, said pharmaceutical composition is for treating a disease selected from the group consisting of tumor angiogenesis, chronic inflammatory disease such as rheumatoid arthritis, atherosclerosis, skin diseases such as psoriasis, eczema, and scleroderma, diabetes, diabetic retinopathy, retinopathy of prematurity, age-related macular degeneration, hemangioma, glioma, melanoma, Kaposi's sarcoma and ovarian, breast, lung, pancreatic, prostate, colon and epidermoid cancer.
The invention also relates to a method of treating a hyperproliferative disorder in a mammal which comprises administering to said mammal a therapeutically effective amount of the compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds. In one embodiment, said method relates to the treatment of cancer such as brain, ophthalmic, squamous cell, bladder, gastric, pancreatic, breast, head, neck, oesophageal, prostate, colorectal, lung, renal, kidney, ovarian, gynecological or thyroid cancer. In another embodiment, said method relates to the treatment of a non-cancerous hyperproliferative disorder such as benign hyperplasia of the skin (e.g., psoriasis) or prostate (e.g., BPH).
The invention also relates to a method for the treatment of a hyperproliferative disorder in a mammal which comprises administering to said mammal a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, in combination with an anti-tumor agent selected from the group consisting of mitotic inhibitors, alkylating agents, anti-metabolites, intercalating antibiotics, growth factor inhibitors, cell cycle inhibitors, enzymes, topoisomerase inhibitors, biological response modifiers, anti-hormones, and anti-androgens.
The treatment of a hyperproliferative disorder in a mammal which comprises administering to said mammal a therapeutically effective amount of a VEGF receptor tyrosine kinase inhibitor may lead to a sustained increase in blood pressure. The compounds of the present invention may be used in conjunction with an anti-hypertensive, such as NORVASC or PROCARDIA XL, commercially available from Pfizer, for use in the treatment of a hyperproliferative disorder in a mammal.
This invention also relates to a pharmaceutical composition for treating a disease related to vasculogenesis or angiogenesis in a mammal comprising (a) therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, (b) a therapeutically effective amount of a compound, salt or solvate of an antihypertensive agent, and (c) a pharmaceutically acceptable carrier.
This invention also relates to a pharmaceutical composition for treating a disease related to vasculogenesis or angiogenesis in a mammal comprising (a) therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, (b) a therapeutically effective amount of a compound, salt or solvate of an inhibitor of tumor necrosis factor alpha, and (c) a pharmaceutically acceptable carrier.
This invention also relates to a pharmaceutical composition for treating a disease related to undesired angiogenesis, endothelial cell migration or endothelial cell proliferation in a mammal comprising (a) therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, (b) a therapeutically effective amount of a compound, salt or solvate of a NADPH oxidase inhibitor, and (c) a pharmaceutically acceptable carrier.
This invention also relates to a pharmaceutical composition for inhibiting abnormal cell growth in a mammal, including a human, comprising an amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, that is effective in inhibiting farnesyl protein transferase, and a pharmaceutically acceptable carrier.
This invention also relates to a pharmaceutical composition for inhibiting abnormal cell growth in a mammal which comprises an amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, in combination with an amount of a chemotherapeutic, wherein the amounts of the compound, salt, or solvate, and of the chemotherapeutic are together effective in inhibiting abnormal cell growth. Many chemotherapeutics are presently known in the art. In one embodiment, the chemotherapeutic is selected from the group consisting of mitotic inhibitors, alkylating agents, anti-metabolites, intercalating antibiotics, growth factor inhibitors, cell cycle inhibitors, enzymes, topoisomerase inhibitors, biological response modifiers, anti-hormones, e.g. anti-androgens.
The compounds described herein may be used in a method for preventing or reducing the growth of tumor cells expressing functional VEGF-1 receptors by administering an effective amount of a small molecule VEGF-1 receptor antagonist to inhibit autocrine stimulation and an effective amount of a compound of Formula (I). Active ingredients in such compositions may be present in free form or in the form of a pharmaceutical acceptable salt and optionally at least one pharmaceutically acceptable carrier.
The compounds described herein also may be used in combination with a selective COX-2-inhibitor for simultaneous, separate or sequential use. The compounds described herein may also be used in combination with a truncated, soluble FlkI/KDR receptor to treat a subjects having disease or disorder associated with VEGF. Active ingredients in such compositions may be present in free form or in the form of a pharmaceutical acceptable salt and optionally at least one pharmaceutically acceptable carrier.
The compounds described herein also may be used in combination with a second active ingredient which decreases the activity of, binds to, or inhibits the epidermal growth factor (EGF). Active ingredients in such compositions may be present in free form or in the form of a pharmaceutical acceptable salt and optionally at least one pharmaceutically acceptable carrier.
The compounds described herein also may be used to inhibit VEGF-mediated angiogenesis in a tissue via several methods including but not limited to, contacting the tissue with an inhibitor of NADPH oxidase and an effective amount of a compound of Formula (I), by contacting the tissue with an inhibitor of reactive oxygen species (ROS) and an effective amount of a compound of Formula (I), or by contacting the tissue with an inhibitor of superoxide dismutase (SOD) and an effective amount of a compound of Formula (I). Active ingredients in such compositions may be present in free form or in the form of a pharmaceutical acceptable salt and optionally at least one pharmaceutically acceptable carrier.
The compounds described herein may also be used in combination with molecules which specifically bind to placenta growth factor in order to suppress or prevent placenta growth factor-induced pathological angiogenesis, vascular leakage (oedema), pulmonary hypertension, tumour formation and/or inflammatory disorders.
The compounds described herein also may be used in combination with molecules chosen from the group comprising: an antibody or any fragment thereof which specifically binds to placenta growth factor, a small molecule specifically binding to placenta growth factor or to vascular endothelial growth factor receptor-1, -vascular endothelial growth factor receptor-1 antagonists or any fragment thereof, -a ribozyme against nucleic acids encoding placenta growth factor or the vascular endothelial growth factor receptor-1, and -anti-sense nucleic acids hybridizing with nucleic acids encoding placenta growth factor or vascular endothelial growth factor receptor-1. Active ingredients in such compositions may be present in free form or in the form of a pharmaceutical acceptable salt and optionally at least one pharmaceutically acceptable carrier.
The compounds described herein may be used in a method of inhibiting the growth of non-solid tumor cells that are stimulated by a ligand of vascular endothelial growth factor receptor (including but not limited to VEGFR2 kinase) in mammals, the method comprising treating the mammals with an effective amount of a compound of Formula (I). The compounds described herein may be used in a method of inhibiting the growth of non-solid tumors that are stimulated by a ligand of vascular endothelial growth factor receptor (including but not limited to VEGFR2 kinase) in mammals, the method comprising treating the mammals with an effective amount of a compound of Formula (I) in combination with radiation.
The compounds described herein may also be used in combination with G2/M agents and with therapeutic agents whose therapeutic effectiveness is dependent, at least in part, on the presence of an internalizing cell surface structure on the target cell. Such G2/M agents include but are not limited to vinorelbine tartrate, cisplatin, carboplatin, paclitaxel, doxorubicin, 5FU, docetaxel, vinblastine, vincristine, cyclophosphamide, apigenin, genistein, cycloxazoline. The compounds described herein may also be used in combination with substances which inhibit signal transduction mediated by human VEGF receptor Flt-1.
The compounds described herein may also be used for treating or preventing a tumor necrosis factor-mediated disease comprising co-administering a tumor necrosis factor alpha antagonist and an effective amount of a compound of Formula (I) to a patient. Contemplated tumor necrosis factor-mediated diseases include but are not limited to autoimmune disease, acute or chronic immune disease, inflammatory disease and neurodegenerative disease.
This invention further relates to a method for inhibiting abnormal cell growth in a mammal which method comprises administering to the mammal an amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, in combination with radiation therapy, wherein the amount of the compound, salt, or solvate is in combination with the radiation therapy effective in inhibiting abnormal cell growth in the mammal. Techniques for administering radiation therapy are known in the art, and these techniques can be used in the combination therapy described herein. The administration of the compound of the invention in this combination therapy can be determined as described herein.
It is believed that the compounds of formula (I) can render abnormal cells more sensitive to treatment with radiation for purposes of killing and/or inhibiting the growth of such cells. Accordingly, this invention further relates to a method for sensitizing abnormal cells in a mammal to treatment with radiation which comprises administering to the mammal an amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, which amount is effective in sensitizing abnormal cells to or enhancing the effects of treatment with radiation. The amount of the compound, salt, or solvate of formula (I) in this method can be determined according to the means for ascertaining effective amounts of such compounds described herein.
This invention also relates to a method of and to a pharmaceutical composition for inhibiting abnormal cell growth in a mammal which comprises an amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, or an isotopically-labelled derivative thereof, and an amount of one or more substances selected from anti-angiogenesis agents, signal transduction inhibitors, and antiproliferative agents.
Anti-angiogenesis agents, such as MMP-2 (matrix-metalloprotienase 2) inhibitors, MMP-9 (matrix-metalloprotienase 9) inhibitors, and COX-II (cyclooxygenase II) inhibitors, can be used in conjunction with a compound of formula (I) and pharmaceutical compositions described herein. Examples of useful COX-II inhibitors include CELEBREX™ (alecoxib), valdecoxib, and rofecoxib. Examples of useful matrix metalloproteinase inhibitors are described in WO 96/33172 (published Oct. 24, 1996), WO 96/27583 (published Mar. 7, 1996), European Patent Application No. 97304971.1 (filed Jul. 8, 1997), European Patent Application No. 99308617.2 (filed Oct. 29, 1999), WO 98/07697 (published Feb. 26, 1998), WO 98/03516 (published Jan. 29, 1998), WO 98/34918 (published Aug. 13, 1998), WO 98/34915 (published Aug. 13, 1998), WO 98/33768 (published Aug. 6, 1998), WO 98/30566 (published Jul. 16, 1998), European Patent Publication 606,046 (published Jul. 13, 1994), European Patent Publication 931,788 (published Jul. 28, 1999), WO 90/05719 (published May 31, 1990), WO 99/52910 (published Oct. 21, 1999), WO 99/52889 (published Oct. 21, 1999), WO 99/29667 (published Jun. 17, 1999), PCT International Application No. PCT/IB98/01113 (filed Jul. 21, 1998), European Patent Application No. 99302232.1 (filed Mar. 25, 1999), Great Britain patent application number 9912961.1 (filed Jun. 3, 1999), U.S. Provisional Application No. 60/148,464 (filed Aug. 12, 1999), U.S. Pat. No. 5,863,949 (issued Jan. 26, 1999), U.S. Pat. No. 5,861,510 (issued Jan. 19, 1999), and European Patent Publication 780,386 (published Jun. 25, 1997), all of which are incorporated herein in their entireties by reference. Preferred MMP-2 and MMP-9 inhibitors are those that have little or no activity inhibiting MMP-1. More preferred, are those that selectively inhibit MMP-2 and/or MMP-9 relative to the other matrix-metalloproteinases (i.e. MMP-1, MMP-3, MMP-4, MMP-5, MMP-6, MMP-7, MMP-8, MMP-10, MMP-11, MMP-12, and MMP-13).
Some specific examples of MMP inhibitors useful in the present invention are Prinomastat, RO 32-3555, RS 13-0830, and the compounds recited in the following list:
3-[[4-(4-fluoro-phenoxy)-benzenesulfonyl]-(1-hydroxycarbamoyl-cyclopentyl)-amino]-propionic acid; 3-exo-3-[4-(4-fluoro-phenoxy)-benzenesulfonylamino]-8-oxa-bicyclo[3.2.1]octane-3-carboxylic acid hydroxyamide; (2R,3R) 1-[4-(2-chloro-4-fluoro-benzyloxy)-benzenesulfonyl]-3-hydroxy-3-methyl-piperidine-2-carboxylic acid hydroxyamide; 4-[4-(4-fluoro-phenoxy)-benzenesulfonylamino]-tetrahydro-pyran-4-carboxylic acid hydroxyamide; 3-[[4-(4-fluoro-phenoxy)-benzenesulfonyl]-(1-hydroxycarbamoyl-cyclobutyl)-amino]-propionic acid; 4-[4-(4-chloro-phenoxy)-benzenesulfonylamino]-tetrahydro-pyran-4-carboxylic acid hydroxyamide; (R) 3-[4-(4-chloro-phenoxy)-benzenesulfonylamino]-tetrahydro-pyran-3-carboxylic acid hydroxyamide; (2R,3R) 1-[4-(4-fluoro-2-methyl-benzyloxy)-benzenesulfonyl]-3-hydroxy-3-methyl-piperidine-2-carboxylic acid hydroxyamide; 3-[[4-(4-fluoro-phenoxy)-benzenesulfonyl]-(1-hydroxycarbamoyl-1-methyl-ethyl)-amino]-propionic acid; 3-[[4-(4-fluoro-phenoxy)-benzenesulfonyl]-(4-hydroxycarbamoyl-tetrahydro-pyran-4-yl)-amino]-propionic acid; 3-exo-3-[4-(4-chloro-phenoxy)-benzenesulfonylamino]-8-oxa-bicyclo[3.2.1]octane-3-carboxylic acid hydroxyamide; 3-endo-3-[4-(4-fluoro-phenoxy)-benzenesulfonylamino]-8-oxa-bicyclo[3.2.1]octane-3-carboxylic acid hydroxyamide; and (R) 3-[4-(4-fluoro-phenoxy)-benzenesulfonylamino]-tetrahydro-furan-3-carboxylic acid hydroxyamide; and pharmaceutically acceptable salts and solvates of said compounds. Other anti-angiogenesis agents, including other COX-II inhibitors and other MMP inhibitors, can also be used in the present invention.
This invention further relates to a method for treating a disease related to vasculogenesis or angiogenesis in a mammal comprising administering to said mammal a therapeutically effective amount of a compound of formula (I), or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, in conjunction with a therapeutically effective amount of an anti-hypertensive agent.
A compound of formula (I) can also be used with signal transduction inhibitors, such as agents that can inhibit EGFR (epidermal growth factor receptor) responses, such as EGFR antibodies, EGF antibodies, and molecules that are EGFR inhibitors; VEGFR (vascular endothelial growth factor receptor) inhibitors, such as organic molecules or antibodies that bind to the VEGF receptor; and erbB2 receptor inhibitors, such as organic molecules or antibodies that bind to the erbB2 receptor, for example, HERCEPTIN™ (Genentech, Inc. of South San Francisco, Calif., USA).
EGFR inhibitors are described in, for example in WO 95/19970 (published Jul. 27, 1995), WO 98/14451 (published Apr. 9, 1998), WO 98/02434 (published Jan. 22, 1998), and U.S. Pat. No. 5,747,498 (issued May 5, 1998), and such substances can be used in the present invention as described herein. EGFR-inhibiting agents include, but are not limited to, the monoclonal antibodies C225 and anti-EGFR 22Mab (ImClone Systems Incorporated of New York, N.Y., USA), the compounds ZD-1839 (AstraZeneca), BIBX-1382 (Boehringer Ingelheim), MDX-447 (Medarex Inc. of Annandale, N.J., USA), and OLX-103 (Merck & Co. of Whitehouse Station, N.J., USA), VRCTC-310 (Ventech Research) and EGF fusion toxin (Seragen Inc. of Hopkinton, Mass.). These and other EGFR-inhibiting agents can be used in the present invention.
VEGFR inhibitors, for example SU-5416 and SU-6668 (Sugen Inc. of South San Francisco, Calif., USA), can also be combined with the compound of the present invention. VEGFR inhibitors are described in, for example in WO 99/24440 (published May 20, 1999), PCT International Application PCT/IB99/00797 (filed May 3, 1999), in WO 95/21613 (published Aug. 17, 1995), WO 99/61422 (published Dec. 2, 1999), U.S. Pat. No. 5,834,504 (issued Nov. 10, 1998), WO 98/50356 (published Nov. 12, 1998), U.S. Pat. No. 5,883,113 (issued Mar. 16, 1999), U.S. Pat. No. 5,886,020 (issued Mar. 23, 1999), U.S. Pat. No. 5,792,783 (issued Aug. 11, 1998), WO 99/10349 (published Mar. 4, 1999), WO 97/32856 (published Sep. 12, 1997), WO 97/22596 (published Jun. 26, 1997), WO 98/54093 (published Dec. 3, 1998), WO 98/02438 (published Jan. 22, 1998), WO 99/16755 (published Apr. 8, 1999), and WO 98/02437 (published Jan. 22, 1998), all of which are incorporated herein in their entireties by reference. Other examples of some specific VEGFR inhibitors useful in the present invention are IM862 (Cytran Inc. of Kirkland, Wash., USA); anti-VEGFR monoclonal antibody of Genentech, Inc. of South San Francisco, Calif.; and angiozyme, a synthetic ribozyme from Ribozyme (Boulder, Colo.) and Chiron (Emeryville, Calif.). These and other VEGFR inhibitors can be used in the present invention as described herein.
ErbB2 receptor inhibitors, such as GW-282974 (Glaxo Wellcome plc), and the monoclonal antibodies AR-209 (Aronex Pharmaceuticals Inc. of The Woodlands, Tex., USA) and 2B-1 (Chiron), can furthermore be combined with the compound of the invention, for example those indicated in WO 98/02434 (published Jan. 22, 1998), WO 99/35146 (published Jul. 15, 1999), WO 99/35132 (published Jul. 15, 1999), WO 98/02437 (published Jan. 22, 1998), WO 97/13760 (published Apr. 17, 1997), WO 95/19970 (published Jul. 27, 1995), U.S. Pat. No. 5,587,458 (issued Dec. 24, 1996), and U.S. Pat. No. 5,877,305 (issued Mar. 2, 1999), which are all hereby incorporated herein in their entireties by reference. ErbB2 receptor inhibitors useful in the present invention are also described in U.S. Provisional Application No. 60/117,341, filed Jan. 27, 1999, and in U.S. Provisional Application No. 60/117,346, filed Jan. 27, 1999, both of which are incorporated in their entireties herein by reference. The erbB2 receptor inhibitor compounds and substance described in the aforementioned PCT applications, U.S. patents, and U.S. provisional applications, as well as other compounds and substances that inhibit the erbB2 receptor, can be used with the compounds of the present invention.
The compounds of the invention can also be used with other agents useful in treating abnormal cell growth or cancer, including, but not limited to, agents capable of enhancing antitumor immune responses, such as CTLA4 (cytotoxic lymphocyte antigen 4) antibodies, and other agents capable of blocking CTLA4; and anti-proliferative agents such as other farnesyl protein transferase inhibitors, and the like. Specific CTLA4 antibodies that can be used in the present invention include those described in U.S. Provisional Application 60/113,647 (filed Dec. 23, 1998) that is incorporated by reference in its entirety, however other CTLA4 antibodies can be used in the present invention.
The subject invention also includes isotopically-labelled compounds, which are identical to those recited in formula (I), but for the fact that one or more atoms are replaced by an atom having an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Examples of isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, fluorine and chlorine, such as 2 H, 3 H, 13 C, 14 C, 15 N, 18 O, 17 O, 31 P, 32 P, 35 S, 18 F, and 36 Cl, respectively. Compounds of the present invention, and pharmaceutically acceptable salts of said compounds which contain the aforementioned isotopes and/or other isotopes of other atoms are within the scope of this invention. Certain isotopically-labelled compounds of the present invention, for example those into which radioactive isotopes such as 3 H and 14 C are incorporated, are useful in drug and/or substrate tissue distribution assays. Tritiated, i.e., 3 H, and carbon-14, i.e., 14 C, isotopes are noted for their ease of preparation and detectability. Further, substitution with heavier isotopes such as deuterium, i.e., 2 H, can afford certain therapeutic advantages resulting from greater metabolic stability, for example increased in vivo half-life or reduced dosage requirements and, hence, may be used in some circumstances. Isotopically labelled compounds of formula (I) of this invention can generally be prepared by carrying out the procedures disclosed in the Schemes and/or in the Examples below, by substituting a readily available isotopically labelled reagent for a non-isotopically labelled reagent.
The compounds of formula (I) or pharmaceutically acceptable salts, or pharmaceutically acceptable solvates of said compounds, can each independently also be used in a palliative neo-adjuvant/adjuvant therapy in alleviating the symptoms associated with the diseases recited herein as well as the symptoms associated with abnormal cell growth. Such therapy can be a monotherapy or can be in a combination with chemotherapy and/or immunotherapy.
If the substituents themselves are not compatible with the synthetic methods of this invention, the substituent may be protected with a suitable protecting group that is stable to the reaction conditions used in these methods. The protecting group may be removed at a suitable point in the reaction sequence of the method to provide a desired intermediate or target compound. Suitable protecting groups and the methods for protecting and de-protecting different substituents using such suitable protecting groups are well known to those skilled in the art; examples of which may be found in T. Greene and P. Wuts, Protecting Groups in Chemical Synthesis (3rd ed.), John Wiley & Sons, NY (1999), which is incorporated herein by reference in its entirety. In some instances, a substituent may be specifically selected to be reactive under the reaction conditions used in the methods of this invention. Under these circumstances, the reaction conditions convert the selected substituent into another substituent that is either useful in an intermediate compound in the methods of this invention or is a desired substituent in a target compound.
The compounds of the present invention may have asymmetric carbon atoms. Such diastereomeric mixtures can be separated into their individual diastereomers on the basis of their physical chemical differences by methods known to those skilled in the art, for example, by chromatography or fractional crystallization. Enantiomers can be separated by converting the enantiomeric mixtures into a diastereomric mixture by reaction with an appropriate optically active compound (e.g., alcohol), separating the diastereomers and converting (e.g., hydrolyzing) the individual diastereomers to the corresponding pure enantiomers. All such isomers, including diastereomer mixtures and pure enantiomers are considered as part of the invention.
The compounds of present invention may in certain instances exist as tautomers. This invention relates to the use of all such tautomers and mixtures thereof.
Preferably, the compounds of the present invention are used in a form that is at least 90% optically pure, that is, a form that contains at least 90% of a single isomer (80% enantiomeric excess (“e.e.”) or diastereomeric excess (“d.e.”)), more preferably at least 95% (90% e.e. or d.e.), even more preferably at least 97.5% (95% e.e. or d.e.), and most preferably at least 99% (98% e.e. or d.e.).
Additionally, the formulae are intended to cover solvated as well as unsolvated forms of the identified structures. For example, Formula I includes compounds of the indicated structure in both hydrated and non-hydrated forms. Additional examples of solvates include the structures in combination with isopropanol, ethanol, methanol, DMSO, ethyl acetate, acetic acid, or ethanolamine.
In the case of agents that are solids, it is understood by those skilled in the art that the inventive compounds and salts may exist in different crystal or polymorphic forms, all of which are intended to be within the scope of the present invention and specified formulas.
DEFINITIONS
As used herein, the following terms have the following meanings, unless expressly indicated otherwise.
The term “comprising” and “including” are used in their open, non-limiting sense.
The terms “abnormal cell growth” and “hyperproliferative disorder” are used interchangeably in this application.
“Abnormal cell growth” refers to cell growth that is independent of normal regulatory mechanisms (e.g., loss of contact inhibition), including the abnormal growth of normal cells and the growth of abnormal cells. This includes, but is not limited to, the abnormal growth of: (1) tumor cells (tumors), both benign and malignant, expressing an activated Ras oncogene; (2) tumor cells, both benign and malignant, in which the Ras protein is activated as a result of oncogenic mutation in another gene; (3) benign and malignant cells of other proliferative diseases in which aberrant Ras activation occurs. Examples of such benign proliferative diseases are psoriasis, benign prostatic hypertrophy, human papilloma virus (HPV), and restinosis. “Abnormal cell growth” also refers to and includes the abnormal growth of cells, both benign and malignant, resulting from activity of the enzyme farnesyl protein transferase.
The term “acyl” includes alkyl, aryl, or heteroaryl substituents attached to a compound via a carbonyl functionality (e.g., —C(O)-alkyl, —C(O)-aryl, etc.).
The term “acylamino” refers to an acyl radical appended to an amino or alkylamino group, and includes —C(O)—NH 2 and —C(O)—NRR′ groups where R and R′ are as defined in conjunction with alkylamino.
The term “acyloxy” refers to the ester group —OC(O)—R, where R is H, alkyl, alkenyl, alkynyl, or aryl.
The term “alkenyl” includes alkyl moieties having at least one carbon-carbon double bond, including E and Z isomers of said alkenyl moiety. The term also includes cycloalkyl moieties having at least one carbon-carbon double bond, i.e., cycloalkenyl. Examples of alkenyl radicals include ethenyl, propenyl, butenyl, 1,4-butadienyl, cyclopentenyl, cyclohexenyl, prop-2-enyl, but-2-enyl, but-3-enyl, 2-methylprop-2-enyl, hex-2-enyl, and the like. An alkenyl group may be optionally substituted.
The term “alkenylene” refers to a divalent straight chain, branched chain or cyclic saturated aliphatic group containing at least one carbon-carbon double bond, and including E and Z isomers of said alkenylene moiety. An alkyenylene group may be optionally substituted.
The term “alkoxy” means an O-alkyl group. Examples of alkoxy radicals include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy and the like.
The term “alkyl” means saturated monovalent hydrocarbon radicals having straight, cyclic or branched moieties. An “alkyl” group may include an optional carbon-carbon double or triple bond where the alkyl group comprises at least two carbon atoms. Cycloalkyl moieties require at least three carbon atoms. Examples of straight or branched alkyl radicals include methyl (Me), ethyl (Et), n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, pentyl, isopentyl, hexyl, heptyl, octyl and the like. An alkyl group may be optionally substituted.
The term “alkylamino” refers to the —NRR′ group, where R and R′ are independently selected from hydrogen (however, R and R′ cannot both be hydrogen), alkyl, and aryl groups; or R and R′, taken together, can form a cyclic ring system.
The term “alkylene” refers to a divalent straight chain, branched chain or cyclic saturated aliphatic group. The latter group may also be referred to more specifically as a cycloalkylene group. An alkylene group may be optionally substituted.
The term “alkylthio” alone or in combination, refers to an optionally substituted alkyl thio radical, alkyl-S—.
The term “alkynyl” refers to straight- and branched-chain alkynyl groups having from two to twelve carbon atoms, preferably from 2 to 6 carbons, and more preferably from 2 to 4 carbons. Illustrative alkynyl groups include prop-2-ynyl, but-2-ynyl, but-3-ynyl, 2-methylbut-2-ynyl, hex-2-ynyl, and the like. An alkynyl group may be optionally substituted.
The term “amide” refers to the radical —C(O)N(R′)(R″) where R′ and R″ are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, —OH, alkoxy, cycloalkyl, heterocycloalkyl, heteroaryl, aryl as defined above; or R′ and R″ cyclize together with the nitrogen to form a heterocycloalkyl or heteroaryl.
The term “amino” refers to the —NH 2 group.
The term “anti-neoplastic agent” refers to agents capable of inhibiting or preventing the growth of neoplasms, or checking the maturation and proliferation of malignant (cancer) cells.
The term “aromatic” refers to compounds or moieties comprising multiple conjugated double bonds. Examples of aromatic moieties include, without limitation, aryl or heteroaryl ring systems.
The term “aryl” (Ar) means an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removal of one hydrogen, such as phenyl or naphthyl. Preferred aryl groups have from 4 to 20 ring atoms, and more preferably from 6 to 14 ring atoms. An aryl group may be optionally substituted. Illustrative examples of aryl groups include the following moieties:
and the like.
The term “aryloxy” means aryl-O—.
The term “arylthio” means an aryl thio radical, aryl-S—.
The term “carbamoyl” or “carbamate” refers to the group —O—C(O)—NRR″ where R and R″ are independently selected from hydrogen, alkyl, and aryl groups; and R and R″ taken together can form a cyclic ring system.
The term “carbocyclyl” includes optionally substituted cycloalkyl and aryl moieties. The term “carbocyclyl” also includes cycloalkenyl moieties having at least one carbon-carbon double bond.
The term “carboxy esters” refers to —C(O)OR where R is alkyl or aryl.
The term “cycloalkyl” refers to a monocyclic or polycyclic radical which contains only carbon and hydrogen, and may be saturated, partially unsaturated, or fully unsaturated. A cycloalkyl group may be optionally substituted. Preferred cycloalkyl groups include groups having from three to twelve ring atoms, more preferably from 5 to 10 ring atoms. Illustrative examples of cycloalkyl groups include the following moieties:
and compounds of the like.
The term “halo” or “halogen” means fluoro, chloro, bromo or iodo. Preferred halo groups are fluoro, chloro and bromo.
The terms haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy include alkyl, alkenyl, alkynyl and alkoxy structures, that are substituted with one or more halo groups or with combinations thereof.
The terms “heteroalkyl” “heteroalkenyl” and “heteroalkynyl” include optionally substituted alkyl, alkenyl and alkynyl radicals and which have one or more skeletal chain atoms selected from an atom other that carbon, e.g., oxygen, nitrogen, sulfur, phosphorus or combinations thereof.
The term “heteroaryl” (heteroAr) refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur. A heteroaryl group may be optionally substituted. The polycyclic heteroaryl group may be fused or non-fused. Illustrative examples of aryl groups include the following moieties:
and the like.
The term “heterocyclyl” refers to aromatic and non-aromatic heterocyclic groups containing one to four heteroatoms each selected from O, S and N, wherein each heterocyclic group has from 4 to 10 atoms in its ring system, and with the proviso that the ring of said group does not contain two adjacent O or S atoms. Non-aromatic heterocyclic groups include groups having only 4 atoms in their ring system, but aromatic heterocyclic groups must have at least 5 atoms in their ring system. The heterocyclic groups include benzo-fused ring systems. An example of a 4 membered heterocyclic group is azetidinyl (derived from azetidine). An example of a 5 membered heterocyclic group is thiazolyl. An example of a 6 membered heterocyclic group is pyridyl, and an example of a 10 membered heterocyclic group is quinolinyl. Examples of non-aromatic heterocyclic groups are pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thioxanyl, piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxepanyl, thiepanyl, oxazepinyl, diazepinyl, thiazepinyl, 1,2,3,6-tetrahydropyridinyl, 2-pyrrolinyl, 3-pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dithianyl, dithiolanyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, 3H-indolyl and quinolizinyl. Examples of aromatic heterocyclic groups are pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, oxadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, and furopyridinyl. The foregoing groups, as derived from the groups listed above, may be C-attached or N-attached where such is possible. For instance, a group derived from pyrrole may be pyrrol-1-yl (N-attached) or pyrrol-3-yl (C-attached). Further, a group derived from imidazole may be imidazol-1-yl or imidazol-3-yl (both N-attached) or imidazol-2-yl, imidazol-4-yl or imidazol-5-yl (all C-attached). The heterocyclic groups include benzo-fused ring systems and ring systems substituted with one or two oxo (═O) moieties such as pyrrolidin-2-one. A heterocyclyl group may be optionally substituted.
The term “heterocyclic” comprises both heterocycloalkyl and heteroaryl groups.
A “heterocycloalkyl” group refers to a cycloalkyl group that includes at least one heteroatom selected from nitrogen, oxygen and sulfur. The radicals may be fused with an aryl or heteroaryl. Illustrative examples of heterocycloalkyl groups include
and the like.
The terms “5 membered heterocyclic”, “5 or 6 membered heterocyclic”, “5 to 8 membered heterocyclic”, “5 to 10 membered heterocyclic” or “5 to 13 membered heterocyclic” includes aromatic and non-aromatic heterocyclic groups containing one to four heteroatoms each selected from O, S and N, wherein each heterocyclic group has from 5, 6, 5 to 8, 5 to 10 or 5 to 13 atoms in its ring system, respectively.
The term “membered ring” can embrace any cyclic structure. The term “membered” is meant to denote the number of skeletal atoms that constitute the ring. Thus, for example, cyclohexyl, pyridine, pyran and thiopyran are 6-membered rings and cyclopentyl, pyrrole, furan, and thiophene are 5-membered rings.
The term “neoplasm” is defined as in Stedman's Medical Dictionary 25th Edition (1990) and refers to an abnormal tissue that grows by cellular proliferation more rapidly than normal and continues to grow after the stimuli that initiated the new growth ceases. Neoplasms show partial or complete lack of structural organization and functional coordination compared with normal tissue, and usually form a distinct mass of tissue that may be either benign (benign tumor) or malignant (cancer).
“Optionally substituted” groups may be substituted or unsubstituted. When substituted, the substituents of an “optionally substituted” group may include, without limitation, one or more substituents independently selected from the following groups or designated subsets thereof: (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )heteroalkyl, (C 1 -C 6 )haloalkyl, (C 2 -C 6 )haloalkenyl, (C 2 -C 6 )haloalkynyl, (C 3 -C 6 )cycloalkyl, phenyl, (C 1 -C 6 )alkoxy, phenoxy, (C 1 -C 6 )haloalkoxy, amino, (C 1 -C 6 )alkylamino, (C 1 -C 6 )alkylthio, phenyl-S—, oxo, (C 1 -C 6 )carboxyester, (C 1 -C 6 )carboxamido, (C 1 -C 6 )acyloxy, H, halogen, CN, NO 2 , NH 2 , N 3 , NHCH 3 , N(CH 3 ) 2 , SH, SCH 3 , OH, OCH 3 , OCF 3 , CH 3 , CF 3 , C(O)CH 3 , CO 2 CH 3 , CO 2 H, C(O)NH 2 , pyridinyl, thiophene, furanyl, (C 1 -C 6 )carbamate, and (C 1 -C 6 )urea. An optionally substituted group may be unsubstituted (e.g., —CH 2 CH 3 ), fully substituted (e.g., —CF 2 CF 3 ), monosubstituted (e.g., —CH 2 CH 2 F) or substituted at a level anywhere in-between fully substituted and monosubstituted (e.g., —CH 2 CF 3 ).
The term “oxo” means an “O” group.
The term “perhalo” refers to groups wherein every C—H bond has been replaced with a C-halo bond on an aliphatic or aryl group. Examples of perhaloalkyl groups include —CF 3 and —CFCl 2 .
The term “substituted” means that the group in question, e.g., alkyl group, etc., may bear one or more substituents.
The term “ureyl” or “urea” refers to the group —N(R)—C(O)—NR′R″ where R, R′, and R″ are independently selected from hydrogen, alkyl, aryl; and where each of R—R′, R′—R″, or R—R″ taken together can form a cyclic ring system.
Pharmaceutical Formulations and Compositions
In addition to compounds of Formula I, the invention includes N-oxides, pharmaceutically acceptable solvates, and pharmaceutically acceptable salts of such compounds and solvates.
The term “pharmaceutically acceptable” means pharmacologically acceptable and substantially non-toxic to the subject being administered the agent.
A “pharmacological composition” refers to a mixture of one or more of the compounds described herein, or physiologically acceptable salts thereof, with other chemical components, such as physiologically acceptable carriers and/or excipients. The purpose of a pharmacological composition is to facilitate administration of a compound to an organism.
A “physiologically acceptable carrier” refers to a carrier or diluent that does not cause significant or otherwise unacceptable irritation to an organism and does not unacceptably abrogate the biological activity and properties of the administered compound.
An “excipient” generally refers to substance, often an inert substance, added to a pharmacological composition or otherwise used as a vehicle to further facilitate administration of a compound. Examples of excipients include but are not limited to calcium carbonate, calcium phosphate, various sugars and types of starch, cellulose derivatives, gelatin, vegetable oils and polyethylene glycols.
“A pharmaceutically acceptable salt” is intended to mean a salt that retains the biological effectiveness of the free acids and bases of the specified compound and that is not biologically or otherwise undesirable. A compound of the invention may possess a sufficiently acidic, a sufficiently basic, or both functional groups, and accordingly react with any of a number of inorganic or organic bases, and inorganic and organic acids, to form a pharmaceutically acceptable salt. Exemplary pharmaceutically acceptable salts include those salts prepared by reaction of the compounds of the present invention with a mineral or organic acid or an inorganic base, such as salts including sulfates, pyrosulfates, bisulfates, sulfites, bisulfites, phosphates, monohydrogenphosphates, dihydrogenphosphates, metaphosphates, pyrophosphates, chlorides, bromides, iodides, acetates, propionates, decanoates, caprylates, acrylates, formates, isobutyrates, caproates, heptanoates, propiolates, oxalates, malonates, succinates, suberates, sebacates, fumarates, maleates, butyne-1,4-dioates, hexyne-1,6-dioates, benzoates, chlorobenzoates, methylbenzoates, dinitrobenzoates, hydroxybenzoates, methoxybenzoates, phthalates, sulfonates, xylenesulfonates, phenylacetates, phenylpropionates, phenylbutyrates, citrates, lactates, γ-hydroxybutyrates, glycolates, tartrates, methane-sulfonates, propanesulfonates, naphthalene-1-sulfonates, naphthalene-2-sulfonates, and mandelates.
If the compound of the invention is a base, the desired pharmaceutically acceptable salt may be prepared by any suitable method available in the art, for example, treatment of the free base with an inorganic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfamic acid, nitric acid, phosphoric acid and the like, or with an organic acid, such as acetic acid, phenylacetic acid, propionic acid, stearic acid, lactic acid, ascorbic acid, maleic acid, hydroxymaleic acid, isethionic acid, succinic acid, mandelic acid, fumaric acid, malonic acid, pyruvic acid, oxalic acid, glycolic acid, salicylic acid, a pyranosidyl acid, such as glucuronic acid or galacturonic acid, an alpha-hydroxy acid, such as citric acid or tartaric acid, an amino acid, such as aspartic acid or glutamic acid, an aromatic acid, such as benzoic acid, 2-acetoxybenzoic acid or cinnamic acid, a sulfonic acid, such as p-toluenesulfonic acid, methanesulfonic acid or ethanesulfonic acid, or the like.
If the compound of the invention is an acid, the desired pharmaceutically acceptable salt may be prepared by any suitable method, for example, treatment of the free acid with an inorganic or organic base, such as an amine (primary, secondary or tertiary), an alkali metal hydroxide or alkaline earth metal hydroxide, or the like. Illustrative examples of suitable salts include organic salts derived from amino acids, such as glycine and arginine, ammonia, carbonates, bicarbonates, primary, secondary, and tertiary amines, and cyclic amines, such as benzylamines, pyrrolidines, piperidine, morpholine and piperazine, and inorganic salts derived from sodium, calcium, potassium, magnesium, manganese, iron, copper, zinc, aluminum and lithium.
Pharmaceutical compositions according to the invention may, alternatively or in addition to a compound of Formula (I), comprise as an active ingredient pharmaceutically acceptable salts of such compounds. Such compounds and salts are sometimes referred to herein collectively as “active agents” or “agents.”
It will be appreciated that any solvate (e.g. hydrate) form of compounds of formula (I) can be used for the purpose of the present invention.
Therapeutically effective amounts of the active agents of the invention may be used to treat diseases mediated by modulation or regulation of protein kinases. An “effective amount” is intended to mean that amount of an agent that significantly inhibits proliferation and/or prevents de-differentiation of a eukaryotic cell, e.g., a mammalian, insect, plant or fungal cell, and is effective for the indicated utility, e.g., specific therapeutic treatment.
The compositions containing the compound(s) of the described herein can be administered for prophylactic and/or therapeutic treatments. In therapeutic applications, the compositions are administered to a patient already suffering from a proliferative disorder or condition (including, but not limited to, cancer), as described above, in an amount sufficient to cure or at least partially arrest the symptoms of the proliferative disorder or condition. An amount adequate to accomplish this is defined as “therapeutically effective amount or dose.” Amounts effective for this use will depend on the severity and course of the proliferative disorder or condition, previous therapy, the patient's health status and response to the drugs, and the judgment of the treating physician. In prophylactic applications, compositions containing the compounds described herein are administered to a patient susceptible to or otherwise at risk of a particular proliferative disorder or condition. Such an amount is defined to be a “prophylactically effective amount or dose.” In this use, the precise amounts also depend on the patient's state of health, weight, and the like. It is considered well within the skill of the art for one to determine such therapeutically effective or prophylactically effective amounts by routine experimentation (e.g., a dose escalation clinical trial).
The terms “enhance” or “enhancing” means to increase or prolong either in potency or duration a desired effect. Thus, in regard to enhancing the effect of therapeutic agents, the term “enhancing” refers to the ability to increase or prolong, either in potency or duration, the effect of other therapeutic agents on a system (e.g., a tumor cell). An “enhancing-effective amount,” as used herein, refers to an amount adequate to enhance the effect of another therapeutic agent in a desired system (including, by way of example only, a tumor cell in a patient). When used in a patient, amounts effective for this use will depend on the severity and course of the proliferative disorder (including, but not limited to, cancer), previous therapy, the patient's health status and response to the drugs, and the judgment of the treating physician. It is considered well within the skill of the art for one to determine such enhancing-effective amounts by routine experimentation.
Once improvement of the patient's conditions has occurred, a maintenance dose is administered if necessary. Subsequently, the dosage or the frequency of administration, or both, can be reduced, as a function of the symptoms, to a level at which the improved proliferative disorder or condition is retained. When the symptoms have been alleviated to the desired level, treatment can cease. Patients can, however, require intermittent treatment on a long-term basis upon any recurrence of the disease symptoms.
The amount of a given agent that will correspond to such an amount will vary depending upon factors such as the particular compound, disease condition and its severity, the identity (e.g., weight) of the subject or host in need of treatment, but can nevertheless be routinely determined in a manner known in the art according to the particular circumstances surrounding the case, including, e.g., the specific agent being administered, the route of administration, the condition being treated, and the subject or host being treated. “Treating” is intended to mean at least the mitigation of a disease condition in a subject such as mammal (e.g., human), that is affected, at least in part, by the activity of one or more kinases, for example protein kinases such as tyrosine kinases, and includes: preventing the disease condition from occurring in a mammal, particularly when the mammal is found to be predisposed to having the disease condition but has not yet been diagnosed as having it; modulating and/or inhibiting the disease condition; and/or alleviating the disease condition.
Agents that potently regulate, modulate, or inhibit cell proliferation are preferred. For certain mechanisms, inhibition of the protein kinase activity associated with CDK complexes, among others, and those which inhibit angiogenesis and/or inflammation are preferred. The present invention is further directed to methods of modulating or inhibiting protein kinase activity, for example in mammalian tissue, by administering a compound of Formula (I). The activity of agents as anti-proliferatives is easily measured by known methods, for example by using whole cell cultures in an MTT assay. The activity of the compounds of Formula (I) as modulators of protein kinase activity, such as the activity of kinases, may be measured by any of the methods available to those skilled in the art, including in vivo and/or in vitro assays. Examples of suitable assays for activity measurements include those described in International Publication No. WO 99/21845; Parast, et al., Biochemistry, 37, 16788-16801 (1998); Connell-Crowley and Harpes, Cell Cycle Materials and Methods , (Michele Pagano, ed. Springer, Berlin, Germany)(1995); International Publication No. WO 97/34876; and International Publication No. WO 96/14843. These properties may be assessed, for example, by using one or more of the biological testing procedures set out in the examples below.
The active agents of the invention may be formulated into pharmaceutical compositions as described below. Pharmaceutical compositions of this invention comprise an effective modulating, regulating, or inhibiting amount of a compound of Formula I and an inert, pharmaceutically acceptable carrier or diluent. In one embodiment of the pharmaceutical compositions, efficacious levels of the compounds of Formula (I) are provided so as to provide therapeutic benefits involving anti-proliferative ability. By “efficacious levels” is meant levels in which proliferation is inhibited, or controlled. These compositions are prepared in unit-dosage form appropriate for the mode of administration, e.g., parenteral or oral administration.
A compound of Formula (I) can be administered in conventional dosage form prepared by combining a therapeutically effective amount of an agent (e.g., a compound of Formula I) as an active ingredient with appropriate pharmaceutical carriers or diluents according to conventional procedures. These procedures may involve mixing, granulating and compressing or dissolving the ingredients as appropriate to the desired preparation.
The pharmaceutical carrier employed may be either a solid or liquid. Exemplary of solid carriers are lactose, sucrose, talc, gelatin, agar, pectin, acacia, magnesium stearate, stearic acid and the like. Exemplary of liquid carriers are syrup, peanut oil, olive oil, water and the like. Similarly, the carrier or diluent may include time-delay or time-release material known in the art, such as glyceryl monostearate or glyceryl distearate alone or with a wax, ethylcellulose, hydroxypropylmethylcellulose, methylmethacrylate and the like.
A variety of pharmaceutical forms can be employed. Thus, if a solid carrier is used, the preparation can be tableted, placed in a hard gelatin capsule in powder or pellet form or in the form of a troche or lozenge. The amount of solid carrier may vary, but generally will be from about 25 mg to about 1 g. If a liquid carrier is used, the preparation will be in the form of syrup, emulsion, soft gelatin capsule, sterile injectable solution or suspension in an ampoule or vial or non-aqueous liquid suspension.
To obtain a stable water-soluble dose form, a pharmaceutically acceptable salt of a compound of Formula (I) can be dissolved in an aqueous solution of an organic or inorganic acid, such as 0.3M solution of succinic acid or citric acid. If a soluble salt form is not available, the agent may be dissolved in a suitable cosolvent or combinations of cosolvents. Examples of suitable cosolvents include, but are not limited to, alcohol, propylene glycol, polyethylene glycol 300, polysorbate 80, glycerin and the like in concentrations ranging from 0-60% of the total volume. In an exemplary embodiment, a compound of Formula I is dissolved in DMSO and diluted with water. The composition may also be in the form of a solution of a salt form of the active ingredient in an appropriate aqueous vehicle such as water or isotonic saline or dextrose solution.
It will be appreciated that the actual dosages of the agents used in the compositions of this invention will vary according to the particular complex being used, the particular composition formulated, the mode of administration and the particular site, host and disease being treated. Optimal dosages for a given set of conditions can be ascertained by those skilled in the art using conventional dosage-determination tests in view of the experimental data for an agent. For oral administration, an exemplary daily dose generally employed is from about 0.001 to about 1000 mg/kg of body weight, with courses of treatment repeated at appropriate intervals.
The compositions of the invention may be manufactured in manners generally known for preparing pharmaceutical compositions, e.g., using conventional techniques such as mixing, dissolving, granulating, dragee-making, levigating, emulsifying, encapsulating, entrapping or lyophilizing. Pharmaceutical compositions may be formulated in a conventional manner using one or more physiologically acceptable carriers, which may be selected from excipients and auxiliaries that facilitate processing of the active compounds into preparations that can be used pharmaceutically.
Proper formulation is dependent upon the route of administration chosen. For injection, the agents of the invention may be formulated into aqueous solutions, preferably in physiologically compatible buffers such as Hanks's solution, Ringer's solution, or physiological saline buffer. For transmucosal administration, penetrants appropriate to the barrier to be permeated are used in the formulation. Such penetrants are generally known in the art.
For oral administration, the compounds can be formulated readily by combining the compounds with pharmaceutically acceptable carriers known in the art. Such carriers enable the compounds of the invention to be formulated as tablets, pills, dragees, capsules, liquids, gels, syrups, slurries, suspensions and the like, for oral ingestion by a patient to be treated. Pharmaceutical preparations for oral use can be obtained using a solid excipient in admixture with the active ingredient (agent), optionally grinding the resulting mixture, and processing the mixture of granules after adding suitable auxiliaries, if desired, to obtain tablets or dragee cores. Suitable excipients include: fillers such as sugars, including lactose, sucrose, mannitol, or sorbitol; and cellulose preparations, for example, maize starch, wheat starch, rice starch, potato starch, gelatin, gum, methyl cellulose, hydroxypropylmethyl-cellulose, sodium carboxymethylcellulose, or polyvinylpyrrolidone (PVP). If desired, disintegrating agents may be added, such as crosslinked polyvinylpyrrolidone, agar, or alginic acid or a salt thereof such as sodium alginate.
Dragee cores are provided with suitable coatings. For this purpose, concentrated sugar solutions may be used, which may optionally contain gum arabic, polyvinyl pyrrolidone, Carbopol gel, polyethylene glycol, and/or titanium dioxide, lacquer solutions, and suitable organic solvents or solvent mixtures. Dyestuffs or pigments may be added to the tablets or dragee coatings for identification or to characterize different combinations of agents.
Pharmaceutical preparations that can be used orally include push-fit capsules made of gelatin, as well as soft, sealed capsules made of gelatin and a plasticizer, such as glycerol or sorbitol. The push-fit capsules can contain the agents in admixture with fillers such as lactose, binders such as starches, and/or lubricants such as talc or magnesium stearate, and, optionally, stabilizers. In soft capsules, the agents may be dissolved or suspended in suitable liquids, such as fatty oils, liquid paraffin, or liquid polyethylene glycols. In addition, stabilizers may be added. All formulations for oral administration should be in dosages suitable for such administration. For buccal administration, the compositions take the form of tablets or lozenges formulated in conventional manners.
For administration intranasally or by inhalation, the compounds for use according to the present invention are conveniently delivered in the form of an aerosol spray presentation from pressurized packs or a nebuliser, with the use of a suitable propellant, e.g., dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. In the case of a pressurized aerosol the dosage unit may be determined by providing a valve to deliver a metered amount. Capsules and cartridges of gelatin for use in an inhaler or insufflator and the like may be formulated containing a powder mix of the compound and a suitable powder base such as lactose or starch.
The compounds may be formulated for parenteral administration by injection, e.g., by bolus injection or continuous infusion. Formulations for injection may be presented in unit-dosage form, e.g., in ampoules or in multi-dose containers, with an added preservative. The compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilizing and/or dispersing agents.
Pharmaceutical formulations for parenteral administration include aqueous solutions of the agents in water-soluble form. Additionally, suspensions of the agents may be prepared as appropriate oily injection suspensions. Suitable lipophilic solvents or vehicles include fatty oils such as sesame oil, or synthetic fatty acid esters, such as ethyl oleate or triglycerides, or liposomes. Aqueous injection suspensions may contain substances that increase the viscosity of the suspension, such as sodium carboxymethyl cellulose, sorbitol, or dextran. Optionally, the suspension may also contain suitable stabilizers or agents that increase the solubility of the compounds to allow for the preparation of highly concentrated solutions.
For administration to the eye, the agent is delivered in a pharmaceutically acceptable ophthalmic vehicle such that the compound is maintained in contact with the ocular surface for a sufficient time period to allow the compound to penetrate the corneal and internal regions of the eye, for example, the anterior chamber, posterior chamber, vitreous body, aqueous humor, vitreous humor, cornea, iris/ciliary, lens, choroid/retina and sclera. The pharmaceutically acceptable ophthalmic vehicle may be an ointment, vegetable oil, or an encapsulating material. A compound of the invention may also be injected directly into the vitreous and aqueous humor. The agents may also be administered in conjunction with other accepted ophthalmic disease treatments, such as photodynamic therapy (PDT).
Alternatively, the agents may be in powder form for constitution with a suitable vehicle, e.g., sterile pyrogen-free water, before use. The compounds may also be formulated in rectal compositions such as suppositories or retention enemas, e.g, containing conventional suppository bases such as cocoa butter or other glycerides.
In addition to the formulations described above, the agents may also be formulated as a depot preparation. Such long-acting formulations may be administered by implantation (for example, subcutaneously or intramuscularly) or by intramuscular injection. Thus, for example, the compounds may be formulated with suitable polymeric or hydrophobic materials (for example, as an emulsion in an acceptable oil) or ion-exchange resins, or as sparingly soluble derivatives, for example, as a sparingly soluble salt.
An exemplary pharmaceutical carrier for hydrophobic compounds is a cosolvent system comprising benzyl alcohol, a nonpolar surfactant, a water-miscible organic polymer, and an aqueous phase. The cosolvent system may be a VPD co-solvent system. VPD is a solution of 3% w/v benzyl alcohol, 8% w/v of the nonpolar surfactant polysorbate 80, and 65% w/v polyethylene glycol 300, made up to volume in absolute ethanol. The VPD co-solvent system (VPD:5W) contains VPD diluted 1:1 with a 5% dextrose in water solution. This co-solvent system dissolves hydrophobic compounds well, and itself produces low toxicity upon systemic administration. Naturally, the proportions of a co-solvent system may be varied considerably without destroying its solubility and toxicity characteristics. Furthermore, the identity of the co-solvent components may be varied: for example, other low-toxicity nonpolar surfactants may be used instead of polysorbate 80; the fraction size of polyethylene glycol may be varied; other biocompatible polymers may replace polyethylene glycol, e.g. polyvinyl pyrrolidone; and other sugars or polysaccharides may be substituted for dextrose.
Alternatively, other delivery systems for hydrophobic pharmaceutical compounds may be employed. Liposomes and emulsions are known examples of delivery vehicles or carriers for hydrophobic drugs. Certain organic solvents such as dimethylsulfoxide also may be employed, although usually at the cost of greater toxicity. Additionally, the compounds may be delivered using a sustained-release system, such as semi-permeable matrices of solid hydrophobic polymers containing the therapeutic agent. Various sustained-release materials have been established and are known by those skilled in the art. Sustained-release capsules may, depending on their chemical nature, release the compounds for a few weeks up to over 100 days. Depending on the chemical nature and the biological stability of the therapeutic reagent, additional strategies for protein stabilization may be employed.
The pharmaceutical compositions also may comprise suitable solid- or gel-phase carriers or excipients. Examples of such carriers or excipients include calcium carbonate, calcium phosphate, sugars, starches, cellulose derivatives, gelatin, and polymers such as polyethylene glycols.
Some of the compounds of the invention may be provided as salts with pharmaceutically compatible counter ions. Pharmaceutically compatible salts may be formed with many acids, including hydrochloric, sulfuric, acetic, lactic, tartaric, malic, succinic, etc. Salts tend to be more soluble in aqueous or other protonic solvents than are the corresponding free-base forms.
The agents of the invention may be useful in combination with known anti-cancer treatments such as: DNA interactive agents such as cisplatin or doxorubicin; topoisomerase II inhibitors such as etoposide; topoisomerase I inhibitors such as CPT-11 or topotecan; tubulin interacting agents such as paclitaxel, docetaxel or the epothilones; hormonal agents such as tamoxifen; thymidilate synthase inhibitors such as 5-fluorouracil; and anti-metalbolites such as methotrexate. They may be administered together or sequentially, and when administered sequentially, the agents may be administered either prior to or after administration of the known anticancer or cytotoxic agent.
The term “chemotherapeutic agent” as used herein includes, for example, hormonal agents, antimetabolites, DNA interactive agents, tubilin-interactive agents, and others such as aspariginase or hydroxyureas.
DNA-interactive agents include alkylating agents, such as cisplatin, cyclophosphamide, altretamine; DNA strand-breakage agents, such as bleomycin; intercalating topoisomerase II inhibitors, e.g., dactinomycin and doxorubicin); nonintercalating topoisomerase II inhibitors such as, etoposide and teniposide; and the DNA minor groove binder plicamydin, for example.
Alkylating agents may form covalent chemical adducts with cellular DNA, RNA, or protein molecules, or with smaller amino acids, glutathione, or similar chemicals. Examples of typical alkylating agents include, but are not limited to, nitrogen mustards, such as chlorambucil, cyclophosphamide, isofamide, mechlorethamine, melphalan, uracil mustard; aziridine such as thiotepa; methanesulfonate esters such as busulfan; nitroso ureas, such as carmustine, lomustine, streptozocin; platinum complexes, such as cisplatin, carboplatin; bioreductive alkylator, such as mitomycin, and procarbazine, dacarbazine and altretamine. DNA strand-breaking agents include bleomycin, for example.
DNA topoisomerase II inhibitors may include intercalators such as the following: amsacrine, dactinomycin, daunorubicin, doxorubicin (adriamycin), idarubicin, and mitoxantrone; as well as nonintercalators such as etoposide and teniposide.
An example of a DNA minor groove binder is plicamycin.
Antimetabolites generally interfere with the production of nucleic acids and thereby growth of cells by one of two major mechanisms. Certain drugs inhibit production of deoxyribonucleoside triphosphates that are the precursors for DNA synthesis, thus inhibiting DNA replication. Examples of these compounds are analogues of purines or pyrimidines and are incorporated in anabolic nucleotide pathways. These analogues are then substituted into DNA or RNA instead of their normal counterparts.
Antimetabolites useful as chemotherapeutic agents include, but are not limited to: folate antagonists such as methotrexate and trimetrexate; pyrimidine antagonists, such as fluorouracil, fluorodeoxyuridine, CB3717, azacitidine, cytarabine, and floxuridine; purine antagonists such as mercaptopurine, 6-thioguanine, fludarabine, pentostatin; and ribonucleotide reductase inhibitors such as hydroxyurea.
Tubulin interactive agents act by binding to specific sites on tubulin, a protein that polymerizes to form cellular microtubules. Microtubules are critical cell structure units and are required for cell division. These therapeutic agents disrupt the formation of microtubules. Exemplary tubulin-interactive agents include vincristine and vinblastine, both alkaloids and paclitaxel (Taxol).
Hormonal agents are also useful in the treatment of cancers and tumors, but only rarely in the case of B cell malignancies. They are used in hormonally susceptible tumors and are usually derived from natural sources. Hormonal agents include, but are not limited to, estrogens, conjugated estrogens and ethinyl estradiol and diethylstilbesterol, chlortrianisen and idenestrol; progestins such as hydroxyprogesterone caproate, medroxyprogesterone, and megestrol; and androgens such as testosterone, testosterone propionate; fluoxymesterone, and methyltestosterone.
Adrenal corticosteroids are derived from natural adrenal cortisol or hydrocortisone and are used to treat B cell malignancies. They are used because of their anti-inflammatory benefits as well as the ability of some to inhibit mitotic divisions and to halt DNA synthesis. These compounds include, but are not limited to, prednisone, dexamethasone, methylprednisolone, and prednisolone.
Leutinizing hormone releasing hormone agents or gonadotropin-releasing hormone antagonists are used primarily the treatment of prostate cancer. These include leuprolide acetate and goserelin acetate. They prevent the biosynthesis of steroids in the testes.
Antihormonal antigens include, for example, antiestrogenic agents such as tamoxifen, antiandrogen agents such as flutamide; and antiadrenal agents such as mitotane and aminoglutethimide.
Other agents include hydroxyurea (which appears to act primarily through inhibition of the enzyme ribonucleotide reductase), and asparaginase (an enzyme which converts asparagine to aspartic acid and thus inhibits protein synthesis).
Included within the scope of cancer therapy agents are radiolabeled antibodies, including but not limited to, Zevalin™ (IDEC Pharmaceuticals Corp.) and Bexxar (Corixa, Inc.); the use of any other radioisotope (e.g., 90 Y and 131 I) coupled to an antibody or antibody fragment that recognizes an antigen expressed by a neoplasm; external beam radiation or any other method for administration of radiation to a patient.
Further included within the scope of cancer therapy agents are cytotoxins, including but not limited to an antibody or antibody fragment linked to a cytotoxin, or any other method for selectively delivering a cytotoxic agent to a tumor cell.
Further included within the scope of cancer therapy agents are selective methods for destroying DNA, or any method for delivering heat to a tumor cells, including by way of example only, nanoparticles.
Further included within the scope of cancer therapy agents is the use of unlabeled antibodies or antibody fragments capable of killing or depleting tumor cells, including by way of example only, Rituxan™ (IDEC Pharmaceuticals Corp.) and Herceptin™ (Genentech).
The agents may be prepared using the reaction routes and synthesis schemes as described below, employing the general techniques known in the art using starting materials that are readily available. The preparation of preferred compounds of the present invention is described in detail in the following examples, but the artisan will recognize that the chemical reactions described may be readily adapted to prepare a number of other anti-proliferatives or protein kinase inhibitors of the invention. For example, the synthesis of non-exemplified compounds according to the invention may be successfully performed by modifications apparent to those skilled in the art, e.g., by appropriately protecting interfering groups, by changing to other suitable reagents known in the art, or by making routine modifications of reaction conditions. Alternatively, other reactions disclosed herein or generally known in the art will be recognized as having applicability for preparing other compounds of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of Formula (I) can act as antagonists of the VEGFR2. Without being bound to any particular theory, the linked rings are thought to provide favorable space-filling and electrostatic complementarity in the active site of the targeted protein: the presence of a quinoline moiety offers structure advantages exemplified by the introduction of ether linked solubilizing groups on 6, or 7-position of the quinoline ring (depicted below):
In addition, and without being bound to any particular theory, physico-chemical changes which result from introducing substituents at the 6 and 7 positions of the quinoline ring include but are not limited to: increased water solubility and selectivity (against FGF) of the prepared compounds and a favorable change in pharmaco-kinetics, dynamics and metabolism (PDM) properties
In the examples described below, unless otherwise indicated, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight. Reagents were purchased from commercial suppliers such as Aldrich Chemical Company or Lancaster Synthesis Ltd. and were used without further purification unless otherwise indicated. Tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dichloromethane, toluene, and dioxane were purchased from Aldrich in Sure seal bottles and used as received. All solvents were purified using standard methods readily known to those skilled in the art, unless otherwise indicated.
The reactions set forth below were done generally under a positive pressure of argon or nitrogen or with a drying tube, at ambient temperature (unless otherwise stated), in anhydrous solvents, and the reaction flasks were fitted with rubber septa for the introduction of substrates and reagents via syringe. Glassware was oven dried and/or heat dried. Analytical thin layer chromatography (TLC) was performed on glass-backed silica gel 60 F 254 plates Analtech (0.25 mm) and eluted with the appropriate solvent ratios (v/v), and are denoted where appropriate. The reactions were assayed by TLC and terminated as judged by the consumption of starting material.
Visualization of the TLC plates was done with a p-anisaldehyde spray reagent or phosphomolybdic acid reagent (Aldrich Chemical 20 wt % in ethanol) and activated with heat. Work-ups were typically done by doubling the reaction volume with the reaction solvent or extraction solvent and then washing with the indicated aqueous solutions using 25% by volume of the extraction volume unless otherwise indicated. Product solutions were dried over anhydrous Na 2 SO 4 prior to filtration and evaporation of the solvents under reduced pressure on a rotary evaporator and noted as solvents removed in vacuo. Flash column chromatography (Still et al., J. Org. Chem., 43, 2923 (1978)) was done using Baker grade flash silica gel (47-61 μm) and a silica gel: crude material ratio of about 20:1 to 50:1 unless otherwise stated. Hydrogenolysis was done at the pressure indicated in the examples or at ambient pressure.
1 H-NMR spectra were recorded on a Bruker instrument operating at 300 MHz and 13 C-NMR spectra were recorded operating at 75 MHz. NMR spectra were obtained as CDCl 3 solutions (reported in ppm), using chloroform as the reference standard (7.25 ppm and 77.00 ppm) or CD 3 OD (3.4 and 4.8 ppm and 49.3 ppm), or internally tetramethylsilane (0.00 ppm) when appropriate. Other NMR solvents were used as needed. When peak multiplicities are reported, the following abbreviations are used: s (singlet), d (doublet), t (triplet), m (multiplet), br (broadened), dd (doublet of doublets), dt (doublet of triplets). Coupling constants, when given, are reported in Hertz (Hz).
Infrared (IR) spectra were recorded on a Perkin-Elmer FT-IR Spectrometer as neat oils, as KBr pellets, or as CDCl 3 solutions, and when given are reported in wave numbers (cm −1 ). The mass spectra were obtained using LSIMS or electrospray. All melting points (mp) are uncorrected.
General Synthetic Schemes Used for the Preparation of Quinoline ANALOGS
In this scheme R is an R 6 substituent as defined in connection with Formula (I). Reference: 1). J. Am. Chem. Soc., 68, 1204-1208, (1946). 2). J. Am. Chem. Soc., 68, 113-116, 1946.
A. Preparation of Compound I-D
A mixture of a substituted aniline I-A (1 eq.), and diethyl (ethoxymethylene) malonate I-B (1 eq.) was placed in a round bottom flask and heated in an oil bath. When the temperature of oil bath reached ˜135° C. EtOH was generated and collected with a condenser. The reaction was heated at 160° C. for 40 minutes to give I-C. The reaction flask was removed from the oil bath. Phenyl ether (about two times volume of the reaction mixture) was added into the flask. The reaction flask was placed in the oil bath, which was preheated to 270° C. The reaction mixture was stirred and heated to 240-245° C. (temperature of reactants inside the flask) for 15 minutes. The reaction flask was removed from heating and slowly poured into hexane. Compound I-D was collected by filtration and washed by hexane to remove phenyl ether. The yields of reactions starting from compound I-A to compound I-D were usually in the range of 60 to 90%.
B. Preparation of Compound I-E
A solution of compound I-D (5 g) and KOH (3 eq.) in 60 ml of H 2 O/OH(CH 2 ) 2 OH (1:1) was placed in a sealed vessel (XP-500 Plus vessel). The reaction was heated by microwave (MARS 5 Microwave System) at 200° C., under 220-240 psi pressure for 30 minutes. The reaction mixture was cooled to room temperature and poured into H 2 O (100 ml). The solution was acidified with 2N HCl to pH˜6, saturated with NaCl and extracted with THF (3×200 ml). The combined oil layer was washed with brine and concentrated to give compound I-E (>80% yield).
C. Preparation of Compound I-F
Compound I-E was dissolved in neat POCl 3 (excess). The solution was heated to reflux for 2 hours. The excess amount of POCl 3 was removed by evaporation under vacuum. The residue was basified with NH 4 OH and extracted with EtOAc. The organic layer was concentrated. The residue was purified by column chromatography using 3:1 to 1:1 hexane/EtOAc to give compound I-F (70-90%).
A solution of 4-chloroqunoline II-A (1 eq.), 4-hydroxylbenzofuran (where X═O) II-B (1 eq.) and Cs 2 CO 3 (1.5-2 eq.) in dry DMSO was heated to 120-130° C. for 2 hours. The dark brown solution was extracted with EtOAc. The organic layer was washed with brine, dried (MgSO 4 ) and concentrated. The residue was purified by silica gel column chromatography using 2-5% MeOH in CH 2 Cl 2 to give compound II-C in 50-90% yield.
A solution of 4-chloroquinoline III-A (1 eq.), 5-amino-N,2-dimethyl-1H-indole-1-carboxamide II-B (1 eq.) and HCl in dioxane (1.0 eq.) in a mixed solvent of EtOH/ClCH 2 CH 2 Cl (1:1) was heated to 80-90° C. for 2 to 6 hours. The solution was extracted with EtOAc. The organic layer was washed with brine, dried (MgSO 4 ) and concentrated. The residue was purified by silica gel column chromatography using 2-5% MeOH in CH 2 Cl 2 to give compound III-C in 50-90% yield.
(i) Method IV(i)
Compound IV-A (1 eq.) was heated to reflux in net SOCl 2 (excess) for 2 minutes. The excess amount of SOCl 2 was removed by evaporation under vacuum. The residue was dissolved in dichloromethane. To this solution Et 3 N (3 eq.) and corresponding amine were added. The solution was stirred at room temperature for 30 minutes, extracted with EtOAc, washed (brine) and concentrated. The residue was purified by silica gel column chromatography using 2-10% MeOH/CH 2 Cl 2 or by HPLC (20-70% CH 3 CN/H 2 O) to give compound IV-B.
(ii) Method IV(ii)
To a solution of compound IV-A (1 eq.) in dichloromethane was added oxalyl chloride (5 eq.) at room temperature. The solution was stirred for 1 hour and concentrated under vacuum. The residue was dissolved in dichloromethane. To this solution Et 3 N (3 eq.) and corresponding amine were added into. The solution was stirred at room temperature for 30 minutes, extracted with EtOAc, washed (brine) and concentrated. The residue was purified by silica gel column chromatography using 2-10% MeOH/CH 2 Cl 2 or by HPLC (20-70% CH 3 CN/H 2 O) to give compound IV-B.
(iii) Method IV(iii)
To a solution of compound IV-A (1 eq.) in DMF was added Et 3 N (1.5 eq.) and HATU (1.2 eq.) at room temperature. After being stirred for 10 minutes to the solution was added corresponding amine. The solution was stirred at room temperature for 30 minutes, extracted with EtOAc, washed (brine) and concentrated. The residue was purified by silica gel column chromatography using 2-10% MeOH/CH 2 Cl 2 or by HPLC (20-70% CH 3 CN/H 2 O) to give compound IV-B.
EXAMPLES
Example 1
Preparation of N-(2-methyl-1H-indol-5-yl)-7-(trifluoromethyl)quinoline-4-amine
This compound was prepared according to the synthetic scheme depicted and described below.
A suspension of 4-chloro-7-(trifluoromethyl)quinoline 1-A (158 mg, 0.68 mmol), 2-methyl-1H-indol-5-amine 1-B (100 mg, 0.68 mmol) and 4N HCl in dioxane (0.25 ml, 1.0 mmol) in a mixed solvent (EtOH/dichloroethane, 1:1, 6 ml) was heated to 90° C. in a sealed tube overnight. The reaction mixture was concentrated and dissolved in 2 ml of DMSO. The solution was purified by HPLC (DionexSystem, 20-60% CH 3 CN/H 2 O over 30 minutes). 40 mg of N-(2-methyl-1H-indol-5-yl)-7-(trifluoromethyl)quinolin-4-amine 1 was obtained.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.50 (s, 3H) 6.26 (s, 1H) 6.75 (d, J=5.46 Hz, 1H) 7.08 (d, J=8.48 Hz, 1H) 7.46 (m, 2H) 7.87 (d, J=8.85 Hz, 1H) 8.24 (s, 1H) 8.54 (d, J=5.27 Hz, 1H) 8.77 (s, 1H) 9.32 (s, 1H) 11.14 (s, 1H). LC/MS (APCI, pos.): 342.1 (M + H).
Example 2
Preparation of 8-chloro-N-(2-methyl-1H-indol-5-yl)quinolin-4-amine
This compound was prepared by methods analogous to those described in Example 1.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.58 (s, 3H) 6.33 (s, 1H) 6.78 (d, J=5.46 Hz, 1H) 7.16 (m, 1H) 7.53 (m, 1H) 7.62 (d, J=7.35 Hz, 1H) 8.04 (d, J=7.35 Hz, 1H) 8.59 (m, 2H) 9.21 (s, 1H) 11.21 (s, 1H). LC/MS (APCI, pos.): 308.1 (M+H).
Example 3
Preparation of N-(2-methyl-1H-indol-5-yl)quinolin-4-amine
This compound was prepared using methods analogous to those described in Example 1 and Scheme III.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.15 (s, 3H) 5.89 (s, 1H) 6.32 (m, 1H) 6.73 (d, J=8.10 Hz, 1H) 7.09 (d, J=6.97 Hz, 2H) 7.23 (s, 1H) 7.40 (d, J=8.10 Hz, 1H) 7.59 (s, 1H) 8.11 (m, 2H) 8.64 (s, 1H) 10.76 (s, 1H). LC/MS (APCI, pos.): 274.1 (M+H).
Example 4
Preparation of 5-[(7-chloroquinazolini-4-yl)amino]-N,2-dimethyl-1H-indole-1-carboxamide
This compound was prepared using methods analogous to those described in Example 1 and Scheme III.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.44 (s, 3H) 2.83 (s, 3H) 7.40 (m, 1H) 7.54 (m, 1H) 7.74 (s, 1H) 7.85 (s, 1H) 8.12 (s, 1H) 8.46 (s, 1H) 8.53 (d, J=9.42 Hz, 1H) 9.88 (s, 1H). LC/MS (APCI, pos.): 366.1 (M+H).
Example 5
Preparation of 6-hydroxy-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
I 2 (40.9 g, 161.1 mmol) was dissolved in CHCl 3 (850 mL) with stirring over 1 hour. The solution was added slowly into a reaction mixture of 3-methoxyphenol 5-A (20 g, 161.1 mmol) and silver trifluoroacetate in 200 mL CHCl 3 over 1.5 hours. The reaction was stirred at room temperature for 16 hours. Solids were removed by filtration. The filtrate was washed with 5% Na 2 S 2 O 3 (500 mL), saturated NaHCO 3 , brine, dried over MgSO 4 and concentrated. The crude mixture was triturated with carbon tetrachloride to give 2-iodo-5-methoxyphenol 5-B (13.6 g) as a white solid. The remaining crude products were purified by silica gel column chromatography eluted with CH 2 Cl 2 to give 28.2 g of compound 5-B.
A solution of compound 5-B (14.6 g, 58.5 mmol), CuI (0.56 g, 2.9 mmol), N,N,N′,N′- tetramethylguanidine (74 mL, 585 mmol) and dichlorobis(triphenyl phosphine) palladium (II) (3.9 g, 5.5 mmol) in 200 mL anhydrous DMF was cooled to −78° C. Propyne gas was bubbled in for 25 minutes. A balloon was placed to catch propyne. The reaction mixture was stirred for 17 hours, allowing temperature to go from −78° C. to room temperature. The solution was poured into 200 mL water and extracted with EtOAc, washed with water, brine and dried over MgSO 4 . Silica gel column chromatography eluted with hexane/ethyl acetate (9:1) gave 6-methoxy-2-methyl-1-benzofuran 5-C (4.4 g, 46% yield).
A suspension of AlCl 3 (18 g, 135 mmol) in dichloromethane (250 mL) was cooled to 0° C. To this suspension oxalyl chloride (12 mL, 135 mmol) was added and stirred for 30 minutes. A solution of 5-C (4.38 g, 27 mmol) in 100 mL of dichloromethane was then added over 10 minutes. The ice bath was removed. The reaction was allowed to be stirred for 2 hours. at room temperature. The reaction mixture was poured into a saturated NaCl/ice and separated. Aqueous layer was extracted with CH 2 Cl 2 . The combined organic layer was dried over MgSO 4 and concentrated to give a crude mixture of compound 5-D (6.5 g).
Without purification the crude 5-D (6.5 g) obtained was dissolved in 50 mL of THF. To this solution was added a solution of methylamine (68 mL, 2.0M in THF). The reaction was stirred at room temperature for 1 hour. The reaction mixture was extracted with EtOAc, washed with brine, dried (MgSO 4 ), concentrated and purified by a silica gel chromatography, eluted with CH 2 Cl 2 /EtOAc (2:1) to give compound 5-E (3.38 g, 57% yield from 5-C).
A solution of 5-E (3.38 g, 15.4 mmol) in 50 mL of dichloromethane was cooled to −5° C. To this a solution of BBr 3 (31 mL, 30.8 mmol) in CH 2 Cl 2 (1.0 M) was added. The solution was stirred at −5° C. for 1 hour. Additional 15 mL of BBr 3 solution was added and the reaction was stirred for 1 hour at 0° C. The solution was poured into saturated NaHCO 3 /ice. The organic layer was then separated. The water layer was extracted with EtOAc. The combined organic layer was washed (brine), dried over MgSO 4 and concentrated to give the title compound 5 (3.16 g, 99%) as a solid.
Reference: Het. 45 (6), 1997, 1137.
Example 6
Preparation of 6-[(7-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A mixture of 3-iodoaniline 6-A (10 g, 45.6 mmol) and diethyl (ethoxymethylene) malonate 6-B (10 g, 45.6 mmol) was heated in an oil bath to 150° C. for 40 minutes. The reaction mixture was poured into 500 mL EtOH slowly with stirring. Diethyl {[(3-iodophenyl)amino]methylene}malonate 6-C (14.5 g, 88% yield) was collected as a white precipitate by filtration.
Compound 6-C (14.5 g) was placed in a round bottom flask equipped with a trap to collect EtOH generated during the reaction. Phenyl ether (60 mL) was added into the flask. When the suspension was heated to 230° C. the solution became clear and EtOH was generated. The reaction mixture was allowed to stay at 240-250° C. for 45 minutes, was cooled to 160° C. and slowly poured into 600 mL of hexane. Ethyl 4-hydroxy-7-iodoquinoline-3-carboxylate 6-D (11.1 g, 87% yield) was precipitated, filtrated, washed with hexane (2 times) and dried.
Compound 6-D (6.0 g) was treated with 20% LiOH (100 mL) in a mixed solvent of MeOH (100 mL) and THF (30 mL) at room temperature overnight. The solution was acidified with AcOH. 4-hydroxy-7-iodoquinoline-3-carboxylic acid 6-E (5.6 g, 100% yield) was obtained as a solid by filtration.
Compound 6-E (5.5 g) was placed I a 100 mL round bottom flask and heated under N 2 in an oil bath to 280° C. for 15 minutes. 7-iodoquinolin-4-ol 6-F (4.6 g, 99% yield) was obtained as a solid.
Compound 6-F (4.5 g) was dissolved in 30 mL of POCl 3 . The solution was heated to reflux for 2 hours. The excess amount of POCl 3 was removed by evaporation under vacuum. The residue was basified with NH 4 OH and extracted with EtOAc. The organic layer was concentrated to give 3.95 g (80% yield) of 4-chloro-7-iodoquinoline 6-G as a yellow solid.
A mixture of compound 6-G (500 mg, 1.7 mmol), 6-hydroxy-N,2-dimethyl-1-benzofuran-3-carboxamide 6-H (354 mg, 1.7 mmol) (the product of Example 5) and Cs 2 CO 3 (920 mg, 2.6 mmol) in DMSO (5 mL) was heated to 120° C. for 1 hours. The solution was extracted with Silica gel column chromatography eluted with hexane/ethyl acetate (3:1 to 1:1) gave the title compound 6 (427 mg, 54% yield).
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 2.67 (s, 3H) 3.00 (d, J=4.90 Hz, 3H) 5.82 (s, 1H) 6.48 (d, J=5.27 Hz, 1H) 7.07 (dd, J=8.57, 2.17 Hz, 1H) 7.23 (d, J=2.07 Hz, 1H) 7.81 (dd, J=8.76, 1.60 Hz, 1H) 8.04 (d, J=8.85 Hz, 1H) 8.51 (d, J=1.32 Hz, 1H) 8.56 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 459.0 (M + H).
Example 7
Preparation of N-2-dimethyl-6-[(7-pyridin-4-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 6-[(7-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 7-A (60 mg, 0.13 mmol), pyridin-4-ylboronic acid 7-B (18 mg, 0.14 mmol), 2M K 2 CO 3 solution (0.2 ml, 0.39 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (10 mg) in DMF (2 ml) was heated to 90° C. for 4 hours. The solution was filtrated and purified by a HPLC (Dionex System) using CH 3 CN/H 2 O (ACOH 0.1%) 40-80% over 30 minutes to yield the title compound 7 (13 mg).
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.59 (s, 3H) 2.77 (d, J=4.52 Hz, 3H) 6.58 (d, J=5.27 Hz, 1H) 7.22 (dd, J=8.48, 2.07 Hz, 1H) 7.61 (d, J=2.07 Hz, 1H) 7.81 (d, J=8.48 Hz, 1H) 7.88 (m, 2H) 7.94 (d, J=4.52 Hz, 1H) 8.05 (dd, J=8.85, 1.70 Hz, 1H) 8.42 (m, 2H) 8.67 (m, 3H). LC/MS (APCI, pos.): 410.1 (M+H).
Example 8
Preparation of N-2-dimethyl-6-[(7-pyridin-3-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 7, using the appropriate boronic acid (pyridin-3-ylboronic acid).
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.58 (s, 3H) 2.77 (d, J=4.52 Hz, 3H) 6.57 (d, J=5.27 Hz, 1H) 7.21 (dd, J=8.48, 2.07 Hz, 1H) 7.51 (dd, J=7.91, 4.71 Hz, 1H) 7.60 (d, J=2.07 Hz, 1H) 7.81 (d, J=8.48 Hz, 1H) 7.93 (d, J=4.52 Hz, 1H) 8.00 (dd, J=8.67, 1.70 Hz, 1H) 8.25 (m, 1H) 8.33 (d, J=1.51 Hz, 1H) 8.40 (d, J=8.67 Hz, 1H) 8.60 (dd, J=4.90, 1.51 Hz, 1H) 8.67 (d, J=5.09 Hz, 1H) 9.05 (d, J=2.26 Hz, 1H) LC/MS (APCI, pos.): 410.1 (M + H).
Example 9
Preparation of N-2-dimethyl-6-[(7-pyridin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 6-[(7-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 9-A (60 mg, 0.13 mmol), 2-(tributylstannyl)pyridine 9-B (16 mg, 0.14 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (10 mg) in DMF (2 ml) was heated to 100° C. for 3 hours. The solution was filtrated and purified by a HPLC (Dionex System) using CH 3 CN/H 2 O (ACOH 0.1%) 40-80% over 30 minutes to yield the title compound 9.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.59 (s, 3H) 2.77 (d, J=4.52 Hz, 3H) 6.55 (d, J=5.27 Hz, 1H) 7.22 (dd, J=8.48, 2.07 Hz, 1H) 7.39 (dd, J=7.06, 5.18 Hz, 1H) 7.62 (d, J=2.26 Hz, 1H) 7.81 (d, J=8.67 Hz, 1H) 7.93 (m, 2H) 8.18 (d, J=8.10 Hz, 1H) 8.39 (s, 2H) 8.66 (m, 2H) 8.71 (m, 1H). LC/MS (APCI, pos.): 410.1 (M + H).
Example 10
Preparation of N-2-dimethyl-6-[(7-pyridin-4-ylquinolin-4-yl]oxy]-1-benzothiophene-3-carboxamide
This compound was prepared according to the methods of Schemes I, II and IV and methods analogous to those described in Examples 5 to 7.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.55 (s, 3H) 2.77 (d, J=4.53 Hz, 3H) 6.60 (d, J=4.91 Hz, 1H) 7.28 (dd, J=8.48, 2.07 Hz, 1H) 7.81 (d, J=8.67 Hz, 1H) 7.87 (m, 2H) 8.05 (d, J=8.69 Hz, 1H) 8.21 (d, J=4.91 Hz, 1H) 8.41 (dd, J=5.10, 3.59 Hz, 1H) 8.68 (dd, J=9.82, 5.67 Hz, 1H). LC/MS (APCI, pos.): 426.0 (M + H).
Example 11
Preparation of N-2-dimethyl-5-[(7-pyridin-4-ylquinolin-4-yl]amino]-1H-indole-1-carboxamide
This compound was prepared according to the synthetic schemes depicted and described below.
A solution of 4-chloro-7-iodoquinoline 11-A (500 mg, 1.73 mmol), pyridin-4-ylboronic acid 11-B (212 mg, 1.73 mmol), 2M K 2 CO 3 solution (2.6 ml, 5.19 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (100 mg) in DMF (5 ml) were heated to 90° C. for 4 hours. The solution was filtrated and extracted with EtOAc. The organic layer was concentrated and purified by column chromatography using hexane/EtOAc (1/1) to give 193 mg of compound 11-C.
A mixture of compound 11-C (70 mg, 0.29 mmol), 5-amino-N,2-dimethyl-1H-indole-1-carboxamide 11-D (59 mg, 0.29 mmol) and 2N HCl (0.2 ml, 0.34 mmol) in 3 ml of a mixed solution of EtOH/Cl (CH 2 ) 2 Cl (1/1) was heated to 80° C. for 1 hour. The title compound 11 (20 mg) was isolated by HPLC (Dionex System) using 30-60% CH 3 CN/H 2 O (0.1% AcOH) over 30 minutes.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.44 (s, 3H) 2.83 (d, J=4.53 Hz, 3H) 6.33 (s, 1H) 6.63 (d, J=5.67 Hz, 1H) 7.11 (d, J=8.69 Hz, 1H) 7.39 (s, 1H) 7.60 (d, J=8.69 Hz, 1H) 7.85 (d, J=5.67 Hz, 2H) 7.91 (d, J=8.69 Hz, 1H) 8.14 (d, J=4.53 Hz, 1H) 8.20 (s, 1H) 8.36 (d, J=5.29 Hz, 1H) 8.53 (d, J=9.07 Hz, 1H) 8.64 (d, J=5.67 Hz, 2H) 9.07 (s, 1H). LC/MS (APCI, pos.): 408.1 (M+H).
Example 12
Preparation of N,2-dimethyl-5-[(7-pyridin-3-ylquinolin-4-yl)amino]-1H-indole-1-carboxamide
This compound was prepared according to the synthetic scheme depicted below and using methods analogous to those described in Example 11.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.45 (s, 3H) 2.84 (d, J=4.29 Hz, 3H) 6.36 (s, 1H) 6.62 (d, J=5.81 Hz, 1H) 7.13 (dd, J=8.84, 2.02 Hz, 1H) 7.44 (d, J=2.02 Hz, 1H) 7.53 (dd, J=8.08, 4.80 Hz, 1H) 7.64 (d, J=8.59 Hz, 1H) 7.98 (dd, J=8.72, 1.64 Hz, 1H) 8.13 (d, J=1.77 Hz, 1H) 8.22 (m, 1H) 8.39 (d, J=6.06 Hz, 1H) 8.62 (m, 2H) 9.03 (d, J=2.02 Hz, 1H). LC/MS (APCI, pos.): 408.1 (M + H).
Example 13
Preparation of 6-{[7-(2-furyl)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those described for preparing Examples 7-9.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.58 (s, 3H) 2.76 (d, J=4.55 Hz, 3H) 6.49 (m, 1H) 6.64 (dd, J=3.54, 1.77 Hz, 1H) 7.21 (m, 2H) 7.60 (d, J=2.02 Hz, 1H) 7.82 (m, 2H) 7.95 (m, 2H) 8.22 (d, J=1.52 Hz, 1H) 8.30 (m, 1H) 8.61 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 408.1 (M+H).
Example 14
Preparation of N-2-dimethyl-6-[(7-pyridin-3-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 4-chloro-7-iodoquinoline 14-A (500 mg, 1.73 mmol), pyridin-3-ylboronic acid 14-B (212 mg, 1.73 mmol), 2M K 2 CO 3 solution (2.6 ml, 5.19 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (100 mg) in DMF (5 ml) were heated to 90° C. for 4 hours. The solution was filtrated and extracted with EtOAC. The organic layer was concentrated and purified by column chromatography using hexane/EtOAC (1/1) to give 234 mg of the compound 14-C.
A mixture of compound 14-C (70 mg, 0.29 mmol), 6-hydroxy-N,2-dimethyl-1-benzothiophene-3-carboxamide 14-D (64 mg, 0.29 mmol) and Cs 2 CO 3 (141 mg, 0.43 mmol) in 3 ml of a mixed solution of EtOH/Cl(CH 2 ) 2 Cl (1/1) was heated to 120° C. for 2 hours. The title compound 14 (20 mg) was isolated by HPLC (Dionex System) using 40-70% CH 3 CN/H 2 O (0.1% AcOH) over 30 minutes.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.53 (s, 3H) 2.76 (d, J=4.80 Hz, 3H) 6.56 (d, J=5.05 Hz, 1H) 7.27 (dd, J=8.59, 2.27 Hz, 1H) 7.49 (dd, J=7.83, 4.80 Hz, 1H) 7.81 (d, J=8.84 Hz, 1H) 7.89 (d, J=2.02 Hz, 1H) 7.99 (dd, J=8.72, 1.89 Hz, 1H) 8.23 (m, 2H) 8.31 (d, J=1.52 Hz, 1H) 8.37 (d, J=8.84 Hz, 1H) 8.57 (s, 1H) 8.66 (d, J=5.31 Hz, 1H) 9.03 (s, 1H). LC/MS (APCI, pos.): 426.1 (M + H).
Example 15
Preparation of 6-[(7-{[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]carbonyl}quinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
Into a solution of 15-A (1 g, 4.1 mmol), Pd(OAc) 2 (46 mg, 0.2 mmol), dppf (455 mg, 0.82 mmol) and KOAc (1.6 g, 16.4 mmol) in DMSO (20 ml) was bubbled CO gas at room temperature for 5 minutes. The solution was heated and stirred at 65° C. under CO gas (a balloon filled with CO gas was used) for 3 hours, poured into water and extracted with EtOAc. The concentrated residue was purified by silica gel column chromatography using hexane/ethylacetate/AcOH (70:30:1) to yield compound 15-B (120 mg).
A solution of compound 15-B (120 mg, 0.57 mmol) in net SOCl 2 (excess) was heated to reflux for 2 minutes. SOCl 2 was removed by evaporation under vacuum. The residue was dissolved in CH 2 Cl 2 . To the solution was added Et 3 N (87 mg, 0.86 mmol) and (2S)-2-(methoxymethyl)pyrrolidine 15-C (78 mg). The solution was stirred at room temperature for 30 minutes. Compound 15-D (140 mg) was isolated by silica gel column chromatography using hexane/EtOAc (1:1).
A solution of compound 15-D (70 mg, 0.23 mmol), 15-E (47 mg, 0.23 mmol) and Cs 2 CO 3 (90 mg, 0.27 mmol) was in DMSO (2 ml) was heated to 120° C. for 2 hours. The title compound 15 was isolated by HPLC (Dionex System) using 40-80% CH 3 CN/H 2 O (0.1% AcOH) over 30 minutes.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.84 (m, 4H) 2.58 (s, 3H) 2.76 (d, J=4.33 Hz, 3H) 2.97 (m, 2H) 3.42 (m, 2H) 3.57 (m, 1H) 6.58 (d, J=5.09 Hz, 1H) 7.23 (s, 1H) 7.64 (m, 2H) 7.81 (d, J=8.48 Hz, 1H) 7.93 (m, 1H) 8.01 (s, 1H) 8.34 (d, J=8.67 Hz, 1H) 8.66 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 474.2 (M+H).
Example 16
Preparation of 6-[(7-{[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]carbonyl}quinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide
This compound was prepared according to the methods described in Example 15, substituting the appropriate benzothiophene intermediate for the benzofuran intermediate (15-E).
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.92 (m, 4H) 2.56 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 2.97 (m, 2H) 3.41 (m, 2H) 3.58 (m, 1H) 6.59 (d, J=5.09 Hz, 1H) 7.28 (dd, J=8.76, 1.98 Hz, 1H) 7.63 (m, 2H) 7.82 (d, J=8.67 Hz, 1H) 7.91 (d, J=2.07 Hz, 1H) 8.01 (s, 1H) 8.22 (d, J=4.52 Hz, 1H) 8.33 (d, J=8.67 Hz, 1H) 8.67 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 490.2 (M + H).
Example 17
Preparation of N,2-dimethyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 4-chloro-7-bromoquinoline 17-A (1 g, 4.1 mmol) (see Scheme I: general preparation of quinolines), hexamethyldistannane 17-B (1.35 g, 4.1 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (237 mg) in 1,4-dioxane (10 ml) was heated to 105-110° C. for 2 hours. The solution was cooled to room temperature. Column chromatography (hexane/EtOAc 5:1) gave 4-chloro-7-(trimethylstannyl)quinoline 17-C (1.26 g, 94%).
A mixture of compound 17-C (500 mg, 1.5 mmol), 2-bromopyrimidine 17-D (366 mg, 2.3 mmol) and [(C 6 H 5 ) 3 P] 4 Pd (87 mg) in 1,4-dioxane (5 ml) was heated to 110° C. for 2 hours, cooled to room temperature and crystallized from dioxane to give 308 mg of 4-chloro-7-pyrimidin-2-ylquinoline 17-E.
A mixture of 17-E (70 mg, 0.29 mmol), 6-hydroxy-N,2-dimethyl-1-benzofuran-3-carboxamide 17-F (60 mg, 0.29 mmol) and Cs 2 CO 3 (141 mg, 0.43 mmol) in 2 ml of DMSO was heated to 120° C. for 2 hours. The title compound (23 mg) was isolated by HPLC (Dionex System) using 20-90% CH 3 CN/H 2 O (0.1% AcOH) over 30 minutes.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.59 (s, 3H) 2.77 (d, J=4.14 Hz, 3H) 6.59 (d, J=4.90 Hz, 1H) 7.22 (d, J=8.48 Hz, 1H) 7.58 (m, 2H) 7.81 (d, J=8.67 Hz, 1H) 8.07 (m, J=8.67 Hz, 1H) 8.43 (d, J=11.30 Hz, 2H) 8.69 (d, J=4.71 Hz, 1H) 9.21 (s, 1H) 9.31 (s, 2H). LC/MS (APCI, pos.): 411.1 (M+H).
Example 18
Preparation of N,2-dimethyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 17, substituting the appropriate benzothiophene intermediate for the benzofuran intermediate (17-F).
1 H NMR (300 MHz, DMSO-d6) ppm 2.56 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 6.61 (d, J=5.27 Hz, 1H) 7.29 (dd, J=8.85, 2.26 Hz, 1H) 7.83 (d, J=8.85 Hz, 1H) 7.91 (d, J=2.26 Hz, 1H) 8.07 (dd, J=8.67, 1.70 Hz, 1H) 8.23 (d, J=4.71 Hz, 1H) 8.42 (d, J=8.67 Hz, 1H) 8.46 (d, J=1.70 Hz, 1H) 8.70 (d, J=5.09 Hz, 1H) 9.21 (s, 1H) 9.31 (s, 2H). LC/MS (APCI, pos.): 427.1 (M + H).
Example 19
Preparation of 6-[(7-bromoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those described in Examples 5 and 6.
1 H NMR (300 MHz, DMSO-d6) ppm 2.58 (s, 3H) 2.76 (s, 3H) 6.56 (s, 1H) 7.20 (d, J=8.29 Hz, 1H) 7.60 (s, 1H) 7.77 (dd, J=14.51, 8.85 Hz, 2H) 7.92 (s, 1H) 8.22 (m, 2H) 8.63 (s, 1H). LC/MS (APCI, pos.): 411.0 (M+H).
Example 20
Preparation of 6-[(7-bromoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide
This compound was prepared using the methods analogous to those described in Examples 5 and 6.
1 H NMR (300 MHz, DMSO-d6) ppm 2.55 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 6.58 (d, J=5.09 Hz, 1H) 7.27 (dd, J=8.67, 2.26 Hz, 1H) 7.77 (m, 2H) 7.89 (d, J=2.07 Hz, 1H) 8.22 (m, 3H) 8.64 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 428.0 (M + H).
Example 21
Preparation of 6-[(6-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A mixture of 4-iodoaniline 21-A (14.5 g, 66.2 mmol) and diethyl (ethoxymethylene) malonate 21-B (14.5 g, 66.2 mmol) was heated in an oil bath to 170° C. for 40 minutes. The reaction mixture was poured into 200 ml of EtOH slowly with stirring. Diethyl {[(4-iodophenyl)amino]methylene}malonate 21-C (23.5 g, 91% yield) was collected as a white solid by filtration.
Compound (23.5 g) 21-C was placed in a round bottom flask. Phenyl ether (60 ml) was added into the flask. When the suspension was heated to 230° C. the solution became clear and EtOH was generated. The reaction was allowed to stay at 250° C. for 45 minutes, cooled to 160° C. and slowly poured into 500 ml of hexane. Ethyl 4-hydroxy-6-iodoquinoline-3-carboxylate (18.2 g, 86% yield) 21-D was precipitated, filtrated, washed with hexane (2 times) and dried.
Compound 21-D (6.0 g) was treated with 20% NaOH (100 ml) in a mixed solvent of MeOH (200 ml) and THF (80 ml) at room temperature overnight. The solution was acidified with 2N HCl to pH˜6. 4-Hydroxy-6-iodoquinoline-3-carboxylic acid 21-E (13.3 g) was obtained as a solid by filtration.
Compound 21-E (5.5 g) was placed in a 100 ml round bottom flask and heated under N 2 in an oil bath to 280° C. for 10 minutes. 6-iodoquinolin-4-ol 21-F (9.9 g, 69% yield from 21-D) was obtained as a solid.
Compound 21-F (4.5 g) was dissolved in 50 ml of POCl 3 . The solution was heated to reflux for 2 hours. The excess amount of POCl 3 was removed by evaporation under vacuum. The residue was neutralized with NH 4 OH to pH ˜7 and extracted with EtOAc. The organic layer was concentrated and purified by chromatography on a silica gel column using hexane/ethylacetate (3:1) to give 7.1 g (66% yield) of 4-chloro-6-iodoquinoline 21-G as a yellow solid.
A mixture of compound 21-G (70 mg, 0.24 mmol), 6-hydroxy-N,2-dimethyl-1-benzothiophene-3-carboxamide 21-H (54 mg, 0.24 mmol) and Cs 2 CO 3 (117 mg, 0.36 mmol) in DMSO (2 ml) was heated to 120° C. for 2 hours. The solution was extracted with EtOAc and purified by HPLC (Dionex System) using 40-80% CH 3 CN/H 2 O over 30 min to give the title compound 21.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.55 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 6.55 (d, J=5.27 Hz, 1H) 7.28 (dd, J=8.85, 2.07 Hz, 1H) 7.79 (dd, J=16.39, 8.85 Hz, 2H) 7.89 (d, J=2.07 Hz, 1H) 8.04 (m, 1H) 8.22 (s, 1H) 8.63 (m, 2H). LC/MS (APCI, pos.): 475.0 (M + H).
Example 22
Preparation of 6-[(6-iodoquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 21, substituting the appropriate benzofuran intermediate for the benzothiophene intermediate 21-H.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.58 (s, 3H) 2.76 (d, J=4.52 Hz, 3H) 6.54 (d, J=5.27 Hz, 1H) 7.21 (dd, J=8.48, 2.07 Hz, 1H) 7.60 (d, J=2.07 Hz, 1H) 7.78 (m, 2H) 7.93 (d, J=4.33 Hz, 1H) 8.03 (m, 1H) 8.62 (m, 2H). LC/MS (APCI, pos.): 459.0 (M + H).
Example 23
Preparation of N,2-dimethyl-6-[(6-pyridin-4-ylquinolin-4-yl)oxy]-1-benzothiophene-3-carboxamide
This compound was prepared according to the synthetic scheme depicted below.
1 H NMR (300 MHz, DMSO-d6) ppm 2.62 (s, 3H) 2.85 (d, J=4.52 Hz, 3H) 6.66 (d, J=5.27 Hz, 1H) 7.38 (dd, J=8.85, 2.26 Hz, 1H) 7.91 (m, 3H) 8.00 (d, J=2.07 Hz, 1H) 8.18 (d, J=8.85 Hz, 1H) 8.28 (m, 2H) 8.72 (m, 4H). LC/MS (APCI, pos.): 426.10 (M + H).
Example 24
Preparation of N,2-dimethyl-6-[(6-pyridin-4-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared according to the method described in Example 23, substituting the appropriate benzofuran intermediate for the benzothiophene intermediate 23-C.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.62 (s, 3H) 2.84 (m, 3H) 2.85 (d, J=4.52 Hz, 3H) 6.66 (d, J=5.27 Hz, 1H) 7.38 (dd, J=8.85, 2.26 Hz, 1H) 7.91 (m, 3H) 8.00 (d, J=2.07 Hz, 1H) 8.18 (d, J=8.85 Hz, 1H) 8.28 (m, 2H) 8.72 (m, 4H). LC/MS (APCI, pos.): 410.10 (M+H).
Example 25
Preparation of N,2-dimethyl-6-({6-[2-(1-methylpyrrolidinyl-2-yl)ethoxy]quinolin-4-yl}oxy)-1-benzothiophene-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
To a solution of 25-A (100 mg, 0.8 mmol) in dichloromethane (4 ml) was added Br 2 P(Ph) 3 (330 mg, 0.8 mmol). The solution was stirred at room temperature for 30 minutes. The solution was poured into water, acidified with Hal to pH˜2 and extracted with Teac. The water layer was basified with NH 4 OH to pH˜9 and extracted with Teac, dried (MgSO 4 ) and concentrated to give a crude compound 25-B (110 mg).
A mixture of compound 25-C (500 mg, 2.6 mol), 6-hydroxy-N,2-dimethyl-1-benzothiophene-3-carboxamide 25-D (573 mg, 2.6 mol) and Cs 2 CO 3 (1.3 g, 3.9 mol) in 6 ml of DMSO was heated to 120° C. for 2 hours. The concentrated residue was purified by silica gel chromatography column using Hexane/Teac (2/1 to 100% Teac) to offer 6-[(6-methoxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide 25-E (361 mg, 37% yield) as a yellow solid.
To a solution of 25-E (320 mg) in dichloromethane (2 ml) was added 1.7 ml solution of BBr 3 (1M in dichloromethane) at −78° C. The solution was stirred at room temperature overnight. The reaction was quenched with MeOH. The residue was purified by a silica gel column using 2-5% MeOH in CH 2 Cl 2 to give 6-[(6-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide 25-F (250 mg, 77% yield).
A solution of 25-F (70 mg, 0.19 mmol), 2-(2-bromoethyl)-1-methylpyrrolidine 25-B (110 mg crude and Cs 2 CO 3 (94 mg, 1.5 mmol) in DMSO (2 ml) was heated to 120° C. for 2 hours. The title compound, N,2-dimethyl-6-({6-[2-(1-methylpyrrolidin-2-yl)ethoxy]quinolin-4-yl}oxy)-1-benzothiophene-3-carboxamide 25 (21 mg) was isolated by HPLC (Dionex System) using 20-60% CH 3 CN/H 2 O (0.1% AcOH) over 30 minutes.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.60-1.84 (m, 4H) 2.06 (m, 2H) 2.30 (s, 3H) 2.55 (s, 3H) 2.63 (m, 2H) 2.78 (d, J=4.52 Hz, 3H) 3.29 (m, 2H) 4.12 (m, 0.5H) 4.77 (m, 0.5H) 6.50 (dd, J=8.67, 3.58 Hz, 1H) 7.24 (m, 1H) 7.39 (m, 1H) 7.50 (m, 2H) 7.84 (m, 3H) 8.22 (s, 1H) 8.46 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 376.20 (M+H).
Example 26
Preparation of 6-[(6-methoxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogues to those depicted and described in Example 25.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.55 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 3.87 (s, 3H) 6.50 (d, J=5.09 Hz, 1H) 7.25 (dd, J=8.76, 2.17 Hz, 1H) 7.41 (dd, J=9.23, 2.83 Hz, 1H) 7.53 (d, J=2.83 Hz, 1H) 7.81 (d, J=8.67 Hz, 1H) 7.88 (m, 2H) 8.22 (d, J=4.52 Hz, 1H) 8.46 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 379.10 (M + H).
Example 27
Preparation of 6-[(6-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in Example 25 using the appropriate 4-chloro-quinoline intermediate.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.61 (s, 3H) 2.84 (d, J=4.52 Hz, 3H) 6.55 (d, J=5.09 Hz, 1H) 7.29 (dd, J=8.85, 2.26 Hz, 1H) 7.36 (dd, J=9.14, 2.73 Hz, 1H) 7.49 (d, J=2.64 Hz, 1H) 7.88 (m, 3H) 8.28 (d, J=4.52 Hz, 1H) 8.47 (d, J=4.90 Hz, 1H) 10.14 (s, 1H). LC/MS (APCI, pos.): 365.10 (M + H).
Example 28
Preparation of 6-[(7-hydroxyquinoline-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A mixture of 3-methoxyaniline (25 g, 204 mmol) 28-A and diethyl (ethoxymethylene) malonate (44 g, 204 mmol) 28-B was heated in an oil bath to 150° C. for 40 minutes. EtOH was generated when the temperature reached 132° C. and collected. The reaction flask was moved away from oil bath and phenyl ether (70 ml) was added into the reaction mixture. The oil bath was preheated to 270° C. The reaction was heated at 270° C. (oil bath temperature) for 15 minutes. The reaction mixture was poured slowly into 800 ml of hexane with stirring. Ethyl 4-hydroxy-7-methoxyquinoline-3-carboxylate 28-C was precipitated, filtrated, washed with hexane and dried (28.4 g, 56% yield).
A solution of compound 28-C (4.2 g) and KOH (3 g, 3 eq.) in 40 ml of EtOH/H 2 O (1:1) was heated by microwave to 180° C. for 50 minutes. The mixture was cooled to room temperature, poured into water (100 ml), neutralized with AcOH to pH 7 and saturated with NaCl. The solution was extracted with THF (3×300 ml) and concentrated to yield 3.1 g of 7-methoxyquinolin-4-ol 28-D as a solid.
Compound 28-D (7.4 g) was dissolved in 20 ml of POCl 3 . The solution was heated to reflux for 2 hours. The excess amount of POCl 3 was removed by evaporation under vacuum. The residue was neutralized with NH 4 OH to pH ˜7 and extracted with EtOAc. The organic layer was concentrated and purified by chromatography on a silica gel column using hexane/ethylacetate (3:1) to give 6.5 g of 4-chloro-7-methoxyquinoline as 28-E as a yellow solid.
A mixture of 28-E (1.4 g, 7.3 mmol), 6-hydroxy-N,2-dimethyl-1-benzofuran-3-carboxamide 28-F (1.5 g, 7.3 mmol) and Cs 2 CO 3 (3.6, 11 mmol) in 12 ml of DMSO was heated to 120° C. for 2 hours, poured into water and extracted with EtOAc. Silica gel chromatography using 2% MeOH/CH 2 Cl 2 offered 1.4 g of 6-[(7-methoxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 28-G.
To a suspension of 6-[(7-methoxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 28-G (1.4 g, 3.8 mmol) in CH 2 Cl 2 was added 10 ml of BBr 3 (1M in CH 2 Cl 2 ) at −78° C. The solution was stirred at room temperature for 6 hours. To the solution 20 ml of toluene was added into, heated to reflux for 4 hours, cooled to 0° C. and quenched with water, extracted with EtOAc and concentrated to give the title compound 28 (1.2 g) as a solid.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.56 (d, J=7.35 Hz, 3H) 2.76 (d, J=4.52 Hz, 3H) 6.28 (d, J=5.27 Hz, 1H) 7.14 (m, 2H) 7.19 (d, J=2.26 Hz, 1H) 7.53 (d, J=2.07 Hz, 1H) 7.77 (d, J=8.48 Hz, 1H) 7.92 (d, J=4.52 Hz, 1H) 8.11 (d, J=9.04 Hz, 1H) 8.45 (d, J=5.27 Hz, 1H) 10.23 (s, 1H). LC/MS (APCI, pos.): 349.10 (M+H).
Example 29
Preparation of 6-[(7-methoxyquinoline-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 28.
1 H NMR (300 MHz, DMSO-d6) ppm 2.57 (s, 3H) 2.76 (d, J=4.52 Hz, 3H) 3.87 (s, 3H) 6.37 (d, J=5.27 Hz, 1H) 7.20 (m, 2H) 7.35 (d, J=2.45 Hz, 1H) 7.56 (d, J=2.07 Hz, 1H) 7.78 (d, J=8.48 Hz, 1H) 7.92 (d, J=4.52 Hz, 1H) 8.17 (d, J=9.04 Hz, 1H) 8.53 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 363.10 (M+H).
Example 30
Preparation of N,2-dimethyl-6-{(7-1,3-thiazol-2-yl)quinolin-4-yl)oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 7-9, 13, and 17.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.59 (s, 3H) 2.77 (d, J=4.33 Hz, 3H) 7.23 (d, J=9.61 Hz, 2H) 7.63 (s, 1H) 7.81 (d, J=8.48 Hz, 1H) 7.89 (d, 2H) 8.00 (d, J=2.83 Hz, 1H) 8.20 (d, J=8.67 Hz, 1H) 8.41 (d, J=8.67 Hz, 1H) 8.48 (s, 1H) 8.68 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 426.10 (M + H).
Example 31
Preparation of N,2-dimethyl-6-[(7-pyridin-2-yl)quinolin-4-yl)oxy}-1-benzothiaphene-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 10.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.56 (s, 3H) 2.78 (d, J=4.52 Hz, 3H) 7.30 (dd, J=8.85, 2.26 Hz, 1H) 7.39 (dd, J=7.54, 4.71 Hz, 1H) 7.83 (d, J=8.85 Hz, 1H) 7.92 (m, 2H) 8.18 (d, J=7.91 Hz, 1H) 8.23 (d, J=4.90 Hz, 1H) 8.38 (s, 2H) 8.67 (m, 2H) 8.71 (dd, J=4.80, 0.85 Hz, 1H). LC/MS (APCI, pos.): 426.10 (M+H).
Example 32
Preparation of N,2-dimethyl-5-[(7-pyridin-2-yl)quinolin-4-yl)amino]-1H-indole-1-carboxamide
This compound was prepared according to methods analogous to those described in Example 11.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.43 (s, 3H) 2.83 (d, J=4.33 Hz, 3H) 6.36 (s, 1H) 6.62 (d, J=6.03 Hz, 1H) 7.13 (dd, J=8.76, 1.98 Hz, 1H) 7.42 (m, 2H) 7.64 (d, J=8.67 Hz, 1H) 7.92 (m, 1H) 8.17 (m, 2H) 8.29 (d, J=8.67 Hz, 1H) 8.38 (d, J=6.03 Hz, 1H) 8.55 (s, 1H) 8.60 (d, J=9.04 Hz, 1H) 8.71 (m, 1H) 9.71 (s, 1H). LC/MS (APCI, pos.): 408.20 (M+H).
Example 33
Preparation of N,2-dimethyl-6-{[7-(pyridin-2-ylmethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to the reaction scheme depicted below.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.57 (s, 3H) 2.76 (d, J=4.52 Hz, 3H) 5.35 (s, 2H) 6.39 (d, J=5.27 Hz, 1H) 7.17 (dd, J=8.48, 2.07 Hz, 1H) 7.36 (m, 1H) 7.41 (d, J=2.45 Hz, 1H) 7.45 (d, J=5.84 Hz, 2H) 7.56 (d, J=1.88 Hz, 1H) 7.78 (d, J=8.48 Hz, 1H) 7.92 (d, J=4.52 Hz, 1H) 8.21 (d, J=9.23 Hz, 1H) 8.53 (m, 3H). LC/MS (APCI, pos.): 441.20 (M+H).
Example 34
Preparation of N,2-dimethyl-6-{[7-(thiazol-2-ylmethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to the methods depicted in Example 33, substituting the appropriate thiazolyl intermediate for the pyridyl intermediate (33-B).
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.57 (s, 3H) 2.62 (s, 3H) 2.76 (d, J=4.52 Hz, 3H) 5.23 (s, 2H) 6.38 (d, J=5.27 Hz, 1H) 7.17 (dd, J=8.57, 2.17 Hz, 1H) 7.29 (dd, J=9.04, 2.45 Hz, 1H) 7.49 (d, J=2.64 Hz, 1H) 7.56 (d, J=2.07 Hz, 1H) 7.58 (s, 1H) 7.78 (d, J=8.48 Hz, 1H) 7.93 (s, 1H) 8.18 (d, J=9.23 Hz, 1H) 8.53 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 461.20 (M+H).
General Synthetic Scheme for the Preparation of the Compounds of Examples 35 to 38
A solution of amine B (0.27 mmol) and Cs 2 CO 3 (175 mg, 0.54 mmol) in DMF (2 ml) was stirred at room temperature for 1 hour. To this solution was added a solution of 6-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide A (70 mg, 0.18 mmol) in DMF (1 ml). The solution was heated to 120° C. for 2 hours. The solids were removed by filtration. The residue was purified by HPLC using 20-60% CH 3 CN/H 2 O over 30 minutes to yield compound C.
Example 35
Preparation of N,2-dimethyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
1 H NMR (300 MHz, DMSO-d6) ppm 1.63 (m, 4H) 2.45 (m, 4H) 2.79 (m, 5H) 4.19 (t, J=5.75 Hz, 2H) 6.37 (d, J=5.27 Hz, 1H) 7.16 (dd, J=8.57, 2.17 Hz, 1H) 7.23 (dd, J=9.14, 2.54 Hz, 1H) 7.35 (d, J=2.45 Hz, 1H) 7.55 (d, J=2.07 Hz, 1H) 7.79 (m, 1H) 7.92 (d, J=4.52 Hz, 1H) 8.16 (d, J=9.23 Hz, 1H) 8.52 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 447.25 (M+H).
Example 36
Preparation of N,2-dimethyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.57 (s, 3H) 2.73 (m, 5H) 3.30 (m, 4H) 3.53 (m, 4H) 4.21 (t, J=5.37 Hz, 2H) 6.37 (d, J=5.27 Hz, 1H) 7.19 (m, 2H) 7.37 (d, J=2.07 Hz, 1H) 7.55 (d, J=1.88 Hz, 1H) 7.78 (d, J=8.67 Hz, 1H) 7.92 (d, J=4.33 Hz, 1H) 8.16 (d, J=9.23 Hz, 1H) 8.52 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 462.10 (M+H).
Example 37
Preparation of 6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-N,2-dimethyl-1-benzofuran-3-carboxamide
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.18 (s, J=5.84 Hz, 6H) 2.58 (s, 3H) 2.64 (t, J=5.65 Hz, 2H) 2.76 (d, J=4.52 Hz, 3H) 4.17 (t, J=5.65 Hz, 2H) 6.37 (d, J=5.27 Hz, 1H) 7.19 (m, 2H) 7.36 (d, J=2.26 Hz, 1H) 7.55 (d, J=2.07 Hz, 1H) 7.78 (d, J=8.48 Hz, 1H) 7.93 (d, J=4.52 Hz, 1H) 8.16 (d, J=9.23 Hz, 1H) 8.52 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 420.20 (M+H).
Example 38
Preparation of N,2-dimethyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-37.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.32 (m, 2H) 1.45 (m, 4H) 2.42 (m, 4H) 2.57 (s, 3H) 2.67 (t, J=5.84 Hz, 2H) 2.76 (d, J=4.52 Hz, 3H) 4.18 (t, J=5.84 Hz, 2H) 6.37 (d, J=5.27 Hz, 1H) 7.16 (dd, J=8.48, 2.26 Hz, 1H) 7.22 (dd, J=9.14, 2.54 Hz, 1H) 7.35 (d, J=2.45 Hz, 1H) 7.55 (d, J=2.07 Hz, 1H) 7.78 (d, J=8.67 Hz, 1H) 7.92 (d, J=4.71 Hz, 1H) 8.15 (d, J=9.23 Hz, 1H) 8.52 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 460.20 (M+H).
Example 39
Preparation of N-butyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-38.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.76 (t, J=7.45 Hz, 3H) 1.22 (m, 2H) 1.38 (m, 2H) 2.46 (s, 3H) 3.13 (m, 2H) 3.77 (s, 3H) 6.27 (d, J=5.31 Hz, 1H) 7.07 (dd, J=8.46, 2.15 Hz, 1H) 7.13 (dd, J=9.09, 2.53 Hz, 1H) 7.25 (d, J=2.53 Hz, 1H) 7.45 (d, J=2.02 Hz, 1H) 7.63 (d, J=8.59 Hz, 1H) 7.89 (t, J=5.68 Hz, 1H) 8.07 (d, J=9.10 Hz, 1H) 8.43 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 405.20 (M+H).
Example 40
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-pyridin-2-yl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-39.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.64 (s, 3H) 3.88 (s, 3H) 6.40 (m, 1H) 7.11 (m, 1H) 7.21 (m, 2H) 7.35 (d, J=2.53 Hz, 1H) 7.60 (d, J=2.27 Hz, 1H) 7.79 (m, 2H) 8.13 (d, J=8.34 Hz, 1H) 8.17 (m, 1H) 8.32 (dd, J=4.80, 1.01 Hz, 1H) 8.53 (t, J=4.29 Hz, 1H) 10.53 (s, 1H). LC/MS (APCI, pos.): 426.10 (M+H).
Example 41
Preparation of N-butyl-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Example 28.
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 0.86 (t, J=7.45 Hz, 3H) 1.31 (m, 2H) 1.47 (m, 2H) 2.56 (s, 3H) 3.23 (m, 2H) 6.28 (d, J=5.05 Hz, 1H) 7.14 (m, 2H) 7.19 (d, J=2.53 Hz, 1H) 7.53 (d, J=2.02 Hz, 1H) 7.73 (d, J=8.59 Hz, 1H) 7.99 (t, J=5.68 Hz, 1H) 8.11 (d, J=9.10 Hz, 1H) 8.45 (d, J=5.31 Hz, 1H) 10.19 (s, 1H). LC/MS (APCI, pos.): 391.20 (M + H).
Example 42
Preparation of 6-{[7-(allyloxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40.
1 H NMR (400 MHz, DMSO-d 6 ) ppm 2.65 (s, 3H) 2.84 (d, J=4.55 Hz, 3H) 4.78 (d, J=5.31 Hz, 2H) 5.34 (d, J=10.61 Hz, 1H) 5.49 (m, 1H) 6.13 (m, 1H) 6.45 (d, J=5.31 Hz, 1H) 7.24 (dd, J=8.46, 2.15 Hz, 1H) 7.33 (dd, J=9.09, 2.27 Hz, 1H) 7.44 (d, J=2.27 Hz, 1H) 7.63 (d, J=2.02 Hz, 1H) 7.86 (d, J=8.34 Hz, 1H) 7.98 (d, J=4.29 Hz, 1H) 8.25 (d, J=9.35 Hz, 1H) 8.60 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 389.10 (M + H).
Example 43
Preparation of N-isopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40 and 42.
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.20 (m, 6H) 2.62 (s, 3H) 3.33 (s, 3H) 3.95 (s, 3H) 4.14 (m, 1H) 6.44 (m, 1H) 7.25 (d, J=2.02 Hz, 1H) 7.31 (dd, J=9.22, 2.40 Hz, 1H) 7.42 (s, 1H) 7.62 (s, 1H) 7.78 (d, J=8.59 Hz, 1H) 7.96 (d, J=7.58 Hz, 1H) 8.25 (m, 1H) 8.60 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 391.10 (M+H).
Example 44
Preparation of N-butyl-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40 and 42-43.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.94 (t, J=7.33 Hz, 3H) 1.37 (m, 2H) 1.56 (m, 2H) 1.71 (m, 4H) 2.57 (m, 4H) 2.64 (s, 3H) 2.89 (t, J=5.68 Hz, 2H) 3.30 (m, 2H) 4.27 (t, J=5.94 Hz, 2H) 6.45 (d, J=5.31 Hz, 1H) 7.24 (dd, J=8.46, 2.15 Hz, 1H) 7.30 (dd, J=9.10, 2.53 Hz, 1H) 7.43 (d, J=2.53 Hz, 1H) 7.62 (d, J=2.27 Hz, 1H) 7.81 (d, J=8.34 Hz, 1H) 8.07 (t, J=6.06 Hz, 1H) 8.24 (d, J=9.10 Hz, 1H) 8.60 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 488.20 (M+H).
Example 45
Preparation of N-butyl-2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40 and 42-44.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.86 (t, J=7.33 Hz, 3H) 1.31 (m, 2H) 1.48 (m, 2H) 2.56 (s, 3H) 2.72 (t, J=5.56 Hz, 2H) 3.53 (m, 4H) 4.21 (t, J=5.68 Hz, 2H) 6.37 (d, J=5.05 Hz, 1H) 7.16 (dd, J=8.59, 2.02 Hz, 1H) 7.23 (dd, J=9.35, 2.53 Hz, 1H) 7.37 (d, J=2.27 Hz, 1H) 7.55 (d, J=2.02 Hz, 1H) 7.73 (d, J=8.59 Hz, 1H) 8.01 (t, J=5.81 Hz, 1H) 8.16 (d, J=9.35 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 504.20 (M+H).
Example 46
Preparation of N-butyl-6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40 and 42-45.
1 H NMR (400 MHz, DMSO-D6) δ ppm 0.86 (t, 3H), 1.32 (m, 2H), 1.48 (m, 2H), 2.18 (s, 6H), 2.40 (m, 2H), 2.56 (s, 3H), 2.63 (t, 2H), 4.18 (t, 2H), 6.36 (d, 1H), 7.17 (dd, 1H), 7.22 (dd, 1H), 7.36 (d, 2H), 7.55 (d, 1H), 7.73 (d, 1H), 8.01 (t, 1H), 8.16 (d, 1H), 8.52 (d, 1H). LC/MS (APCI, pos.): 462.20 (M+H).
Example 47
Preparation of N-butyl-2-methyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Examples 33-40 and 42-46.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.86 (t, J=7.45 Hz, 3H) 1.31 (m, 2H) 1.47 (m, 2H) 2.18 (s, 6H) 2.56 (s, 3H) 2.63 (m, 2H) 4.17 (t, J=5.68 Hz, 2H) 6.37 (d, J=5.05 Hz, 1H) 7.17 (dd, J=8.46, 2.15 Hz, 1H) 7.22 (dd, J=9.10, 2.53 Hz, 1H) 7.36 (d, J=2.27 Hz, 1H) 7.55 (d, J=2.27 Hz, 1H) 7.73 (d, J=8.59 Hz, 1H) 8.01 (t, J=5.56 Hz, 1H) 8.16 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 502.20 (M+H).
Example 48
Preparation of N-cyclopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
To a solution of 6-methoxy-2-methyl-1-benzothiophene-3-carboxylic acid 48-A (5 g, 22.5 mmol) in CH 2 Cl 2 (50 ml) was added BBr 3 (33 ml, 1M CH 2 Cl 2 solution) at −78° C. After being stirred for 1 hour the cooling bath was removed. The reaction was stirred at room temperature overnight. The reaction was quenched with water at 0° C. The mixture was extracted with EtOAc. Insoluble was collected by filtration to yield 2.1 g of 6-hydroxy-2-methyl-1-benzothiophene-3-carboxylic acid (B). The organic layer was washed with brine, dried (MgSO 4 ) and concentrated to give 2.7 g of 48-B.
A mixture of 48-B (1.5 g, 7.2 mmol), 4-chloro-7-methoxyquinoline 48-C (1.4 g, 7.2 mmol) and Cs 2 CO 3 (7 g, 21.6 mmol) in 40 ml of DMSO was heated to 120° C. for 2 hours, poured into water, acidified with AcOH to pH˜6 and extracted with EtOAc (3×100 ml) and concentrated. The residue was purified by silica gel chromatography using 5% AcOH in EtOAc to offered 1.4 g of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxylic acid 48-D.
Compound 48-D (90 mg, 0.24 mmol) was dissolved in SoCl 2 (2 ml). The solution was heated to reflux to 5 minutes. SOCl 2 was removed under vacuum. The residue was dissolved in 2 ml of CH 2 Cl 2 and cyclopropanamine 48-E (34 mg, 0.6 mmol) was added into. The solution was stirred at room temperature for 20 minutes. The title compound 48 (79 mg) was isolated by silica gel column using 5% MeOH in CH 2 Cl 2 .
1 H NMR (300 MHz, DMSO-d6) δ ppm 0.51 (m, 2H) 0.65 (m, 2H) 2.51 (s, 3H) 2.83 (m, 1H) 3.93 (s, 3H) 6.67 (d, J=6.41 Hz, 1H) 7.32 (dd, J=8.76, 2.17 Hz, 1H) 7.46 (m, 1H) 7.49 (m, 1H) 7.80 (d, J=8.85 Hz, 1H) 7.96 (d, J=2.07 Hz, 1H) 8.37 (d, J=4.33 Hz, 1H) 8.40 (s, 1H) 8.78 (d, J=6.41 Hz, 1H). LC/MS (APCI, pos.): 405.10 (M+H).
Example 49
Preparation of N-[2-(dimethylamino)ethyl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.25 (s, 6H) 2.63 (s, 3H) 3.33 (m, 2H) 3.43 (q, J=6.15 Hz, 2H) 3.95 (s, 3H) 6.46 (d, J=5.09 Hz, 1H) 7.31 (m, 2H) 7.43 (d, J=2.26 Hz, 1H) 7.91 (m, 2H) 8.23 (d, J=9.04 Hz, 1H) 8.30 (t, J=5.37 Hz, 1H) 8.61 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 436.10 (M+H).
Example 50
Preparation of [(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-propyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (300 MHz, DMSO-d6) δ ppm 0.95 (t, J=7.35 Hz, 3H) 1.58 (m, 2H) 2.61 (s, 3H) 3.28 (m, 2H) 3.94 (s, 3H) 6.46 (d, J=5.27 Hz, 1H) 7.30 (m, 2H) 7.42 (d, J=2.45 Hz, 1H) 7.83 (d, J=8.85 Hz, 1H) 7.92 (d, J=2.26 Hz, 1H) 8.23 (d, J=9.04 Hz, 1H) 8.38 (t, J=5.75 Hz, 1H) 8.60 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 407.10 (M+H).
Example 51
Preparation of N-[3-(dimethylamino)propyl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.80 (m, 2H) 2.36 (s, 6H) 2.58 (m, 2H) 2.63 (s, 3H) 3.34 (m, 2H) 3.95 (s, 3H) 7.30 (m, 2H) 7.42 (s, 1H) 7.87 (d, J=8.48 Hz, 1H) 7.93 (s, 1H) 8.22 (m, 1H) 8.45 (m, 1H) 8.61 (m, 1H). LC/MS (APCI, pos.): 451.20 (M+H).
Example 52
Preparation of N-cyclohexyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.33 (m, 4H) 1.61 (m, 2H) 1.75 (m, J=2.78 Hz, 2H) 1.93 (m, 2H) 2.62 (s, 3H) 3.84 (m, 1H) 4.01 (s, 3H) 6.68 (d, J=6.06 Hz, 1H) 7.39 (dd, J=8.84, 2.27 Hz, 1H) 7.48 (dd, J=9.22, 2.40 Hz, 1H) 7.55 (d, J=2.53 Hz, 1H) 7.87 (d, J=8.59 Hz, 1H) 8.02 (d, J=2.27 Hz, 1H) 8.30 (d, J=8.08 Hz, 1H) 8.41 (d, J=9.35 Hz, 1H) 8.80 (d, J=6.06 Hz, 1H). LC/MS (APCI, pos.): 447.10 (M+H).
Example 53
Preparation of N-cyclopentyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.57 (m, 4H) 1.71 (m, 2H) 1.93 (m, 2H) 2.60 (s, 3H) 3.95 (s, 3H) 4.31 (m, 1H) 6.46 (d, J=5.05 Hz, 1H) 7.31 (m, 2H) 7.43 (d, J=2.53 Hz, 1H) 7.81 (d, J=8.59 Hz, 1H) 7.91 (d, J=2.27 Hz, 1H) 8.24 (d, J=9.10 Hz, 1H) 8.36 (d, J=7.33 Hz, 1H) 8.61 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 433.10 (M + H).
Example 54
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-3-ylmethyl)-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in connection with Example 48, substituting the appropriate amine intermediate for cyclopropylamine (48-E).
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.63 (s, 3H) 3.95 (s, 3H) 4.57 (d, J=6.06 Hz, 1H) 6.48 (d, J=5.31 Hz, 1H) 7.32 (m, 2H) 7.41 (m, 1H) 7.43 (d, J=2.27 Hz, 1H) 7.82 (m, 1H) 7.86 (d, J=8.84 Hz, 1H) 7.94 (d, J=2.27 Hz, 1H) 8.23 (d, J=9.09 Hz, 1H) 8.50 (dd, J=4.80, 1.52 Hz, 1H) 8.61 (d, J=5.05 Hz, 1H) 8.63 (d, J=1.77 Hz, 1H) 8.97 (t, J=5.94 Hz, 1H). LC/MS (APCI, pos.): 456.10 (M + H).
Example 55
Preparation of 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-N-propyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.99 (q, J=7.16 Hz, 3H) 1.62 (m, 2H) 2.65 (d, J=6.06 Hz, 3H) 3.32 (m, 2H) 6.41 (t, J=5.68 Hz, 1H) 7.24 (m, 1H) 7.32 (m, 2H) 7.86 (m, 1H) 7.93 (d, J=4.29 Hz, 1H) 8.21 (dd, J=8.59, 6.57 Hz, 1H) 8.40 (s, 1H) 8.57 (t, J=5.68 Hz, 1H) 10.29 (d, J=6.32 Hz, 1H). LC/MS (APCI, pos.): 393.1 (M+H).
Example 56
Preparation of N-cyclopentyl-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.50 (m, 4H) 1.61 (m, 2H) 1.85 (m, 2H) 2.52 (s, 3H) 4.23 (m, 1H) 6.30 (d, J=5.05 Hz, 1H) 7.13 (dd, J=8.97, 2.40 Hz, 1H) 7.21 (m, 2H) 7.73 (d, J=8.84 Hz, 1H) 7.82 (d, J=2.27 Hz, 1H) 8.28 (d, J=7.33 Hz, 1H) 8.46 (d, J=5.05 Hz, 1H) 10.18 (s, 1H). LC/MS (APCI, pos.): 419.1 (M+H).
Example 57
Preparation of N-[2-(dimethylamino)ethyl]-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.46 (d, J=4.04 Hz, 6H) 2.68 (d, J=4.55 Hz, 3H) 2.83 (s, 2H) 3.76 (m, 2H) 6.30 (s, 1H) 6.98 (s, 1H) 7.10 (s, 1H) 7.26 (d, J=5.05 Hz, 1H) 7.37 (s, 2H) 7.49 (d, J=2.53 Hz, 1H) 7.90 (dd, J=8.34, 4.80 Hz, 1H) 8.06 (d, J=4.04 Hz, 1H) 8.30 (s, 1H). LC/MS (APCI, pos.): 422.1 (M+H).
Example 58
Preparation of N-[3-(dimethylamino)propyl]-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.74 (m, 2H) 2.43 (s, 6H) 2.56 (s, 3H) 2.62 (m, J=6.32 Hz, 2H) 3.29 (m, 2H) 6.30 (d, J=5.31 Hz, 1H) 7.13 (dd, J=9.10, 2.27 Hz, 1H) 7.22 (m, 3H) 7.78 (d, J=8.84 Hz, 1H) 7.84 (d, J=2.27 Hz, 1H) 8.10 (d, J=9.10 Hz, 1H) 8.36 (t, J=5.56 Hz, 1H) 8.46 (d, J=5.31 Hz, 1H) 10.19 (s, 1H). LC/MS (APCI, pos.): 422.1 (M+H).
Example 59
Preparation of 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-3-ylmethyl)-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.56 (s, 3H) 4.49 (d, J=6.06 Hz, 2H) 6.37 (d, J=5.05 Hz, 1H) 7.17 (dd, J=8.97, 1.64 Hz, 1H) 7.21 (s, 1H) 7.25 (dd, J=8.84, 1.77 Hz, 1H) 7.34 (dd, J=7.83, 4.80 Hz, 1H) 7.74 (d, J=8.08 Hz, 1H) 7.79 (d, J=8.59 Hz, 1H) 7.86 (s, 1H) 8.15 (d, J=9.09 Hz, 1H) 8.43 (d, J=4.29 Hz, 1H) 8.51 (d, J=5.31 Hz, 1H) 8.55 (s, 1H) 8.89 (t, J=6.06 Hz, 1H) 10.38 (s, 1H). LC/MS (APCI, pos.): 442.1 (M+H).
Example 60
Preparation of N,2-dimethyl-6-{[7-(trifluoromethyl)quinolin-4-yl]oxy}-1-benzothiophene-3-carboxamide
This compound was prepared according to methods analogous to those described in Scheme I and Example 21, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.63 (s, 3H) 2.85 (t, J=4.93 Hz, 3H) 6.78 (d, J=5.05 Hz, 1H) 7.37 (dd, J=8.84, 2.27 Hz, 1H) 7.91 (d, J=8.84 Hz, 1H) 7.95 (dd, J=8.84, 1.52 Hz, 1H) 7.99 (d, J=2.27 Hz, 1H) 8.27 (m, 1H) 8.41 (s, 1H) 8.60 (d, J=8.84 Hz, 1H) 8.85 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 417.1 (M+H).
Example 61
Preparation of N,2-dimethyl-6-{[7-(trifluoromethyl)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those described in Schemes I and II and Examples 5 and 6 and using the appropriate starting materials.
1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 2.75 (d, J=1.77 Hz, 3H) 3.09 (s, 3H) 5.90 (s, 1H) 6.63 (s, 1H) 7.17 (d, J=8.34 Hz, 1H) 7.32 (s, 1H) 7.78 (d, J=7.33 Hz, 2H) 8.41 (s, 1H) 8.53 (d, J=7.07 Hz, 1H) 8.75 (s, 1H). LC/MS (APCI, pos.): 401.1 (M+H).
Example 62
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.99 (m, 2H) 2.66 (s, 3H) 3.19 (m, J=12.43 Hz, 4H) 3.41 (m, 6H) 3.65 (t, J=11.68 Hz, 2H) 4.00 (m, 3H) 6.64 (d, J=5.84 Hz, 1H) 7.39 (dd, J=8.76, 2.35 Hz, 1H) 7.44 (m, 1H) 7.47 (s, 1H) 7.91 (d, J=8.67 Hz, 1H) 8.03 (d, J=2.26 Hz, 1H) 8.37 (d, J=9.04 Hz, 1H) 8.52 (t, J=5.75 Hz, 1H) 8.77 (d, J=5.46 Hz, 1H) 9.52 (s, 1H). LC/MS (APCI, pos.): 491.2 (M+H).
Example 63
Preparation of N-cyclopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 0.55 (m, J=3.86, 3.86 Hz, 2H) 0.65 (m, 2H) 2.53 (s, 3H) 2.80 (m, 1H) 3.87 (s, 3H) 6.36 (d, J=5.09 Hz, 1H) 7.15 (dd, J=8.48, 2.07 Hz, 1H) 7.23 (dd, J=9.14, 2.54 Hz, 1H) 7.35 (d, J=2.45 Hz, 1H) 7.54 (d, J=2.07 Hz, 1H) 7.68 (d, J=8.48 Hz, 1H) 8.12 (d, J=3.77 Hz, 1H) 8.17 (d, J=9.23 Hz, 1H) 8.52 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 389.1 (M+H).
Example 64
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.83 (m, 2H) 2.42 (m, J=24.11 Hz, 8H) 2.74 (s, 3H) 3.66 (m, 4H) 4.04 (s, 3H) 6.54 (d, J=5.27 Hz, 1H) 7.34 (dd, J=8.57, 2.17 Hz, 1H) 7.40 (dd, J=9.14, 2.54 Hz, 1H) 7.52 (d, J=2.64 Hz, 1H) 7.73 (d, J=2.26 Hz, 1H) 7.92 (d, J=8.48 Hz, 1H) 8.19 (m, 1H) 8.34 (d, J=9.23 Hz, 1H) 8.69 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 476.2 (M+H).
Example 65
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-benzofuran-3-carboxylic acid (3-dimethylamino-propyl)-amide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.70 (m, 2H) 2.15 (d, J=3.96 Hz, 6H) 2.65 (s, 3H) 3.32 (m, 4H) 3.95 (s, 3H) 6.45 (d, J=5.27 Hz, 1H) 7.25 (dd, J=8.48, 2.07 Hz, 1H) 7.30 (dd, J=9.14, 2.54 Hz, 1H) 7.42 (d, J=2.64 Hz, 1H) 7.63 (d, J=2.26 Hz, 1H) 7.83 (d, J=8.67 Hz, 1H) 8.16 (t, J=5.46 Hz, 1H) 8.24 (d, J=9.23 Hz, 1H) 8.60 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 434.2 (M+H).
Example 66
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(pyridin-2-ylmethyl)-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.63 (s, 3H) 3.87 (s, 3H) 4.56 (d, J=5.84 Hz, 2H) 6.39 (d, J=5.27 Hz, 1H) 7.21 (m, 3H) 7.35 (m, J=1.88 Hz, 2H) 7.58 (d, J=2.07 Hz, 1H) 7.73 (m, 1H) 7.85 (d, J=8.48 Hz, 1H) 8.17 (d, J=9.04 Hz, 1H) 8.48 (dd, J=4.05, 0.85 Hz, 1H) 8.53 (d, J=5.27 Hz, 1H) 8.58 (m, 1H). LC/MS (APCI, pos.): 440.1 (M+H).
Example 67
Preparation of N-(3-hydroxypropyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.75 (m, 2H) 2.64 (s, 3H) 3.34 (m, 4H) 3.94 (s, 3H) 4.57 (s, 1H) 6.44 (d, J=5.27 Hz, 1H) 7.23 (dd, J=8.57, 2.17 Hz, 1H) 7.30 (dd, J=9.04, 2.64 Hz, 1H) 7.42 (d, J=2.45 Hz, 1H) 7.62 (d, J=1.88 Hz, 1H) 7.82 (d, J=8.48 Hz, 1H) 8.06 (t, J=5.46 Hz, 1H) 8.24 (m, J=9.04 Hz, 1H) 8.59 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 407.1 (M+H).
Example 68
Preparation of N-(5-hydroxy-1H-pyrazol-3-yl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.54 (s, 3H) 3.96 (s, 3H) 4.87 (s, 1H) 6.54 (d, J=5.27 Hz, 1H) 6.86 (s, 1H) 7.33 (m, 2H) 7.44 (d, J=2.45 Hz, 1H) 7.58 (d, J=8.67 Hz, 1H) 7.96 (d, J=2.26 Hz, 1H) 8.26 (d, J=9.04 Hz, 1H) 8.66 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 447.0 (M+H).
Example 69
Preparation of 6-[(7-hydroxyquinolin-4-yl)oxy]-N-isopropyl-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28 using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.02 (d, J=6.59 Hz, 6H) 2.42 (s, 3H) 3.96 (m, 1H) 6.16 (d, J=5.27 Hz, 1H) 7.02 (m, 3H) 7.07 (d, J=2.07 Hz, 1H) 7.41 (d, J=2.07 Hz, 1H) 7.57 (d, J=8.48 Hz, 1H) 7.76 (d, J=7.54 Hz, 1H) 8.00 (d, J=9.04 Hz, 1H) 8.33 (d, J=5.09 Hz, 1H) 10.10 (s, 1H). LC/MS (APCI, pos.): 477.1 (M+H).
Example 70
Preparation of 6-[(7-hydroxyquinolin-4-yl)oxy]-N-isopropyl-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.17 (d, J=6.59 Hz, 6H) 2.57 (s, 3H) 3.30 (s, 3H) 4.14 (m, 1H) 6.35 (d, J=5.27 Hz, 1H) 7.23 (m, 3H) 7.79 (d, J=8.67 Hz, 1H) 7.88 (d, J=2.26 Hz, 1H) 8.16 (d, J=9.04 Hz, 1H) 8.25 (d, J=7.72 Hz, 2H) 8.52 (d, J=5.27 Hz, 1H) 10.31 (s, 1H). LC/MS (APCI, pos.): 393.1 (M+H).
Example 71
Preparation of N-isopropyl-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.27 (d, J=6.41 Hz, 6H) 2.67 (s, 3H) 4.01 (s, 3H) 4.22 (m, 1H) 6.52 (d, J=5.27 Hz, 1H) 7.38 (m, 2H) 7.49 (d, J=2.45 Hz, 1H) 7.89 (d, J=8.67 Hz, 1H) 7.99 (d, J=2.26 Hz, 1H) 8.30 (d, J=9.04 Hz, 1H) 8.35 (d, J=7.91 Hz, 1H) 8.68 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 407.1 (M+H).
General Preparation of the Compounds of Examples 72 to 74
These compounds were prepared according to the reaction scheme depicted below and using methods analogous to those described in connection with Schemes I and IV (described hereinabove).
Example 72
Preparation of N-isopropyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.33 (d, J=6.41 Hz, 6H) 2.74 (s, 3H) 4.36 (m, J=6.41 Hz, 1H) 5.67 (d, J=7.72 Hz, 1H) 6.54 (d, J=4.90 Hz, 1H) 7.16 (dd, J=8.48, 2.07 Hz, 1H) 7.31 (s, 1H) 7.46 (d, J=9.23 Hz, 1H) 7.73 (d, J=8.29 Hz, 1H) 7.95 (s, 1H) 8.45 (d, J=9.04 Hz, 1H) 8.69 (d, J=4.71 Hz, 1H). LC/MS (APCI, pos.): 445.0 (M+H).
Example 73
Preparation of N-cyclopropyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 0.69 (m, 2H) 0.93 (m, J=6.97, 5.46 Hz, 2H) 2.75 (s, 3H) 2.94 (m, 1H) 6.02 (s, 1H) 6.53 (d, J=5.27 Hz, 1H) 7.15 (dd, J=8.48, 2.07 Hz, 1H) 7.31 (d, J=2.07 Hz, 1H) 7.46 (dd, J=9.14, 1.79 Hz, 1H) 7.70 (d, J=8.48 Hz, 1H) 7.95 (s, 1H) 8.45 (d, J=9.04 Hz, 1H) 8.69 (d, J=5.27 Hz, 1H). LC/MS (APCI, pos.): 443.0 (M+H).
Example 74
Preparation of N-butyl-2-methyl-6-{[7-(trifluoromethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.00 (t, J=7.33 Hz, 3H) 1.47 (m, 2H) 1.67 (m, 2H) 3.52 (m, 2H) 5.87 (s, 1H) 6.56 (d, J=4.80 Hz, 1H) 7.16 (dd, J=8.46, 1.89 Hz, 1H) 7.32 (d, J=2.02 Hz, 1H) 7.48 (d, J=9.35 Hz, 1H) 7.75 (d, J=8.34 Hz, 1H) 7.99 (s, 1H) 8.46 (d, J=9.10 Hz, 1H) 8.70 (d, J=4.04 Hz, 1H). LC/MS (APCI, pos.): 459.0 (M+H).
Preparation of Compounds of Example 75 to 77
These compounds were prepared according to the synthetic scheme depicted below and using methods described in connection with Scheme II.
Example 75
Preparation of [(7-methoxyquinolin-4-yl)oxy]-N,1,2-trimethyl-1H-indole-3-carboxamide
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.61 (s, 3H) 2.80 (d, J=4.52 Hz, 3H) 3.67 (s, 3H) 3.93 (s, 3H) 6.36 (d, J=5.27 Hz, 1H) 7.00 (dd, J=8.57, 2.17 Hz, 1H) 7.29 (dd, J=9.14, 2.54 Hz, 1H) 7.40 (d, J=2.45 Hz, 1H) 7.49 (d, J=2.07 Hz, 1H) 7.56 (m, 1H) 7.84 (d, J=8.48 Hz, 1H) 8.26 (d, J=9.04 Hz, 1H) 8.56 (d, J=5.27 Hz, 1H) MS (APCI, m/z) 376.1 (M+1) Anal. (C 22 H 21 N 3 O 3 1.3H 2 O)
Example 76
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-N,1,2-trimethyl-1H-indole-3-carboxamide
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.60 (s, 3H) 2.80 (d, J=4.52 Hz, 3H) 3.67 (s, 3H) 6.27 (d, J=5.27 Hz, 1H) 6.98 (dd, J=8.67, 2.07 Hz, 1H) 7.19 (m, 1H) 7.24 (d, J=2.26 Hz, 1H) 7.47 (d, J=2.26 Hz, 1H) 7.55 (m, J=4.52 Hz, 1H) 7.83 (d, J=8.48 Hz, 1H) 8.21 (d, J=9.04 Hz, 1H) 8.48 (d, J=5.27 Hz, 1H) 10.21 (s, 1H). MS (APCI, m/z) 362.1 (M+1) Anal. (C 21 H 19 N 3 O 3 — 0.7H 2 O)
Example 77
Preparation of N,1,2-trimethyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 2.63 (d, J=4.71 Hz, 2H) 2.65 (d, J=4.52 Hz, 2H) 2.75 (s, 3H) 2.92 (t, J=5.56 Hz, 2H) 3.08 (d, J=4.90 Hz, 3H) 3.67 (s, 3H) 3.76 (d, J=4.71 Hz, 2H) 3.78 (d, J=4.52 Hz, 2H) 4.30 (t, J=5.56 Hz, 2H) 5.89 (m, 1H) 6.39 (d, J=5.27 Hz, 1H) 7.04 (dd, J=8.67, 2.07 Hz, 1H) 7.15 (d, J=1.88 Hz, 1H) 7.25 (dd, J=9, 3 Hz, 1H) 7.42 (d, J=2.45 Hz, 1H) 7.77 (d, J=8.67 Hz, 1H) 8.31 (d, J=9.04 Hz, 1H) 8.56 (d, J=5.27 Hz, 1H) MS (APCI, m/z) 475.1 (M+1) Anal. (C 27 H 30 N 4 O 4 — 0.5H 2 O□0.5 CH 3 COOH)
Example 78
Preparation of N,1,2-trimethyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide
This compound was prepared according to methods analogous for those used to prepare the compounds of Example 75 to Example 77.
1 H NMR (300 MHz, DMSO-d6) δ ppm 1.70 (m, 4H) 2.54 (m, J=6.41 Hz, 4H) 2.60 (s, 3H) 2.80 (d, J=4.52 Hz, 3H) 2.87 (t, J=5.75 Hz, 2H) 3.67 (s, 3H) 4.25 (t, J=5.75 Hz, 2H) 6.35 (d, J=5.27 Hz, 1H) 7.00 (dd, J=8.48, 1.88 Hz, 1H) 7.29 (dd, J=9.14, 2.54 Hz, 1H) 7.40 (d, J=2.26 Hz, 1H) 7.49 (d, J=1.88 Hz, 1H) 7.56 (q, J=4.46 Hz, 1H) 7.84 (d, J=8.67 Hz, 1H) 8.25 (d, J=9.04 Hz, 1H) 8.55 (d, J=5.27 Hz, 1H) MS (APCI, m/z) 459.1 (M+1) Anal. (C 27 H 30 N 4 O 3 — 0.5H 2 O — 1 CH 3 COOH)
Example 79
Preparation of N,1,2-trimethyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1H-indole-3-carboxamide
This compound was prepared according to methods analogous to those used to prepare the compounds of Example 75 to Example 77.
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.49 (m, 2H) 1.76 (s, 4H) 2.68 (s, 3H) 2.80 (s, 4H) 3.01 (d, J=4.90 Hz, 3H) 3.09 (m, 2H) 3.60 (s, 3H) 4.40 (m, 2H) 5.81 (m, 1H) 6.32 (d, J=5.27 Hz, 1H) 6.97 (dd, J=8.76, 1.60 Hz, 1H) 7.08 (s, 1H) 7.16 (d, J=2.07 Hz, 1H) 7.36 (d, J=1.88 Hz, 1H) 7.71 (d, J=8.67 Hz, 1H) 8.25 (d, J=9.23 Hz, 1H) 8.49 (d, J=5.27 Hz, 1H) MS (APCI, m/z) 473.1 (M+1) Anal. (C 28 H 32 N 4 O 3 — 1.25H 2 O — 0.5 CH 3 COOH)
Example 80
Preparation of N-(2-hydroxypropyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.31 (m, 3H) 2.71 (d, J=13.94 Hz, 3H) 3.38 (m, 1H) 3.79 (m, 1H) 3.98 (s, 3H) 4.13 (m, 1H) 6.34 (m, 1H) 6.42 (d, J=5.27 Hz, 1H) 7.22 (m, 2H) 7.44 (d, J=2.45 Hz, 1H) 7.56 (d, J=2.07 Hz, 1H) 8.01 (d, J=8.85 Hz, 1H) 8.26 (d, J=9.23 Hz, 1H) 8.57 (d, J=5.27 Hz, 1H)
Example 81
Preparation of N-(2-hydroxybutyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.05 (t, J=7.44 Hz, 3H) 1.61 (m, 2H) 2.74 (s, 3H) 3.40 (m, 1H) 3.81 (m, J=14.32 Hz, 2H) 3.98 (s, 3H) 6.31 (m, 1H) 6.42 (d, J=5.27 Hz, 1H) 7.22 (m, 2H) 7.43 (d, J=2.45 Hz, 1H) 7.56 (d, J=2.07 Hz, 1H) 8.00 (d, J=8.85 Hz, 1H) 8.26 (d, J=9.04 Hz, 1H) 8.58 (d, J=5.27 Hz, 1H)
Example 82
Preparation of N-(3-hydroxybutyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzothiophene-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 1.29 (d, J=6.41 Hz, 3H) 1.76 (m, 2H) 2.73 (s, 3H) 3.41 (m, 1H) 3.98 (s, 3H) 4.01 (m, 2H) 6.42 (d, J=5.27 Hz, 1H) 6.47 (m, 1H) 7.23 (m, 2H) 7.43 (d, J=2.45 Hz, 1H) 7.56 (d, J=2.07 Hz, 1H) 7.99 (d, J=8.85 Hz, 1H) 8.26 (d, J=9.04 Hz, 1H) 8.58 (d, J=5.27 Hz, 1H)
Example 83
Preparation of 6-{[7-(1,3-dioxolan-2-ylmethoxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.57 (s, 3H) 2.76 (d, J=4.52 Hz, 3H) 3.84 (m, 2H) 3.94 (m, 2H) 4.14 (d, J=3.77 Hz, 2H) 5.24 (m, 1H) 6.38 (d, J=5.09 Hz, 1H) 7.17 (dd, J=8.57, 2.17 Hz, 1H) 7.25 (dd, J=9.04, 2.45 Hz, 1H) 7.37 (d, J=2.26 Hz, 1H) 7.56 (d, J=1.88 Hz, 1H) 7.78 (d, J=8.48 Hz, 1H) 7.92 (d, J=4.33 Hz, 1H) 8.18 (d, J=9.04 Hz, 1H) 8.53 (d, J=5.09 Hz, 1H). LC/MS (APCI, pos.): 435.1 (M+H).
Example 84
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[(2R)-tetrahydrofuran-2-ylmethyl]-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.70 (m, 1H) 1.97 (m, 3H) 2.70 (s, 3H) 3.42 (t, J=5.94 Hz, 2H) 3.73 (m, 1H) 3.87 (m, 1H) 4.01 (s, 3H) 4.09 (m, 1H) 6.51 (d, J=5.31 Hz, 1H) 7.30 (dd, J=8.46, 2.15 Hz, 1H) 7.36 (dd, J=9.10, 2.53 Hz, 1H) 7.48 (d, J=2.53 Hz, 1H) 7.68 (d, J=2.02 Hz, 1H) 7.86 (d, J=8.59 Hz, 1H) 8.19 (t, J=5.94 Hz, 1H) 8.30 (d, J=9.10 Hz, 1H) 8.66 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 433.1 (M+H).
Example 85
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[(2S)-tetrahydrofuran-2-ylmethyl]-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.57 (m, 1H) 1.84 (m, 3H) 2.57 (s, 3H) 3.29 (t, J=5.94 Hz, 2H) 3.60 (m, 1H) 3.74 (m, 1H) 3.88 (s, 3H) 3.96 (m, 1H) 6.38 (d, J=5.31 Hz, 1H) 7.17 (dd, J=8.46, 2.15 Hz, 1H) 7.23 (dd, J=9.09, 2.53 Hz, 1H) 7.35 (d, J=2.53 Hz, 1H) 7.55 (d, J=2.02 Hz, 1H) 7.73 (d, J=8.59 Hz, 1H) 8.06 (t, J=5.68 Hz, 1H) 8.17 (d, J=9.09 Hz, 1H) 8.53 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 433.1 (M+H).
Example 86
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[ethoxy-ethyl]-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.21 (t, J=6.95 Hz, 3H) 2.70 (s, 3H) 3.55 (m, 6H) 4.01 (s, 3H) 6.51 (d, J=5.31 Hz, 1H) 7.30 (dd, J=8.59, 2.02 Hz, 1H) 7.37 (dd, J=9.09, 2.53 Hz, 1H) 7.49 (d, J=2.53 Hz, 1H) 7.69 (d, J=2.02 Hz, 1H) 7.88 (d, J=8.59 Hz, 1H) 8.15 (t, J=5.43 Hz, 1H) 8.31 (d, J=9.09 Hz, 1H) 8.66 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 421.10 (M+H).
Example 87
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-[2-methoxy-1-methyl-ethyl]-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 1.11 (d, J=6.82 Hz, 3H) 2.55 (s, 3H) 3.27 (m, 5H) 3.38 (m, 1H) 3.88 (s, 3H) 4.16 (m, J=14.40, 6.57 Hz, 1H) 6.37 (d, J=5.31 Hz, 1H) 7.17 (dd, J=8.46, 2.15 Hz, 1H) 7.23 (dd, J=9.35, 2.53 Hz, 1H) 7.35 (d, J=2.53 Hz, 1H) 7.55 (d, J=2.02 Hz, 1H) 7.69 (d, J=8.34 Hz, 1H) 7.86 (d, J=8.34 Hz, 1H) 8.17 (d, J=9.09 Hz, 1H) 8.53 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 421.10 (M+H).
Example 88
Preparation of N-(2-methoxyethyl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.46 (s, 3H) 3.13 (s, 3H) 3.32 (m, 4H) 3.77 (s, 3H) 6.27 (d, J=5.31 Hz, 1H) 7.07 (dd, J=8.59, 2.02 Hz, 1H) 7.13 (dd, J=9.35, 2.53 Hz, 1H) 7.25 (d, J=2.53 Hz, 1H) 7.45 (d, J=2.02 Hz, 1H) 7.64 (d, J=8.59 Hz, 1H) 7.93 (t, J=5.05 Hz, 1H) 8.07 (d, J=9.35 Hz, 1H) 8.42 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 407.1 (M+H).
Example 89
Preparation of N-cyclopropyl-2-methyl-6-[(7-pyrimidin-2-ylquinolin-4-yl)oxy]-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 48, 33 and 28, using the appropriate starting materials.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.56 (m, 2H) 0.66 (m, 2H) 2.54 (s, 3H) 2.81 (m, 1H) 6.57 (d, J=4.80 Hz, 1H) 7.22 (m, 1H) 7.48 (m, 1H) 7.61 (d, J=1.52 Hz, 1H) 7.72 (d, J=8.59 Hz, 1H) 8.13 (m, 1H) 8.43 (d, J=9.09 Hz, 1H) 8.60 (d, J=9.60 Hz, 1H) 8.69 (d, J=4.80 Hz, 1H) 8.96 (d, J=4.80 Hz, 2H) 8.98 (m, 1H). LC/MS (APCI, pos.): 437.1 (M+H).
Example 90
Preparation of N-cyclopropyl-2-methyl-6-({7-[2-(methylamino)ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
7-(benzyloxy)-4-chloroquinoline 90-B was prepared (see general synthesis Scheme I) from the commercially available compound 90-A (from Aldrich). A mixture of 90-B (2.8 g, 10.4 mmol), 6-hydroxy-2-methyl-1-benzofuran-3-carboxylic acid 90-C (2 g, 10.4 mmol) and Cs 2 CO 3 (10.1 g, 31.4 mmol) in DMSO (70 ml) was heated to 130° C. for 2 hours. The solution was poured into water, neutralized with AcOH and extracted with EtOAc. The concentrated residue was purified by silica gel chromatography using 2-5% MeOH in CH 2 Cl 2 to give 6-{[7-(benzyloxy)quinolin-4-yl]oxy}-2-methyl-1-benzofuran-3-carboxylic acid 90-D (4.2 g, 94% yield) as a solid.
Compound 90-D (2.4 g) was treated with TFA (net) by refluxing for 2 hours. The solution was cooled to room temperature, poured into water and extracted with EtOAc. The organic layer was washed (brine), dried (MgSO 4 ) and concentrated to give 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylic acid 90-E (1.4 g, 86% yield).
A solution of 90-E (1.6 g, 4.8 mmol), HATU (2.1 g, 5.7 mmol) and triethylamine (970 mg, 9.6 mmol) in DMF (10 ml) was stirred at room temperature for 20 minutes. To the solution was added cyclopropanamine 90-F (547 mg, 9.6 mmol). The reaction mixture was stirred for 30 minutes, poured into water and extracted with EtOAc. Silica gel column chromatography using 5% MeOH in CH 2 Cl 2 yield N-cyclopropyl-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide 90-G (1.4 g, 77% yield) as a solid.
A solution of 90-G (1.4 g, 3.7 mmol), Br(CH 2 ) 2 Br 90-H (2.1 g, 11.2 mmol) and K 2 CO 3 (1.5 g, 11.2 mmol) in DMF (40 ml) was heated to 50° C. overnight. The reaction mixture was extracted with EtOAc. The concentrated residue was purified by silica gel column chromatography using 5% MeOH/CH 2 Cl 2 to yield 6-{[7-(2-bromoethoxy)quinolin-4-yl]oxy}-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide 90-1 (1.1 g, 61%).
A solution of compound 90-1 (100 mg, 0.21 mmol) and 0.3 ml of methylamine 90-J (R′═CH 3 , R′═H) in THF (2N) in DMSO (2 ml) was heated to 60° C. for 1 hour. The reaction mixture was purified by HPLC (Dionex System) using 10-50% CH 3 CN/H 2 O+0.1% AcOH over 30 minutes to give N-cyclopropyl-2-methyl-6-({7-[2-(methylamino)ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide 90 (42 mg).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.55 (m, 2H) 0.65 (m, J=7.07, 4.55 Hz, 2H) 2.30 (s, 3H) 2.53 (s, 3H) 2.80 (m, 1H) 2.84 (t, J=5.56 Hz, 2H) 4.13 (t, J=5.56 Hz, 2H) 6.36 (d, J=5.05 Hz, 1H) 7.14 (dd, J=8.46, 2.15 Hz, 1H) 7.23 (dd, J=9.10, 2.53 Hz, 1H) 7.34 (d, J=2.27 Hz, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.59 Hz, 1H) 8.11 (d, J=4.29 Hz, 1H) 8.16 (d, J=9.35 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 432.1 (M+H).
Example 91
Preparation of N-cyclopropyl-2-methyl-6-({7-[2-(diethylamino)ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.54 (m, 2H) 0.65 (m, 2H) 0.93 (t, J=7.07 Hz, 6H) 2.52 (m, 4H) 2.53 (s, 3H) 2.79 (m, 3H) 4.14 (t, J=6.06 Hz, 2H) 6.35 (d, J=5.05 Hz, 1H) 7.14 (dd, J=8.46, 2.15 Hz, 1H) 7.21 (dd, J=9.10, 2.53 Hz, 1H) 7.34 (d, J=2.53 Hz, 1H) 7.53 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.34 Hz, 1H) 8.11 (d, J=4.04 Hz, 1H) 8.15 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 474.2 (M+H).
Example 92
Preparation of N-cyclopropyl-2-methyl-6-({7-[2-hydroxy-ethoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.55 (m, 2H) 0.65 (m, 2H) 2.53 (s, 3H) 2.81 (d, J=3.79 Hz, 1H) 3.75 (s, 2H) 4.11 (t, J=5.05 Hz, 2H) 4.89 (m, 1H) 6.36 (d, J=5.05 Hz, 1H) 7.15 (dd, J=8.46, 2.15 Hz, 1H) 7.24 (dd, J=9.10, 2.53 Hz, 1H) 7.34 (d, J=2.27 Hz, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.34 Hz, 1H) 8.11 (d, J=3.79 Hz, 1H) 8.16 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 419.1 (M+H).
Example 93
Preparation of 6-{[7-(2-bromoethoxy)quinolin-4-yl]oxy}-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90.
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.54 (m, 2H) 0.65 (m, 2H) 2.53 (s, 3H) 2.80 (m, 1H) 3.84 (m, 2H) 4.47 (m, 2H) 6.38 (d, J=5.31 Hz, 1H) 7.15 (dd, J=8.46, 2.15 Hz, 1H) 7.27 (dd, J=9.09, 2.53 Hz, 1H) 7.38 (d, J=2.53 Hz, 1H) 7.55 (d, J=2.02 Hz, 1H) 7.69 (d, J=8.34 Hz, 1H) 8.12 (d, J=3.79 Hz, 1H) 8.19 (d, J=9.09 Hz, 1H) 8.54 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 481.0 (M+H).
Example 94
Preparation of N-cyclopropyl-2-methyl-6-{7-[2-(4-ethyl-piperazin-1-yl)-ethoxy]quinolin-4-yloxy}-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.43 (m, 2H) 0.53 (m, 2H) 0.80 (t, J=7.20 Hz, 3H) 2.12 (q, J=7.33 Hz, 2H) 2.30 (m, 8H) 2.41 (s, 3H) 2.59 (t, J=5.68 Hz, 2H) 2.68 (m, 1H) 4.07 (t, J=5.56 Hz, 2H) 6.23 (d, J=5.31 Hz, 1H) 7.00 (dd, J=8.59, 2.02 Hz, 1H) 7.09 (dd, J=9.10, 2.53 Hz, 1H) 7.22 (d, J=2.27 Hz, 1H) 7.37 (d, J=2.02 Hz, 1H) 7.56 (d, J=8.34 Hz, 1H) 7.98 (d, J=4.04 Hz, 1H) 8.03 (d, J=9.10 Hz, 1H) 8.39 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 515.2 (M+H).
Example 95
Preparation of N-cyclopropyl-6-({7-[2-(isopropylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) ppm 0.54 (m, 2H) 0.65 (m, 2H) 0.95 (d, J=6.32 Hz, 6H) 2.53 (s, 3H) 2.73 (m, J=12.38, 6.06 Hz, 1H) 2.80 (m, J=7.20, 3.92 Hz, 1H) 2.89 (t, J=5.56 Hz, 2H) 4.12 (t, J=5.56 Hz, 2H) 6.35 (d, J=5.31 Hz, 1H) 7.15 (dd, J=8.59, 2.02 Hz, 1H) 7.24 (dd, J=9.22, 2.40 Hz, 1H) 7.33 (m, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.59 Hz, 1H) 8.12 (d, J=3.79 Hz, 1H) 8.16 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 460.1 (M+H).
Example 96
Preparation of N-cyclopropyl-6-({7-[2-(cyclopropylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d 6 ) ppm 0.02 (m, 2H) 0.16 (m, 2H) 0.37 (m, 2H) 0.47 (m, 2H) 1.94 (m, 1H) 2.36 (s, 3H) 2.64 (m, 1H) 2.79 (t, J=5.68 Hz, 2H) 3.96 (t, J=5.68 Hz, 2H) 6.18 (d, J=5.05 Hz, 1H) 6.98 (dd, J=8.46, 2.15 Hz, 1H) 7.06 (dd, J=9.09, 2.27 Hz, 1H) 7.16 (m, 1H) 7.37 (d, J=2.02 Hz, 1H) 7.51 (d, J=8.34 Hz, 1H) 7.95 (d, J=3.79 Hz, 1H) 7.99 (d, J=9.10 Hz, 1H) 8.35 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 458.1 (M+H).
Example 97
Preparation of N-cyclopropyl-6-[(7-{2-[(2-methoxy-1-methylethyl)amino]ethoxy}quinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 0.54 (m, 2H) 0.65 (m, 2H) 0.91 (d, J=6.57 Hz, 3H) 2.53 (s, 3H) 2.81 (m, 2H) 2.92 (m, 2H) 3.15 (m, 2H) 3.18 (m, 4H) 3.20 (m, 3H) 4.13 (m, 2H) 6.35 (d, J=5.31 Hz, 1H) 7.15 (dd, J=8.46, 2.15 Hz, 1H) 7.23 (dd, J=9.10, 2.53 Hz, 1H) 7.34 (d, J=2.27 Hz, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.34 Hz, 1H) 8.12 (d, J=4.04 Hz, 1H) 8.16 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 490.1 (M+H).
Example 98
Preparation of 6-({7-[2-(tert-butylamino)ethoxy]quinolin-4-yl}oxy)-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) ppm 0.56 (m, 2H) 0.67 (m, 2H) 1.04 (s, 9H) 2.55 (s, 3H) 2.82 (m, 1H) 2.91 (t, J=5.81 Hz, 2H) 4.14 (t, J=5.68 Hz, 2H) 6.37 (d, J=5.31 Hz, 1H) 7.16 (dd, J=8.46, 2.15 Hz, 1H) 7.25 (dd, J=9.10, 2.53 Hz, 1H) 7.35 (d, J=2.53 Hz, 1H) 7.56 (d, J=2.27 Hz, 1H) 7.70 (d, J=8.59 Hz, 1H) 8.14 (d, J=4.04 Hz, 1H) 8.18 (d, J=9.10 Hz, 1H) 8.53 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 474.1 (M+H).
Example 99
Preparation of N-cyclopropyl-2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 1.04 (m, 2H) 1.15 (m, 2H) 3.02 (s, 3H) 3.21 (t, J=5.56 Hz, 2H) 3.30 (m, 1H) 3.76 (m, 4H) 4.03 (m, 4H) 4.71 (t, J=5.68 Hz, 2H) 6.85 (d, J=5.31 Hz, 1H) 7.64 (dd, J=8.46, 2.15 Hz, 1H) 7.72 (dd, J=9.10, 2.53 Hz, 1H) 7.86 (d, J=2.53 Hz, 1H) 8.03 (d, J=2.27 Hz, 1H) 8.18 (d, J=8.34 Hz, 1H) 8.62 (m, 1H) 8.65 (d, J=9.10 Hz, 1H) 9.01 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 488.1 (M+H).
Example 100
Preparation of 6-({7-[2-(cyclobutylamino)ethoxy]quinolin-4-yl}oxy)-N-cyclopropyl-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.54 (m, 2H) 0.65 (m, 2H) 1.56 (m, 4H) 2.05 (m, 2H) 2.53 (s, 3H) 2.81 (t, J=5.68 Hz, 2H) 3.36 (m, 1H) 4.08 (m, J=5.68, 5.68 Hz, 2H) 6.35 (d, J=5.31 Hz, 1H) 7.15 (dd, J=8.46, 2.15 Hz, 1H) 7.23 (dd, J=9.10, 2.53 Hz, 1H) 7.32 (d, J=2.53 Hz, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (d, J=8.59 Hz, 1H) 8.12 (d, J=3.79 Hz, 1H) 8.16 (d, J=9.09 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 472.1 (M+H).
Example 101
Preparation of N-cyclopropyl-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.53 (m, 2H) 0.65 (m, 2H) 1.63 (m, 4H) 2.50 (m, 3H) 2.53 (m, 3H) 2.80 (m, 4H) 4.19 (t, J=5.81 Hz, 2H) 6.36 (d, J=5.31 Hz, 1H) 7.14 (m, 1H) 7.23 (dd, J=9.10, 2.53 Hz, 1H) 7.35 (d, J=2.53 Hz, 1H) 7.54 (d, J=2.02 Hz, 1H) 7.68 (m, 1H) 8.12 (m, 1H) 8.15 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 472.1 (M+H).
Example 102
Preparation of N-cyclopropyl-2-methyl-6-{[7-(2-piperazin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.54 (m, 2H) 0.65 (m, 2H) 2.38 (m, 2H) 2.66 (m, 4H) 2.81 (m, 1H) 3.12 (m, 4H) 4.19 (t, J=5.68 Hz, 2H) 6.36 (d, J=5.31 Hz, 1H) 7.15 (m, 2H) 7.21 (m, 2H) 7.53 (dd, J=7.20, 2.15 Hz, 1H) 7.68 (m, 1H) 8.14 (m, 2H) 8.52 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 487.1 (M+H).
Example 103
Preparation of N-cyclopropyl-6-({7-[2-(ethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.54 (m, 2H) 0.66 (m, 2H) 0.98 (t, J=7.07 Hz, 3H) 2.53 (s, 3H) 2.58 (m, 2H) 2.80 (m, 1H) 2.89 (m, 2H) 4.13 (t, J=5.56 Hz, 2H) 6.35 (d, J=5.31 Hz, 1H) 7.15 (d, J=8.59 Hz, 1H) 7.24 (d, J=8.84 Hz, 1H) 7.34 (s, 1H) 7.54 (s, 1H) 7.68 (d, J=8.34 Hz, 1H) 8.12 (d, J=3.54 Hz, 1H) 8.16 (d, J=9.09 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 446.1 (M+H).
Example 104
Preparation of N-cyclopropyl-2-methyl-6-{[7-(2-piperidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-d6) δ ppm 0.55 (m, 2H) 0.66 (m, J=5.05 Hz, 2H) 1.35 (m, 2H) 1.45 (m, 4H) 2.60 (m, 2H) 2.67 (m, 2H) 2.81 (m, 2H) 4.19 (t, J=5.68 Hz, 2H) 6.36 (d, J=5.31 Hz, 1H) 7.14 (m, 1H) 7.20 (d, J=10.36 Hz, 1H) 7.36 (s, 1H) 7.54 (s, 1H) 7.68 (m, 1H) 8.13 (d, J=9.35 Hz, 1H) 8.15 (d, J=9.10 Hz, 1H) 8.52 (d, J=5.05 Hz, 1H). LC/MS (APCI, pos.): 486.1 (M+H).
Example 105
Preparation of N-cyclopropyl-6-({7-[2-(dimethylamino)ethoxy]quinolin-4-yl}oxy)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, using the appropriate amine in place of methylamine (90-J).
1 H NMR (400 MHz, CD 3 OD) ppm 0.58 (m, 2H) 0.75 (m, 2H) 2.33 (s, 6H) 2.53 (s, 3H) 2.79 (m, 1H) 2.84 (t, J=5.18 Hz, 2H) 4.21 (t, J=5.31 Hz, 2H) 6.40 (d, J=5.31 Hz, 1H) 7.08 (m, 1H) 7.24 (dd, J=9.22, 2.40 Hz, 1H) 7.29 (m, J=8.46, 2.15 Hz, 2H) 8.21 (d, J=9.35 Hz, 1H) 8.42 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 446.1 (M+H).
Example 106
Preparation of 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-{6-[(3-methylbutyl)amino]pyridin-3-yl}-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
To a solution of 2-chloro-5-nitropyridine 106-A and EtN 3 (4.7 g, 46.5 mmol) in CH 3 CN (150 ml) was added N,N-dimethylethlenediamine 106-B (4.1 g, 46.5 mmol). The solution was stirred at room temperature for 3 hours, extracted with EtOAc, washed (brine), dried(MgSO 4 ) and concentrated to give N,N-dimethyl-N′-(5-nitropyridin-2-yl)ethane-1,2-diamine 106-C (5.2 g) as a yellow solid.
Hydrogenation of compound 106-C (5.2 g) (with 10% Pd/C) in EtOH (150 ml) under [H 2 ] (40 psi) at room temperature for 15 hours gave compound 106-D (4.7 g) as dark brown oil.
To a solution of compound 106-D (120 mg) in DMF was added Et 3 N (1.5 eq.) and HATU (1.2 eq.) at room temperature. After being stirred for 10 minutes, to the solution was added 6-[(6-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylic acid 106-E (1.0 eq.) The solution was stirred at room temperature for 30 minutes, extracted with EtOAc, washed (brine) and concentrated. The residue was purified by HPLC (10-40% CH 3 CN/H 2 O, over 30 minutes) to give the title compound 106.
1 H NMR (400 MHz, CHLOROFORM-D) ppm 2.38 (s, 6H) 2.69 (m, 2H) 2.79 (s, 3H) 3.46 (t, J=5.81 Hz, 2H) 3.98 (s, 3H) 6.43 (t, J=5.43 Hz, 1H) 6.50 (d, J=8.84 Hz, 1H) 7.21 (m, 2H) 7.34 (d, J=2.02 Hz, 1H) 7.39 (s, 1H) 7.44 (d, J=2.53 Hz, 1H) 7.79 (m, 2H) 8.17 (d, J=2.27 Hz, 1H) 8.27 (m, 1H) 8.60 (m, 1H). LC/MS (APCI, pos.): 512.1.1 (M+H).
Example 107
Preparation of 6-{[7-(benzyloxy)quinolin-4-yl]oxy}-N-(4,6-dimethylpyridin-2-yl)-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 106, 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, CHLOROFORM-d) δ ppm 2.42 (s, 3H) 2.50 (s, 3H) 2.85 (s, 3H) 5.30 (s, 2H) 6.61 (d, J=6.22 Hz, 1H) 6.85 (s, 1H) 7.22 (dd, J=8.48, 2.26 Hz, 1H) 7.41 (m, 5H) 7.54 (m, 2H) 8.03 (d, J=8.67 Hz, 2H) 8.09 (m, 1H) 8.39 (d, J=9.23 Hz, 1H) 8.59 (d, J=6.22 Hz, 1H). MS (APCI, m/z) 530.1 (M+1) HRMS Calculated Mass for C33H27N3O4 (M+): 530.2075 Observed Mass (M+): 530.2091 Mass Error: 3.08 ppm
Example 108
Preparation of N-(4,6-dimethylpyridin-2-yl)-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 106, 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.31 (s, 3H) 2.39 (s, 3H) 2.68 (s, 3H) 3.93 (s, 3H) 6.46 (d, J=4.33 Hz, 1H) 6.88 (s, 1H) 7.25 (d, J=9.98 Hz, 1H) 7.29 (d, J=8.85 Hz, 1H) 7.41 (s, 1H) 7.65 (s, 1H) 7.80 (d, J=9.61 Hz, 1H) 7.88 (s, 1H) 8.24 (d, J=8.29 Hz, 1H) 8.59 (d, J=4.14 Hz, 1H) 10.46 (s, 1H) MS (APCI, m/z) 454.1 (M+1) HRMS Calculated Mass for C27H23N3O4 (M+): 454.1762 Observed Mass (M+): 454.1769 Mass Error: 1.66 ppm
Example 109
Preparation of N-(4,6-dimethylpyridin-2-yl)-6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Examples 106, 48, 33 and 28, using the appropriate starting materials.
1 H NMR (300 MHz, DMSO-d6) δ ppm 2.32 (s, 3H) 2.40 (s, 3H) 2.70 (s, 3H) 5.75 (s, 1H) 6.56 (s, 1H) 6.78 (d, J=6.59 Hz, 1H) 6.90 (s, 1H) 7.37 (dd, J=8.29, 1.51 Hz, 1H) 7.45 (m, 2H) 7.82 (s, 1H) 7.88 (d, J=6.03 Hz, 2H) 8.48 (d, J=8.85 Hz, 1H) 8.85 (d, J=6.59 Hz, 1H) 10.56 (s, 1H) MS (APCI, m/z) 440.1 (M+1) HRMS Calculated Mass for C26H21N3O 4 (M+): 440.1605 Observed Mass (M+): 440.1617 Mass Error: 2.89 ppm
Example 110
Preparation of N,2-dimethyl-6-({7-[(2-oxo-1,3-dioxolan-4-yl)methoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 6-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 110-A (500 mg, 1.43 mmol), 2-(bromomethyl)oxirane (286 mg, 2.1 mmol) and K 2 CO 3 (386 mg, 2.8 mmol) in DMF (15 mL) was stirred at 90° C. for 3 h. The mixture was then extracted with EtOAc. The concentrated residue was purified by silica gel column chromatography using 0-5% MeOH/CH 2 Cl 2 to give N,2-dimethyl-6-({7-[(2-oxo-1,3-dioxolan-4-yl)methoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide 110 (323 mg).
1 H NMR (400 MHz, CHLOROFORM-D) d ppm 2.75 (s, 3H) 3.08 (d, J=4.80 Hz, 3H) 4.33 (dd, J=10.86, 3.54 Hz, 1H) 4.47 (m, 1H) 4.61 (dd, J=8.59, 6.06 Hz, 1H) 4.69 (t, J=8.59 Hz, 1H) 5.16 (m, J=8.34, 5.81 Hz, 1H) 5.88 (s, 1H) 6.49 (d, J=5.31 Hz, 1H) 7.16 (dd, J=8.59, 2.02 Hz, 1H) 7.31 (m, 2H) 7.55 (d, J=2.02 Hz, 1H) 7.76 (m, 1H) 8.34 (d, J=9.10 Hz, 1H) 8.62 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 449.1 (M+H).
Example 111
Preparation of 7-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
The first step of the reaction was carried out according to Scheme II discussed previously to yield 7-{[7-(benzyloxy)quinolin-4-yl]oxy}-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide 111-C. Following the addition of TFA and reflux, 7-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide 111 was obtained.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.50 (s, 3H) 2.79 (d, J=4.55 Hz, 3H) 6.75 (d, J=5.31 Hz, 1H) 6.98 (dd, J=7.58, 2.53 Hz, 1H) 7.19 (dd, J=9.10, 2.27 Hz, 1H) 7.25 (d, J=2.27 Hz, 1H) 7.37 (d, J=2.02 Hz, 1H) 7.73 (q, J=4.38 Hz, 1H) 8.10 (d, J=9.10 Hz, 1H) 8.62 (d, J=5.31 Hz, 1H) 9.08 (d, J=7.58 Hz, 1H) 10.55 (s, 1H). LC/MS (ACPI, pos.): 349.1 (M+H).
Note that 7-hydroxy-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide 111-B was obtained by the following procedure. To a solution of 4-methoxypyridin-2-amine (prepared as in Org. Prep. & Proc. Int., 29, 1, 117-122, 1997) 2.8 g, 22.6 mmol in ethanol (100 ml) was added ethyl 2-chloro-3-oxobutanoate (6.2 ml, 45.2 mmol) and the resulting solution heated to reflux for 16 hours under a nitrogen atmosphere. The solvents were removed in-vacuo and the yellow solid was titrated with dichloromethane to extract the crude product. The dichloromethane extracts were concentrated and purified by flash chromatography (eluting with ethyl acetate) to yield ethyl 7-methoxy-2-methylimidazo[1,2-α]pyridine-3-carboxylate, 2 g, 38%, as a yellow solid.
1 H NMR 400 MHz (CDCl 3 ) δ 9.10 (1H, d, J=7.7 Hz), 6.87 (1H, d, J=2.5 Hz), 6.64 (1H, dd, J=2.7, 7.8 Hz), 4.39 (2H, q, J=7.0 Hz), 3.87 (3H, s), 2.65 (3H, s), 1.41 (3H, t, J=7.2 Hz). APCI (pos) m/z: 235.1 [MH+].
To a solution of ethyl 7-methoxy-2-methylimidazo[1,2-α]pyridine-3-carboxylate (1.8 g, 7.7 mmol) in THF (100 ml) and MeOH (50 ml) was added aq. NaOH (11.5 ml, 2M, 23.1 mmol) and the resulting emulsion heated to reflux for 2 hours. A further aliquot of NaOH was then added (3.8 ml, 2M, 7.7 mmol) and the resulting mixture heated for a further 2 hours. The solvents were removed in-vacuo and the residue was acidified with 1.5 N HCl to pH 3, and the resulting solid was filtered off, washed with water and dried in vacuo to yield 7-methoxy-2-methylimidazo[1,2-α]pyridine-3-carboxylic acid, 1.2 g, 76%, as an off white solid.
1 H NMR 400 MHz (DMSO D 6 ) δ 12.76 (1H, bs), 9.02 (1H, d, J=7.7 Hz), 6.99 (1H, d, J=2.5 Hz), 6.76 (1H, dd, J=2.6, 7.5 Hz), 3.82 (3H, s), 2.45 (3H, s). APCI pos) m/z: 207.1 [MH+].
To a stirred solution of 7-methoxy-2-methylimidazo[1,2-α]pyridine-3-carboxylic acid (1.2 g, 5.82 mmol) in DMF (25 ml) was added EDCl (1.23 g, 6.41 mmol), HOBt (0.87 g, 6.41 mmol), N-methyl morpholine (767 ul, 11.64 mmol), methylamine (2M in THF, 6 ml, 11.64 mmol) and DMAP (70 mg, 0.58 mmol) sequentially, and the resulting mixture stirred at ambient temperature for 16 hours. The resulting solution was concentrated in-vacuo and pre-absorbed onto SiO 2 and then purified by flash chromatography (eluting with 5-8% MeOH/DCM) to yield 7-Methoxy-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide, 1.11 g, 87%, as a white solid.
1 H NMR 400 MHz (CDCl 3 ) δ 9.23 (1H, d, J=7.9 Hz), 6.84 (1H, d, J=2.5 Hz), 6.59 (1H, dd, J=2.5, 7.5 Hz), 5.70 (1H, bs), 3.86 (3H, s), 3.03 (3H, d, J=4.8 Hz), 2.64 (3H, s). APCI m/z: 220.1 [MH+].
To a solution of 7-methoxy-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide (985 mg, 4.49 mmol) in DMF (20 ml) was added sodium thioethylate (80% pure, 1.86 g, 18 mmol) and the mixture heated to 120° C. for 2 hours. After cooling to ambient temperature, the reaction was neutralized to pH 6 with 1N HCl and concentrated in vacuo. The residue was dissolved in MeOH/H 2 O, pre-absorbed onto SiO 2 , and purified by flash chromatography (eluting with 90/10/1-80/20/5, DCM/MeOH/cNH 3 ) to yield the crude product as a yellow solid, which was titrated with MeOH to yield 7-hydroxy-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide 111-B, 700 mg, 78%, as a pale yellow solid.
1 H NMR 400 MHz (DMSO d 6 ) δ 10.44 (1H, bs), 8.88 (1H, d, J=7.6 Hz), 7.46 (1H, d, J=4.6 Hz), 6.66 (1H, d, J=2.0 Hz), 6.60 (1H, dd, J=2.5, 7.3 Hz), 2.80 (3H, d, J=4.6 Hz), 2.46 (3H, s). APCI m/z: 206.1 [MH+].
Example 112
Preparation of N,2-dimethyl-7-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}imidazo[1,2-α]pyridine-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
Note that 7-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethylimidazo[1,2-α]pyridine-3-carboxamide 112-A was prepared according to Example 111.
1 H NMR (400 MHz, DMSO-d6) δ ppm 2.49 (s, 3H) 2.70 (m, 2H) 2.78 (d, J=4.80 Hz, 3H) 3.54 (m, 4H) 4.23 (m, 2H) 6.75 (d, J=5.05 Hz, 1H) 6.95 (dd, J=7.58, 2.53 Hz, 1H) 7.24 (dd, J=9.10, 2.53 Hz, 1H) 7.31 (d, J=2.53 Hz, 1H) 7.41 (d, J=2.02 Hz, 1H) 7.70 (d, J=4.55 Hz, 1H) 8.07 (d, J=9.09 Hz, 1H) 8.62 (d, J=5.31 Hz, 1H) 9.07 (d, J=7.58 Hz, 1H). LC/MS (PCPI, pos.): 462.2 (M+H).
Example 113
Preparation of 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(6-morpholin-4-ylpyridin-3-yl)-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
2-fluoro-3-methoxyphenol 113-A, which was prepared in a similar manner to a published procedure (Bioorg. Med. Chem. Lett.; EN; 10; 18; 2000; 2115-2118), was dissolved in anhydrous THF (75 mL) to which NaH (3.8 g, 95.0 mmol) was added and stirred for 0.5 h at 0° C. Next, 3-bromo-2-oxopropanoic acid 113-B was added to the reaction mixture. Note that 3-bromo-2-oxopropanoic acid was prepared according to a published procedure (J. Biol. Chem.; 164; 1946; 437) except that NBS was used in place of bromine. The reaction mixture was then stirred for 1.5 h. The solution was diluted with 100 mL with EtOAc and partitioned between H 2 O (50 mL). The aqueous layer was neutralized with 3N HCl to about a pH of about 2, after which 100 mL of EtOAc was added and extracted with supplementary EtOAc (2×50 mL). The combined organic layers were dried over Na 2 SO 4 and concentrated to give 3-(2-fluoro-3-methoxyphenoxy)-2-oxobutanoic acid 113-C.
The residue was taken up in 50 mL of CH 2 Cl 2 and MSA (2.0 mL, 30.4 mmol) and stirred for 10 h. H 2 O (50 mL) was then added to the solution and partitioned with EtOAc (50 mL) followed by concentration of the organic layer. The crude product was then dissolved in 20 mL of diethyl ether (20 mL) and n-heptane (50 mL) was added to the mixture to give 7-fluoro-6-methoxy-2-methyl-1-benzofuran-3-carboxylic acid 113-D (1.86 g, 28%) as a white solid. HPLC: R t 3.76 min. (95% area).
1 H NMR (DMSO-d 3 , 400 MHz) δ: 13.12 (1H, bs), 7.62 (1H, d, J=8.8 Hz), 7.23, (1H, t, J=8.4 Hz), 3.93 (3H, s), 2.75 (3H, s). LRMS (ESI) (M+H + ) m/z: 223.1.
Dissolved 113-D (0.78 g, 3.49 mmol) in CH 2 Cl 2 (10 mL) and cooled to 0° C. BBr 3 (7.0 mL, 7.0 mmol, 1.0 M in CH 2 Cl 2 ) was then added to the solution in a drop-wise fashion and stirred for 1 hour with a precipitate forming. The reaction was diluted with H 2 O (20 mL) and filtered to yield 7-fluoro-6-hydroxy-2-methyl-1-benzofuran-3-carboxylic acid 113-E (0.65 g, 89%) as a tan solid. HPLC: R t 3.17 min. (98% area).
1 H NMR (DMSO-d 3 , 400 MHz) δ: 13.01 (1H, bs), 10.01 (1H, bs), 7.44 (1H, d, J=8.8 Hz), 6.95, (1H, t, J=8.4 Hz), 2.08 (3H, s). LRMS (ESI) (M+H + ) m/z: 209.2.
4-chloro-7-methoxyquinoline 113-F (prepared according to Scheme I described previously) was then added according to Scheme II described previously to yield 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylic acid 113-G. 6-morpholin-4-ylpyridin-3-amine 113-H, which is commercially available from BIONET, was then added according to Scheme IV(iii) to yield the final product 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(6-morpholin-4-ylpyridin-3-yl)-1-benzofuran-3-carboxamide 113.
1 H NMR (DMSO-d 3 , 400 MHz) δ: 10.05 (1H, s), 8.56 (1H, d, J=5.3 Hz), 8.40 (1H, s), 8.22 (1H, d, J=9.1 Hz), 7.86 (1H, dd, J=9.0, 1.9 Hz), 7.60 (1H, d, J=8.6 Hz), 7.38-7.34 (2H, m), 7.28 (1H, dd, J=9.1, 2.5 Hz), 6.83 (1H, d, J=9.1 Hz), 6.43 (1H, d, J=5.1 Hz), 3.89 (3H, s), 3.65 (4H, t, J=5.0 Hz), 3.34 (4H, t, J=5.0 Hz), 2.66 (3H, s). HRMS (ESI) C 29 H 26 FN 4 O 5 (M+H + ) m/z: Calc. 529.1887. Found: 529.1888. Anal. (C 29 H 26 FN 4 O 5 1.0H 2 O) Calc'd: C, 63.73; H, 4.98; N, 10.25. Found: C, 63.49; H, 4.75; N, 9.94.
Example 114
Preparation of 7-fluoro-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-N-(3-morpholin-4-ylpropyl)-1-benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 113, but where the appropriate amine (commercially available from ALDRICH) was added in place of 113-H.
1 H NMR (DMSO-d 3 , 400 MHz) δ: 1 H NMR (DMSO-d 3 , 400 MHz) δ: 8.62 (1H, d, J=5.3 Hz), 8.30 (1H, d, J=9.1 Hz), 8.20 (1H, t, J=5.6 Hz), 7.64 (1H, d, J=8.6 Hz), 7.46-7.39 (2H, m), 7.34 (1H, dd, J=9.4, 2.5 Hz), 6.50 (1H, d, J=5.1 Hz), 3.96 (3H, s), 3.58 (4H, t, J=4.3 Hz), 3.46-3.30 (4H, m), 2.68 (3H, s), 2.61 (4H, t, J=6.6 Hz). HRMS (ESI) C 27 H 29 FN 3 O 5 (M+H + ) m/z: Calc. 494.2091. Found: 494.2103. Anal. (C 27 H 28 FN 3 O 5 1.2H 2 O) Calc'd: C, 62.95; H, 5.95; N, 8.16. Found: C, 62.59; H, 5.56; N, 8.09.
Example 115
Preparation of N-cyclopropyl-2-methyl-6-{[7-(2-piperazin-1-ylethoxy)quinolin-4-yl]oxy}-1 benzofuran-3-carboxamide
This compound was prepared using methods analogous to those depicted and described in Example 90, where the appropriate amine (commercially available from ALDRICH) was used in place of methylamine (90-J).
1 H NMR (400 MHz, DMSO-D6) d ppm 0.54 (m, 2H) 0.65 (m, 2H) 2.38 (m, 2H) 2.66 (m, 4H) 2.81 (m, 1H) 3.12 (m, 4H) 4.19 (t, J=5.68 Hz, 2H) 6.36 (d, J=5.31 Hz, 1H) 7.15 (m, 2H) 7.21 (m, 2H) 7.53 (dd, J=7.20, 2.15 Hz, 1H) 7.68 (m, 1H) 8.14 (m, 2H) 8.52 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 487.1 (M+H).
Example 116
Preparation of 6-{[7-(2,3-dihydroxypropoxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
120 mg of N,2-dimethyl-6-({7-[(2-oxo-1,3-dioxolan-4-yl)methoxy]quinolin-4-yl}oxy)-1-benzofuran-3-carboxamide 116-A (as prepared in Example 110) was treated with 20% NaOH (0.5 mL) in MeOH (2 mL) at room temperature for 1 h. The solution was then extracted with EtOAc. The concentrated residue was purified by HPLC using 10-40% CH 3 CN/H 2 O over 30 min. to give 6-{[7-(2,3-dihydroxypropoxy)quinolin-4-yl]oxy}-N,2-dimethyl-1-benzofuran-3-carboxamide 116.
1 H NMR (400 MHz, DMSO-D6) δ ppm 2.57 (s, 3H) 2.76 (d, J=4.55 Hz, 3H) 3.44 (t, J=5.56 Hz, 2H) 3.82 (m, 1H) 3.98 (dd, J=10.11, 6.32 Hz, 1H) 4.13 (dd, J=10.11, 4.04 Hz, 1H) 4.68 (t, J=5.68 Hz, 1H) 4.99 (d, J=5.05 Hz, 1H) 6.37 (d, J=5.31 Hz, 1H) 7.16 (dd, J=8.46, 2.15 Hz, 1H) 7.24 (dd, J=9.10, 2.53 Hz, 1H) 7.33 (d, J=2.53 Hz, 1H) 7.56 (d, J=2.02 Hz, 1H) 7.78 (d, J=8.34 Hz, 1H) 7.92 (m, 1H) 8.17 (d, J=9.09 Hz, 1H) 8.52 (d, J=5.31 Hz, 1H). LC/MS (APCI, pos.): 423.0 (M+H).
Example 117
Preparation of N-[5-(aminomethyl)pyridin-2-yl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
To a solution of 6-aminonicotinonitrile 117-A (5.0 g, 42 mmol) was added a solution of 1 M BH 3 -THF (294 mL, 294 mmol) at 0° C. (prepared as in J. Org. Chem., Vol. 38, No. 5, 1973). The reaction was stirred at room temperature for 1 hour. The reaction mixture was then slowly pored into ice water. 100 mL 4N HCl was added and stirred for 20 min. The solution was basified with NH 4 OH to pH of about 11, and then concentrated. THF (300 mL×2) was added to the mixture followed by addition of solid KOH (excess). The suspension was stirred. The THF layer was collected by filtration and concentrated to give 5-(aminomethyl)pyridin-2-amine 117-B (4.3 g).
A solution of 117-B (4 g, 32.5 mmol), (Boc) 2 O (7 g, 32.5 mmol) and Et 3 N (6.5 g, 64.5 mmol) in THF (150 mL) was stirred at room temperature overnight. 2.1 g of tert-butyl (6-aminopyridin-3-yl)methylcarbamate 117-C was isolated by silica gel chromatography (0-5% MeOH/CH 2 Cl 2 ).
117-C was coupled with 6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylic acid 117-D (as prepared in Scheme II discussed previously). After work up the mixture was treated with 50% TFA in CH 2 Cl 2 to give N-[5-(aminomethyl)pyridin-2-yl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide 117-E.
1 H NMR (400 MHz, DMSO-D6) δ ppm 2.65 (s, 3H) 3.93 (d, J=10.61 Hz, 3H) 4.02 (q, J=5.56 Hz, 2H) 6.70 (d, J=6.32 Hz, 1H) 7.30 (dd, J=8.59, 2.02 Hz, 1H) 7.47 (m, 2H) 7.75 (d, J=2.02 Hz, 1H) 7.81 (d, J=8.34 Hz, 1H) 7.89 (dd, J=8.59, 2.27 Hz, 1H) 8.17 (m, 4H) 8.39 (m, 1H) 8.79 (d, J=6.06 Hz, 1H) 10.74 (s, 1H). LC/MS (APCI, pos.): 455.1 (M+H).
Example 118
Preparation of N-[6-(aminomethyl)pyridin-3-yl]-6-[(7-methoxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxamide
This compound was prepared according to methods analogous to those depicted and described in Example 117 using appropriate starting materials.
1 H NMR (400 MHz, DMSO-D6) δ ppm 2.65 (d, J=8.84 Hz, 3H) 3.94 (s, 3H) 4.13 (m, 2H) 6.65 (d, J=6.06 Hz, 1H) 7.31 (dd, J=8.46, 2.15 Hz, 1H) 7.45 (m, 3H) 7.76 (d, J=2.02 Hz, 1H) 7.86 (d, J=8.59 Hz, 1H) 8.15 (dd, J=8.34, 2.53 Hz, 1H) 8.22 (m, 2H) 8.36 (d, J=9.10 Hz, 1H) 8.78 (d, J=6.06 Hz, 1H) 8.91 (d, J=2.53 Hz, 1H) 10.41 (s, 1H) LC/MS (APCI, pos.): 455.1 (M+H).
Example 119
Preparation of 4-{[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}butanoic acid
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 6-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 119-A (200 mg, 0.57 mmol), methyl 4-bromobutanoate (155 mg, 0.85 mmol), and Cs 2 CO 3 (433 mg, 1.14 mmol) in a mixed solvent of CH 3 CN (4 mL)/DMF (1 mL) was heated to 65° C. overnight. The reaction mixture was extracted with EtOAc, concentrated and dissolved in 5 mL of MeOH. To the solution was added 1N NaOH (1 mL). The solution was stirred at room temperature for 2 hours and then heated to 60° C. for 2 hours. The solution was acidified with AcOH to a pH of about 6 and extracted with EtOAc. The concentrated residue was purified by HPLC using 20-60% CH 3 CN/H 2 O over 30 min. to give 4-{[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}butanoic acid 119.
1 H NMR (400 MHz, DMSO-D6) δ ppm 2.27 (m, 2H) 2.69 (t, J=7.20 Hz, 2H) 2.88 (s, 3H) 3.06 (d, J=4.55 Hz, 2H) 4.42 (t, J=6.44 Hz, 2H) 6.67 (d, J=5.31 Hz, 1H) 7.47 (dd, J=8.46, 2.15 Hz, 1H) 7.53 (dd, J=9.22, 2.40 Hz, 1H) 7.63 (d, J=2.53 Hz, 1H) 7.86 (d, J=2.27 Hz, 1H) 8.08 (d, J=8.34 Hz, 1H) 8.22 (d, J=4.55 Hz, 1H) 8.47 (d, J=9.10 Hz, 1H) 8.82 (d, J=5.31 Hz, 1H) 12.41 (s, 1H). LC/MS (APCI, pos.): 435.1 (M+H).
Example 120
Preparation of {[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}acetic acid
This compound was prepared according to methods analogous to those depicted and described in Example 119, except that methyl 2-bromoethanoate is used instead of methyl 4-bromobutanoate.
1 H NMR (400 MHz, CHLOROFORM-D) δ ppm 2.72 (s, 3H) 3.04 (d, J=4.04 Hz, 2H) 4.85 (s, 2H) 6.56 (m, 1H) 7.15 (dd, J=8.59, 2.02 Hz, 1H) 7.32 (d, J=2.02 Hz, 1H) 7.39 (m, 1H) 7.47 (dd, J=9.35, 2.27 Hz, 1H) 7.55 (d, J=2.27 Hz, 1H) 7.83 (d, J=8.34 Hz, 1H) 8.38 (m, 1H) 8.54 (m, 1H). LC/MS (APCI, pos.): 407.0 (M+H).
Example 121
Preparation of N-(4,6-dimethylpyridin-2-yl)-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of methyl 6-{[7-(benzyloxy)quinolin-4-yl]oxy}-2-methyl-1-benzofuran-3-carboxylate 121-C (9.38 g) in TFA (100 ml) was heated to reflux for 2 hours. TFA was removed by evaporation under vacuum. The residue was extracted with EtOAC, washed (sat. NaCl), dried over MgSO 4 and concentrated. Methyl 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylate 121-D (6.4 g) was purified by silica gel chromatography using 5% MeOH in CH 2 Cl 2 .
To a solution of methyl 6-[(7-hydroxyquinolin-4-yl)oxy]-2-methyl-1-benzofuran-3-carboxylate 121-D (2.4 g, 7.2 mmol) in DMF (20 ml) was added K 2 CO 3 (5 g, 35.8 mmol) and dibromoethane (2.7 g, 14.3 mmol). The reaction mixture was stirred at room temperature overnight. Column chromatography gave methyl 6-{[7-(2-bromoethoxy)quinolin-4-yl]oxy}-2-methyl-1-benzofuran-3-carboxylate 121-E (1.5 g). A solution of compound 121-E (750 mg) and pyrrolidine (351 mg) in DMF (3 ml) was heated to 60° C. for 45 min. The reaction mixture was extracted with EtOAc. Methyl 2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxylate 121-F (110 mg) was purified by silica gel chromatography using 5-10% MeOH/CH 2 Cl 2 . Compound 121-F (110 mg) was treated with 20% NaOH (1 ml) in MeOH (1 ml) overnight. The reaction mixture was acidified with AcOH and extracted with EtOAc. The residue was purified by silica gel chromatography using 0-10% MeOH in CH 2 Cl 2 to give 2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxylic acid 121-G (100 mg).
A solution of 121-G (43 mg), 4,6-dimethylpyridin-2-amine (25 mg), HATU (132 mg) and Et 3 N (47 mg) in DMF (2 ml) was heated to 70° C. for 4 hours. A small amount of product was seen by TLC. The reaction was allowed to stay for another 48 hours at room temperature. The reaction mixture was purified by HPLC (20-60% CH 3 CN/H 2 O, 0.1% AcOH over 30 min.) to give N-(4,6-dimethylpyridin-2-yl)-2-methyl-6-{[7-(2-pyrrolidin-1-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide 121.
1 H NMR (400 MHz, CHLOROFORM-D) δ ppm 1.87-1.97 (m, 4H) 2.38 (s, 3H) 2.45 (s, 3H) 2.82 (s, 3H) 2.79-2.89 (m, 4H) 3.08-3.20 (m, 2H) 4.35 (t, 2H) 6.45 (d, J=5.31 Hz, 1H) 6.80 (s, 1H) 7.21 (dd, J=8.46, 2.15 Hz, 1H) 7.29 (dd, 1H) 7.33 (d, J=2.02 Hz, 1H) 7.43 (d, J=2.53 Hz, 1H) 7.91 (d, J=8.34 Hz, 1H) 8.00 (s, 1H) 8.28 (d, J=9.35 Hz, 2H) 8.60 (d, J=5.31 Hz, 1H) LCMS: (APCI) m/z (M+1) 537.1 HRMS (Observed) 537.2492 (Calculated) 537.2497. Mass Error −0.92 ppm
Example 122
Preparation of methyl 2-methyl-6-{[7-(2-morpholin-4-ylethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxylate
This compound was prepared according to the synthetic scheme depicted and described below.
1 H NMR (400 MHz, CHLOROFORM-D) δ ppm 2.77-2.82 (m, 3H) 2.82-2.95 (m, 3H) 3.03-3.18 (m, 3H) 3.82-3.94 (m, 4H) 3.95-4.01 (m, 3H) 4.42-4.55 (m, 2H) 6.54 (d, J=5.81 Hz, 1H) 7.16 (dd, J=8.59, 2.02 Hz, 1H) 7.30 (d, J=2.53 Hz, 1H) 7.36 (d, J=4.55 Hz, 1H) 7.73 (s, 1H) 8.06 (d, J=8.59 Hz, 1H) 8.35 (d, J=9.35 Hz, 1H) 8.57 (d, J=6.06 Hz, 1H) LCMS: (APCI) m/z (M+1) 463.1
Example 123
Preparation of 6-({7-[2-hydroxy-3-(methylamino)propoxy]quinolin-4-yl}oxy)-N,2-dimethyl-1-benzofuran-3-carboxamide
This compound was prepared according to the synthetic scheme depicted and described below.
A solution of 6-[(7-hydroxyquinolin-4-yl)oxy]-N,2-dimethyl-1-benzofuran-3-carboxamide 123-A (1 g, 2.9 mmol), 2-(bromomethyl)oxirane (467 mg, 3.4 mmol) and Cs 2 CO 3 (1.4 g, 4.2 mmol) in CH 3 CN (25 ml) was heated to 65° C. for 3 hours. The solution was extracted with EtOAc. N,2-dimethyl-6-{[7-(oxiran-2-ylmethoxy)quinolin-4-yl]oxy}-1-benzofuran-3-carboxamide 123-B (1.1 g) was isolated by a silica gel column using 1-5% MeOH in CH 2 Cl 2 . To a solution of 123-B (150 mg, 0.35 mmol) in THF (5 ml) was added a solution of methylamine in MeOH (1N, 1 ml). The solution was heated to 65° C. for 2 hours. The crude product was purified by HPLC (10-40% CH 3 CN/H 2 O over 30 min.) to give 6-({7-[2-hydroxy-3-(methylamino)propoxy]quinolin-4-yl}oxy)-N,2-dimethyl-1-benzofuran-3-carboxamide 123.
1 H NMR (400 MHz, Solvent) δ ppm 1.80 (s, 3H) 2.56 (s, 3H) 2.88 (s, 3H) 3.03 (m, 2H) 3.21 (m, 3H) 4.10 (m, 2H) 4.22 (m, 1H) 6.42 (m, 1H) 7.09 (dd, J=8.46, 2.15 Hz, 1H) 7.28 (m, 3H) 7.74 (d, J=8.59 Hz, 1H) 8.23 (m, 1H) 8.44 (d, J=5.31 Hz, 1H). LC/MS (ACPI, pos.): 436.1 (M+H).
Example 124
Preparation of methyl 4-{[4-({2-methyl-3-[(methylamino)carbonyl]-1-benzofuran-6-yl}oxy)quinolin-7-yl]oxy}butanoate
This compound was prepared according to the synthetic scheme depicted and described below.
1 H NMR (400 MHz, DMSO-D6) δ ppm 2.03 (m, 2H) 2.49 (t, J=7.20 Hz, 2H) 2.59 (s, 3H) 2.76 (d, J=4.55 Hz, 3H) 3.56 (s, 3H) 4.17 (t, J=6.19 Hz, 2H) 6.62 (d, J=6.06 Hz, 1H) 7.24 (dd, J=8.59, 2.02 Hz, 1H) 7.40 (d, J=11.87 Hz, 1H) 7.41 (s, 1H) 7.66 (d, J=1.77 Hz, 1H) 7.83 (d, J=8.34 Hz, 1H) 7.93 (m, 1H) 8.34 (d, J=8.84 Hz, 1H) 8.72 (d, J=6.06 Hz, 1H). LC/MS (ACPI, pos.): 450.1 (M+H).
Example 125
Preparation of 7-Methoxy-4-(2-methyl-benzofuran-6-yloxy)-quinoline
This compound was prepared according to the synthetic scheme described below.
To a stirred solution of 6-Methoxy-2-methyl-benzofuran 125-A (1.76 g, 10.85 mmol) in 45 ml of CH 2 Cl 2 at −5° C. was added BBr 3 (24 ml of 1M BBr 3 in CH 2 Cl 2 , 16.28 mmol). The reaction was allowed to warm to 0° C. and stirred at that temperature for 1.5 hr. The reaction was poured into a mixture of ice and saturated aqueous NaHCO 3 and layers were separated. The aqueous layer was re-extracted with CH 2 Cl 2 . The combined organic layers were dried (MgSO 4 ) and concentrated under reduced pressure to a brown oil. The residue was chromatographed on silica gel eluting CH 2 Cl 2 to give 872 mg (54%) of 6-Hydroxy-2-methyl-benzofuran 125-B. Anal calc'd for C 9 H 8 O 2 : C, 72.96; H, 5.44. Found: C, 72.72; H, 5.43.
1 H NMR (400 MHz, DMSO-D6) ppm 9.31 (s, 1H) 7.24 (d, J=8.34 Hz, 1H) 6.81 (d, J=1.77 Hz, 1H) 6.64 (dd, J=8.34, 2.02 Hz, 1H) 6.38 (s, 1H) 2.35 (s, 3H).
To a degassed solution of 4-Chloro-7-methoxy-quinoline 125-C (76 mg, 0.39 mmol) and 6-Hydroxy-2-methyl-benzofuran 125-B (58 mg, 0.39 mmol) in 1.5 ml of dmso, was added Cesium Carbonate (320 mg, 0.98 mmol). The reaction mixture was heated at 130° C. for 1.5 hr, cooled, poured into saturated aqueous NaCl solution, and extracted with EtOAc and Et 2 O. The combined extracts washed again with saturated aqueous NaCl solution, dried (MgSO 4 ), and concentrated under reduced pressure. The residue was chromatographed on silica gel eluting a gradient of 9% to 10% of EtOAc in CH 2 Cl 2 . In this manner 7-Methoxy-4-(2-methyl-benzofuran-6-yloxy)-quinoline 125 was prepared as a yellow solid (70 mg, 58%).
1 H NMR (400 MHz, DMSO-D6) δ ppm 8.57 (d, J=5.05 Hz, 1H) 8.23 (d, J=9.35 Hz, 1H) 7.62 (d, J=8.34 Hz, 1H) 7.52 (d, J=1.77 Hz, 1H) 7.40 (d, J=2.53 Hz, 1H) 7.28 (dd, J=9.09, 2.53 Hz, 1H) 7.11 (dd, J=8.34, 2.02 Hz, 1H) 6.65 (s, 1H) 6.41 (d, J=5.31 Hz, 1H) 3.93 (s, 3H) 2.46 (s, 3H). The biological activity of this compound (125) is indicated by the following assay results: FLVK: 68% inhibition @ 1 μM; FGF: 32% inhibition @ 1 μM. See also the results shown in Table 1.
Example 126
Preparation of 4-(2-Methyl-benzofuran-6-yloxy)-7-(2-morpholin-4-yl-ethoxy)-quinoline
This compound was prepared according to the scheme described below.
Using the general procedure shown in Example 125, using 6-Hydroxy-2-methyl-benzofuran 126-A and 7-Benzyloxy-4-chloro-quinoline 126-B, 7-Benzyloxy-4-(2-methyl-benzofuran-6-yloxy)-quinoline 126-C was prepared in 82% yield.
1 H NMR (400 MHz, DMSO-D6) δ ppm 8.56 (d, J=5.31 Hz, 1H) 8.24 (d, J=9.35 Hz, 1H) 7.62 (d, J=8.34 Hz, 1H) 7.46-7.57 (m, 4H) 7.42 (t, J=7.33 Hz, 2H) 7.29-7.39 (m, 2H) 7.11 (dd, J=8.46, 2.15 Hz, 1H) 6.64 (s, 1H) 6.42 (d, J=5.31 Hz, 1H) 5.31 (s, 2H) 2.45 (s, 3H).
A solution of 7-Benzyloxy-4-(2-methyl-benzofuran-6-yloxy)-quinoline 126-C (349 mg, 0.91 mmol) in TFA (1.5 ml) was heated to reflux for 2 hr. The volatiles were removed under reduced pressure, the residue dissolved in EtOAc, and washed sequentially with saturated aqueous NaHCO 3 then brine. The organic layer was dried (MgSO 4 ) and concentrated under reduced pressure. The residue was triturated with TBME and used without further purification in the next step.
A suspension of 4-(2-Chloro-ethyl)-morpholine hydrochloride (153 mg, 0.82 mmol) and Cesium Carbonate (537 mg, 1.65 mmol) in CH 3 CN (2 ml) was stirred at room temperature for 1 hr. The 4-(2-Methyl-benzofuran-6-yloxy)-quinolin-7-ol 126-D (120 mg, 0.41 mmol) in CH 3 CN (2 ml) was added and the reaction was heated to reflux for 2 hr. The bright yellow reaction was cooled, poured into brine, and extracted with EtOAc (2 times). The combined organic layers were washed with brine, dried (MgSO 4 ), and concentrated under reduced pressure. The residue was chromatographed on silica gel eluting with 10% MeOH in EtOAc/CH 2 Cl 2 (1:1). This gave slightly impure material which was re-purified by HPLC to give 110 mg (42%) of 4-(2-Methyl-benzofuran-6-yloxy)-7-(2-morpholin-4-yl-ethoxy)-quinoline 126 as the bis TFA salt.
1 H NMR (400 MHz, DMSO-D6) δ ppm 9.77-10.27 (broad s, 2H) 8.85 (none, 1H) 8.76 (d, J=5.56 Hz, 1H) 8.42 (d, J=9.09 Hz, 1H) 7.68 (d, J=8.34 Hz, 1H) 7.56 (d, J=2.27 Hz, 1H) 7.47 (d, 1H) 7.17 (dd, J=8.34, 2.02 Hz, 1H) 6.61-6.73 (m, 2H) 4.60 (d, J=4.29 Hz, 2H) 3.06-4.18 (m, 10H) 2.38-2.49 (m, 3H).
The biological activity of this compound (126) is indicated by the following assay results: FLVK: Ki=32 nM; FGF: 38% inhibition @ 1 μM.
Biological Testing—Enzyme Assays
The stimulation of cell proliferation by growth factors such as VEGF, FGF, and others is dependent upon their induction of autophosphorylation of each of their respective receptor's tyrosine kinases. Therefore, the ability of a protein kinase inhibitor to block cellular proliferation induced by these growth factors is directly correlated with its ability to block receptor autophosphorylation. To measure the protein kinase inhibition activity of the compounds, the following constructs were devised.
(i) VEGF-R2 Construct for Assay:
This construct determines the ability of a test compound to inhibit tyrosine kinase activity. A construct (VEGF-R2D50) of the cytosolic domain of human vascular endothelial growth factor receptor 2 (VEGF-R2) lacking the 50 central residues of the 68 residues of the kinase insert domain was expressed in a baculovirus/insect cell system. Of the 1356 residues of full-length VEGF-R2, VEGF-R2D50 contains residues 806-939 and 990-1171, and also one point mutation (E990V) within the kinase insert domain relative to wild-type VEGF-R2. Autophosphorylation of the purified construct was performed by incubation of the enzyme at a concentration of 4 mM in the presence of 3 mM ATP and 40 mM MgCl 2 in 100 mM HEPES, pH 7.5, containing 5% glycerol and 5 mM DTT, at 4° C. for 2 h. After autophosphorylation, this construct has been shown to possess catalytic activity essentially equivalent to the wild-type autophosphorylated kinase domain construct. See Parast et al., Biochemistry, 37, 16788-16801 (1998).
(ii) FGF-R1 Construct for Assay:
The intracellular kinase domain of human FGF-R1 was expressed using the baculovirus vector expression system starting from the endogenous methionine residue 456 to glutamate 766, according to the residue numbering system of Mohammadi et al., Mol. Cell. Biol., 16, 977-989 (1996). In addition, the construct also has the following 3 amino acid substitutions: L457V, C488A, and C584S.
Example A
VEGF-R2 Assay
Coupled Spectrophotometric (FLVK-P) Assay
The production of ADP from ATP that accompanies phosphoryl transfer was coupled to oxidation of NADH using phosphoenolpyruvate (PEP) and a system having pyruvate kinase (PK) and lactic dehydrogenase (LDH). The oxidation of NADH was monitored by following the decrease of absorbance at 340 nm (e 340 =6.22 cm −1 mM −1 ) using a Beckman DU 650 spectrophotometer. Assay conditions for phosphorylated VEGF-R2D50 (indicated as FLVK-P in the tables below) were the following: 1 mM PEP; 250 mM NADH; 50 units of LDH/mL; 20 units of PK/mL; 5 mM DTT; 5.1 mM poly(E 4 Y 1 ); 1 mM ATP; and 25 mM MgCl 2 in 200 mM HEPES, pH 7.5. Assay conditions for unphosphorylated VEGF-R2D50 (indicated as FLVK in the tables) were the following: 1 mM PEP; 250 mM NADH; 50 units of LDH/mL; 20 units of PK/mL; 5 mM DTT; 20 mM poly(E 4 Y 1 ); 3 mM ATP; and 60 mM MgCl 2 and 2 mM MnCl 2 in 200 mM HEPES, pH 7.5. Assays were initiated with 5 to 40 nM of enzyme. K i values were determined by measuring enzyme activity in the presence of varying concentrations of test compounds. The percent inhibition at 50 nM (% inhibition @ 50 nM) was determined by linear least-squares regression analysis of absorbance as a function of time. The binding inhibitions were fitted to equation as described by Morrison. The data were analyzed using Enzyme Kinetic and Kaleidagraph software.
Example B
FGF-R Assay
The spectrophotometric assay was carried out as described above for VEGF-R2, except for the following changes in concentration: FGF-R=50 nM, ATP=2 mM, and poly(E4Y1)=15 mM.
Example C
HUVEC+VEGF Proliferation Assay
This assay determines the ability of a test compound to inhibit the growth factor-stimulated proliferation of human umbilical vein endothelial cells (“HUVEC”). HUVEC cells (passage 3-4, Clonetics, Corp.) were thawed into EGM2 culture medium (Clonetics Corp) in T75 flasks. Fresh EGM2 medium was added to the flasks 24 hours later. Four or five days later, cells were exposed to another culture medium (F12K medium supplemented with 10% fetal bovine serum (FBS), 60 mg/mL endothelial cell growth supplement (ECGS), and 0.1 mg/mL heparin). Exponentially-growing HUVEC cells were used in experiments thereafter. Ten to twelve thousand HUVEC cells were plated in 96-well dishes in 100 ml of rich, culture medium (described above). The cells were allowed to attach for 24 hours in this medium. The medium was then removed by aspiration and 105 ml of starvation media (F12K+1% FBS) was added to each well. After 24 hours, 15 ml of test agent dissolved in 1% DMSO in starvation medium or this vehicle alone was added into each treatment well; the final DMSO concentration was 0.1%. One hour later, 30 ml of VEGF (30 ng/mL) in starvation media was added to all wells except those containing untreated controls; the final VEGF concentration was 6 ng/mL. Cellular proliferation was quantified 72 hours later by MTT dye reduction, at which time cells were exposed for 4 hours MTT (Promega Corp.). Dye reduction was stopped by addition of a stop solution (Promega Corp.) and absorbance at 595 nm was determined on a 96-well spectrophotometer plate reader.
Example D
Mouse PK Assay
The pharmacokinetics (e.g., absorption and elimination) of drugs in mice were analyzed using the following experiment. Test compounds were formulated as a suspension in a 30:70 (PEG 400: acidified H 2 O) vehicle. This solution was administered orally (p.o.) and intraperitoneally (i.p.) at 50 mg/kg to two distinct groups (n=4) of B6 female mice. Blood samples were collected via an orbital bleed at time points: 0 hour (pre-dose), 0.5 hr, 1.0 hr, 2.0 hr, and 4.0 hr post dose. Plasma was obtained from each sample by centrifugation at 2500 rpm for 5 min. Test compound was extracted from the plasma by an organic protein precipitation method. For each time bleed, 50 μL of plasma was combined with 1.0 mL of acetonitrile, vortexed for 2 min. and then spun at 4000 rpm for 15 min. to precipitate the protein and extract out the test compound. Next, the acetonitrile supernatant (the extract containing test compound) was poured into new test tubes and evaporated on a hot plate (25° C.) under a steam of N 2 gas. To each tube containing the dried test compound extract, 125 μL of mobile phase (60:40, 0.025 M NH 4 H 2 PO 4 +2.5 mL/L TEA:acetonitrile) was added. The test compound was resuspended in the mobile phase by vortexing and more protein was removed by centrifugation at 4000 rpm for 5 min. Each sample was poured into an HPLC vial for test compound analysis on an Hewlett Packard 1100 series HPLC with UV detection. From each sample, 95 μL was injected onto a Phenomenex-Prodigy reverse phase C-18, 150×3.2 mm column and eluted with a 45-50% acetonitrile gradient run over 10 min. Test-compound plasma concentrations (μg/mL) were determined by a comparison to standard curve (peak area vs. conc. μg/mL) using known concentrations of test compound extracted from plasma samples in the manner described above. Along with the standards and unknowns, three groups (n=4) of quality controls (0.25 μg/mL, 1.5 μg/mL, and 7.5 μg/mL) were run to insure the consistency of the analysis. The standard curve had an R 2 >0.99 and the quality controls were all within 10% of their expected values. The quantitated test samples were plotted for visual display using Kalidagraph software and their pharmacokinetic parameters were determined using WIN NONLIN software.
Example E
Human Liver Microsome (HLM) Assay
Compound metabolism in human liver microsomes was measured by LC-MS analytical assay procedures as follows. First, human liver microsomes (HLM) were thawed and diluted to 5 mg/mL with cold 100 mM potassium phosphate (KPO 4 ) buffer. Appropriate amounts of KPO 4 buffer, NADPH-regenerating solution (containing B-NADP, glucose-6-phosphate, glucose-6-phosphate dehydrogenase, and MgCl 2 ), and HLM were preincubated in 13×100 mm glass tubes at 37° C. for 10 min. (3 tubes per test compound—triplicate). Test compound (5 μM final) was added to each tube to initiate reaction and was mixed by gentle vortexing, followed by incubation at 37° C. At t=0, and 2 h, a 250-uL sample was removed from each incubation tube to separate 12×75 mm glass tubes containing 1 mL ice-cold acetonitrile with 0.05 μM reserpine. Samples were centrifuged at 4000 rpm for 20 min. to precipitate proteins and salt (Beckman Allegra 6KR, S/N ALK98D06, #634). Supernatant was transferred to new 12×75 mm glass tubes and evaporated by Speed-Vac centrifugal vacuum evaporator. Samples were reconstituted in 200 μL 0.1% formic acid/acetonitrile (90/10) and vortexed vigorously to dissolve. The samples were then transferred to separate polypropylene microcentrifuge tubes and centrifuged at 14000×g for 10 min. (Fisher Micro 14, S/N M0017580). For each replicate (#1-3) at each timepoint (0 and 2 h), an aliquot sample of each test compound was combined into a single HPLC vial insert (6 total samples) for LC-MS analysis, which is described below.
The combined compound samples were injected into the LC-MS system, composed of a Hewlett-Packard HP1100 diode array HPLC and a Micromass Quattro II triple quadruple mass spectrometer operating in positive electrospray SIR mode (programmed to scan specifically for the molecular ion of each test compound). Each test compound peak was integrated at each timepoint. For each compound, peak area at each timepoint (n=3) was averaged, and this mean peak area at 2 h was divided by the average peak area at time 0 hour to obtain the percent test compound remaining at 2 h.
Example F
KDR (VEGFR2) Phosphorylation in PAE-KDR Cells Assay
This assay determines the ability of a test compound to inhibit the autophosphorylation of KDR in porcine aorta endothelial (PAE)-KDR cells. PAE cells that overexpress human KDR were used in this assay. The cells were cultured in Ham's F12 media supplemented with 10% fetal bovine serum (FBS) and 400 μg/mL G418. Thirty thousands cells were seeded into each well of a 96-well plate in 75 mL of growth media and allowed to attach for 6 hours at 37° C. Cells were then exposed to the starvation media (Ham's F12 media supplemented with 0.1% FBS) for 16 hours. After the starvation period was over, 10 mL of test agent in 5% DMSO in starvation media were added to the test wells and 10 mL of the vehicle (5% DMSO in starvation media) were added into the control wells. The final DMSO concentration in each well was 0.5%. Plates were incubated at 37° C. for 1 hour and the cells were then stimulated with 500 ng/ml VEGF (commercially available from R & D System) in the presence of 2 mM Na 3 VO 4 for 8 minutes. The cells were washed once with 1 mm Na 3 VO 4 in HBSS and lysed by adding 50 mL per well of lysis buffer. One hundred mL of dilution buffer were then added to each well and the diluted cell lysate was transferred to a 96-well goat ant-rabbit coated plate (commercially available from Pierce) which was pre-coated with Rabbit anti Human Anti-flk-1 C-20 antibody (commercially available from Santa Cruz). The plates were incubated at room temperature for 2 hours and washed seven times with 1% Tween 20 in PBS. HRP-PY20 (commercially available from Santa Cruz) was diluted and added to the plate for a 30-minute incubation. Plates were then washed again and TMB peroxidase substrate (commercially available from Kirkegaard & Perry) was added for a 10-minute incubation. One hundred mL of 0.09 N H 2 SO 4 was added to each well of the 96-well plates to stop the reaction. Phosphorylation status was assessed by spectrophotometer reading at 450 nm. IC 50 values were calculated by curve fitting using a four-parameter analysis.
Example G
PAE-PDGFRb Phosphorylation in PAE-PDGFRB Cells Assay
This assay determines the ability of a test compound to inhibit the autophosphorylation of PDGFRb in porcine aorta endothelial (PAE)-PDGFRb cells. PAE cells that overexpress human PDGFRb were used in this assay. The cells were cultured in Ham's F12 media supplemented with 10% fetal bovine serum (FBS) and 400 ug/ml G418. Twenty thousands cells were seeded in each well of a 96-well plate in 50 mL of growth media and allowed to attach for 6 hours at 37° C. Cells were then exposed to the starvation media (Ham's F12 media supplemented with 0.1% FBS) for 16 hours. After the starvation period was over, 10 mL of test agent in 5% DMSO in starvation media were added to the test wells and 10 mL of the vehicle (5% DMSO in starvation media) were added into the control wells. The final DMSO concentration in each well was 0.5%. Plates were incubated at 37° C. for 1 hour and the cells were then stimulated with 1 mg/mL PDGF-BB (R & D System) in the presence of 2 mM Na 3 VO 4 for 8 minutes. The cells were washed once with 1 mm Na 3 VO 4 in HBSS and lysed by adding 50 mL per well of lysis buffer. One hundred mL of dilution buffer were then added to each well and the diluted cell lysate was transferred to a 96-well goat ant-rabbit coated plate (Pierce), which was pre-coated with Rabbit anti Human PDGFRb antibody (Santa Cruz). The plates were incubated at room temperature for 2 hours and washed seven times with 1% Tween 20 in PBS. HRP-PY20 (Santa Cruz) was diluted and added to the plate for a 30-minute incubation. Plates were then washed again and TMB peroxidase substrate (Kirkegaard & Perry) was added for a 10-minute incubation. One hundred mL of 0.09 N H 2 SO 4 was added into each well of the 96-well plate to stop the reaction. Phosphorylation status was assessed by spectrophotometer reading at 450 nm. IC 50 values were calculated by curve fitting using a four-parameter analysis.
The results of the testing of the compounds using various assays are summarized in Table 1.
FLVK Ki (nM)
A = >10 nm
B = 1-10 nm
C = <1 nm
HUVEC + VEGF
Example
NT = Not tested
IC50 (nM) AVG
1
NT
NT
2
NT
NT
3
NT
NT
4
NT
NT
6
B
B
7
C
NT
8
C
C
9
C
B
10
B
B
11
B
C
12
A
Nt
13
C
B
14
B
B
15
B
NT
16
A
NT
17
NT
NT
18
A
NT
19
B
B
20
A
NT
21
NT
NT
22
NT
NT
23
A
NT
24
B
NT
25
NT
NT
26
NT
NT
27
A
NT
28
NT
B
29
C
B
30
C
NT
31
B
C
32
NT
B
33
B
NT
34
C
B
35
NT
C
36
B
C
37
B
C
38
B
C
39
NT
C
40
NT
C
41
NT
B
42
NT
C
43
NT
B
44
B
C
45
B
B
46
B
C
47
B
C
48
B
B
49
A
NT
50
B
B
51
A
B
52
B
B
53
B
B
54
A
NT
55
A
NT
56
A
NT
57
A
NT
58
NT
NT
59
NT
NT
60
A
NT
61
A
NT
62
NT
A
63
NT
C
64
NT
B
65
NT
NT
66
A
B
67
B
B
68
NT
NT
69
NT
B
70
NT
NT
71
B
NT
72
NT
NT
73
B
B
74
NT
NT
75
A
NT
76
A
NT
77
A
NT
78
A
NT
79
A
NT
80
A
NT
81
A
NT
82
A
NT
83
C
NT
84
B
B
85
A
NT
86
B
B
87
A
NT
88
B
B
89
C
NT
90
C
NT
91
C
Nt
92
C
NT
93
C
NT
94
C
NT
95
C
NT
96
C
NT
97
C
NT
98
C
NT
99
NT
NT
100
NT
B
101
NT
NT
102
NT
NT
103
NT
NT
104
NT
NT
105
NT
NT
106
NT
NT
107
NT
NT
108
NT
B
109
NT
A
110
NT
NT
111
NT
NT
112
NT
NT
113
NT
NT
114
NT
NT
115
NT
NT
116
NT
NT
117
NT
NT
118
NT
NT
119
NT
NT
120
NT
NT
121
NT
NT
122
NT
NT
123
NT
NT
124
NT
NT
125
NT
NT
126
A
NT
Examples of Pharmaceutical Formulations
The pharmaceutical composition may, for example, be in a form suitable for oral administration as a tablet, capsule, pill, powder, sustained release formulations, solution, suspension, for parenteral injection as a sterile solution, suspension or emulsion, for topical administration as an ointment or cream or for rectal administration as a suppository. The pharmaceutical composition may be in unit dosage forms suitable for single administration of precise dosages. The pharmaceutical composition will include a conventional pharmaceutical carrier or excipient and a compound according to the invention as an active ingredient. In addition, it may include other medicinal or pharmaceutical agents, carriers, adjuvants, etc. Exemplary parenteral administration forms include solutions or suspensions of active compounds in sterile aqueous solutions, for example, aqueous propylene glycol or dextrose solutions. Such dosage forms can be suitably buffered, if desired.
Suitable pharmaceutical carriers include inert diluents or fillers, water and various organic solvents. The pharmaceutical compositions may, if desired, contain additional ingredients such as flavorings, binders, excipients and the like. Thus for oral administration, tablets containing various excipients, such as citric acid may be employed together with various disintegrants such as starch, alginic acid and certain complex silicates and with binding agents such as sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often useful for tableting purposes. Solid compositions of a similar type may also be employed in soft and hard filled gelatin capsules. Preferred materials, therefor, include lactose or milk sugar and high molecular weight polyethylene glycols. When aqueous suspensions or elixirs are desired for oral administration the active compound therein may be combined with various sweetening or flavoring agents, coloring matters or dyes and, if desired, emulsifying agents or suspending agents, together with diluents such as water, ethanol, propylene glycol, glycerin, or combinations thereof.
Methods of preparing various pharmaceutical compositions with a specific amount of active compound are known, or will be apparent, to those skilled in this art. For examples, see Remington's Pharmaceutical Sciences , Mack Publishing Company, Easter, Pa., 15th Edition (1975).
The exemplary compounds described above may be formulated into pharmaceutical compositions according to the following general examples.
Example I
Parenteral Composition
To prepare a parenteral pharmaceutical composition suitable for administration by injection, 100 mg of a water-soluble salt of a compound of Formula I is dissolved in DMSO and then mixed with 10 mL of 0.9% sterile saline. The mixture is incorporated into a dosage unit form suitable for administration by injection.
Example II
Oral Composition
To prepare a pharmaceutical composition for oral delivery, 100 mg of a compound of Formula I is mixed with 750 mg of lactose. The mixture is incorporated into an oral dosage unit for, such as a hard gelatin capsule, which is suitable for oral administration.
It is to be understood that the foregoing description is exemplary and explanatory in nature, and is intended to illustrate the invention and its preferred embodiments. Through routine experimentation, the artisan will recognize apparent modifications and variations that may be made without departing from the spirit of the invention. Thus, the invention is intended to be defined not by the above description, but by the following claims and their equivalents. | The invention relates to compounds represented by Formula (I):
and to pharmaceutically acceptable salts or solvates of said compounds, wherein each of A, R 3-8 , X 3 , X 5 , m, and n are defined herein. The invention also relates to pharmaceutical compositions containing the compounds of Formula (I) and to methods of treating hyperproliferative disorders in a mammal by administering compounds of Formula (I). | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to German Patent Application No. DE 10 2006 038 103.3 filed on Aug. 14, 2006, the contents of which is incorporated in its entirety herein by reference.
BACKGROUND
The present invention relates to devices for injecting, dispensing, administering, delivering or infusing substances, and to methods of making and using such devices. More particularly, the present invention relates to such devices comprising one or more of the following components or features: a rod or rod-like member which may be threaded and thought of or referred to as a plunger rod; a real-time display for displaying various quantities of a substance, e.g., the quantity to be injected or dispensed, the quantity available for dispensing, the quantity dispensed, etc.; a mechanical lock for use prior to mixing an ampoule, possibly a 2-chamber ampoule; a guide for the rod or rod-like member; and a claw lock.
In some embodiments of injection devices, to set or select the quantity of a substance to dispensed, a setting movement is performed on a setting element. The setting element may be a dose setting knob or a dose setting ring and the setting movement may be a rotating or turning movement of the knob or ring wherein the extent of the rotation, in other words, a rotation or rotational angle, defines what quantity of substance will be dispensed from the injection device in an injection operation. In the case of injection devices designed to dispense a fixed and possibly pre-set quantity of a substance, for example, fixed-dose injection pens, the setting movement may be effected to prime the device for dispensing a pre-defined dose.
SUMMARY
One object of the present invention is to provide for the robust and simple setting or selection of a dose or quantity of a substance to be injected or delivered from an injection device.
In one embodiment, the present invention comprises a rod or rod-like member for use in an injection device. In some embodiments, the rod or rod-like member is threaded and designed to be able to assume predefined fixed rotated positions. Catch elements associated with the device are able to engage with the threaded rod and thus establish a coupling between the threaded rod and the injection device or with a setting element of the device. The catch elements may comprise snapper or engagement elements pre-tensioned elastically and/or radially inwardly or outwardly. In some embodiments, the threaded rod has longitudinally extending engagement regions, grooves or channels which interrupt the thread on the external face of the rod so that it assumes a cross-section in the form of a star, for example, with three, four or alternatively more than four, for example five or six, points and/or webs.
In one embodiment, a sturdy, easy-to-sense and simple setting of a predefined fixed dose is enabled by providing a threaded rod of a cruciform design with four points, for example. The rod can be rotated into only four defined and stable rotated positions. In the stable rotated positions, one or more engaging elements which are suitably arranged around the rod depending on its shape engage in the grooves or webs between the points and hold the rod in one of the positions. Rotating the threaded rod by only 90°, 180°, 270° and other multiples of 90° causes the threaded rod to assume stable and defined rotated positions.
In some embodiments, the threaded rod may be designed so that at least in the region of the grooves or axially or longitudinally extending engagement regions, the outer or peripheral regions of the threaded rod are provided with a slight chamfer. Thus, the engaging elements, which are radially pre-tensioned toward the rod and advantageously permit a rotation of the rod in one direction due to a sliding movement across the chamfered regions and block a rotation in the locking or opposite direction by engaging in the engagement regions, can be easily disengaged when the threaded rod is rotated opposite the locking direction and are pushed out of or can be pushed out of the engagement regions so that they are guided across the chamfered outer regions into the adjacent engagement region. Providing a chamfer at the outer regions means that a point or web of the threaded rod between two grooves or engagement regions has a higher and a lower face, in which case the higher face is disposed on the side from which the engagement element no longer has to be pushed out to move across the chamfered outer region so that the rotation of the threaded rod can be blocked by the engagement element. The smaller face, on the other hand, makes it easier to turn the threaded rod further because the engagement element only has to be pushed along the smaller face to the chamfered region to permit a rotation of the threaded rod. In some embodiments, the engagement elements may be provided with a ramp, which is of a design matching the ramp of the peripheral region of the threaded rod, for example, and which facilitates or enables an outward pushing movement of the engagement element due to a rotating movement in a releasing direction.
In some embodiments, the threaded rod has a wider portion at the proximal or rear end, such as a circumferentially extending ring or radially projecting web or area, from which at least one engagement element projects in the distal or forward direction. The at least one engagement element may take the form of one or more webs, for example, suitable to engage and/or lock with matching co-operating elements after the threaded rod has been fully pushed in. The engagement of the complementary or co-operating elements blocks any further rotating movement of the threaded rod or the dose setting element relative to the injection device and the injection device can therefore no longer be used.
In another embodiment, the present invention comprises an injection device comprising a rod or rod-like element as described above.
In some embodiments, a dose setting element is advantageously provided on the injection device, such as a dose setting knob or a rotating knob for example, which may be connected to other elements such as a rotating sleeve or rotating element, for example. The dose to be dispensed can be set by the dose setting element, and/or the injection device may be primed and the dose set. In some preferred embodiments, a rotating movement of the dose setting element tautens a spring element such as a torsion spring for example, which stores the energy for the subsequent injection and forward drive of the threaded rod and releases it when a trigger element is operated. A rotating sleeve connected to the dose setting element and/or the dose setting element itself has at least one and, in some embodiments, at least two engagement elements lying opposite one another and pre-tensioned radially inwardly for example. The engagement elements are able to engage in co-operating engagement regions of the threaded rod and permit a rotating movement of the threaded rod relative to the rotating sleeve or to the dose setting element in one direction. When the rotating sleeve or the dose setting element is rotated in the opposite direction, the engagement elements remain engaged with the threaded rod and drive it with them so that the energy stored in the torsion spring due to the setting movement can be converted into a rotating movement of the threaded rod.
In some embodiments, at least one engagement element pre-tensioned radially outwardly is also provided on the rotating sleeve or dose setting element, and is able to engage in a window or a groove or recess of the injection device for example, thereby holding or locking the rotating sleeve or the dose setting element in a predefined rotated position after setting the dose or priming the injection device. The element used for locking purposes may be released again by a release button for example, and when the release button is operated, the engagement element pre-tensioned radially outwardly is pushed back in a direction oriented radially inwardly for example, so that the rotating sleeve or the dose setting element is no longer coupled with the injection device and a rotating movement is possible.
In some embodiments, integrated as part of the injection device, fixedly connected to the injection device or provided as a separate element, the injection device comprises at least one guide element, which has an elastic retaining element which is pre-tensioned radially inwardly for example. The guide element is able to engage in at least one engagement region of the threaded rod to permit a rotating movement of the threaded rod in one direction relative to the injection device and block it in the other direction. The guide element also has an internal thread, which may also comprise one or more partial thread segments. This internal thread or the partial thread segments may be designed so that they have several contact faces, as is the case with the thread illustrated in accompanying FIG. 9 for example, thereby permitting a thread engagement for threads of different pitches. For example, the thread segments may be designed so that different threaded rods with a different external thread of a different pitch can be reliably guided between a minimum pitch defined by first contact faces of the internal thread and by a maximum pitch defined by second faces of the internal thread. This, for example, makes it possible to set different doses by the same rotating movement depending on the substance to be administered by using threaded rods with an external thread of a different pitch.
In some embodiments, the injection device has engagement elements or claws to establish a claw coupling with co-operating engagement elements or claws of the threaded rod. The engagement elements of the injection device may be provided on a surface of a rotating sleeve pointing in the proximal direction, a guide sleeve or the injection device itself.
By virtue of another aspect of the present invention, the invention comprises an injection device with a transmission element, which is coupled with a dispensing element such as a plunger rod or a threaded rod of the injection device and which can be coupled with a display element for use with an ampoule which can be inserted in the injection device.
When using injection devices, it is of advantage to provide a display, on which data relating to the doses already administered or doses still contained in the injection device or about the current dispensing operation can be read. However, problems can occur if this display is not functioning correctly because a user might wrongly assume that the injection device contains a bigger quantity of substance than is actually the case.
Therefore, one objective of the present invention is to provide a display, and an injection device comprising the display, which permits a reliable display of a quantity of substance or dose.
In one embodiment, display element in accordance with the present invention for displaying an administering parameter, such as a quantity of a substance still contained in an injection device or already dispensed from an ampoule inserted in the injection device, is coupled as far as possible directly with a dispensing element of the injection device, for example with a plunger rod or threaded rod which drives a stopper into an ampoule or into a reservoir. Coupling the display element as far as possible directly with the drive element means that there are no or few intermediate elements which can cause errors or are susceptible to errors. This enables a robust and reliable display to be provided directly, which may be used to display a remaining quantity or as a real-time display. In terms of administering parameters, the display element may also display the administering or dispensing time, thereby enabling a user to check the dispensing time, or the dispensing time may be stored and used for evaluation purposes, for example.
In some preferred embodiments, the display element is connected to the dispensing element directly, in which case it is connected to it so that it is not able to move or rotate relative to it, and has a marking on an external face in the circumferential direction and/or longitudinal direction for displaying the dose, which can be read through a window or by a marking past which the display element can be moved by sliding or rotating it.
Alternatively, the display element may be coupled with the driving or dispensing element, in other words not directly connected to it, in which case the coupling is achieved by a thread engagement or other movement or a force-transmitting mechanism, such as a screw, a gear, a gear mechanism, link, etc. For example, the display element may have a thread and, if the display element is provided in the form of a sleeve, an internal thread, which engages in an external thread of a plunger rod or threaded rod so that the display element mounted in the injection device cannot move axially but can be rotated. Thus, the display element is rotated directly by rotating or displacing the threaded rod or plunger rod and, on rotation, a reading can be taken from printed information on the external face of the display element about the dose that was dispensed or is still available in conjunction with a scale which does not rotate. In the situation where a thread engagement is used, the thread is advantageously of a design that is not retained by friction so that the display element can simply be rotated and the display element does not obstruct a dose priming or dispensing movement.
In some embodiments, the display element may advantageously be provided not on an injection device but on an ampoule which is inserted in the injection device, which is not coupled with a coupling element of the injection device until or after it is fitted in the injection device, and a movement of a stopper of the ampoule can be converted into a corresponding movement of the display element, thereby providing a real-time display.
By virtue of another aspect of the present invention, the invention comprises an injection device with a display element of the type outlined above.
In some embodiments, the injection device advantageously has at least one orifice, for example a viewing window, where a reading can be taken from a marking of the display element on an external face of the display element fitted in the injection device.
To mount the display element so that it can not be displaced in translation but is able to rotate, an annular groove or an annular web may be provided on the injection device for example, in which a matching co-operating element such as an annular web or an annular groove of the display element engages.
The injection device may be designed so that the display element can be moved inside the injection device, for example when an ampoule is fitted, in which case the display of the display element can not be read from a window when no ampoule is fitted and a colour code on the peripheral face of the display element indicates that there is no ampoule fitted. It is only when or after an ampoule is inserted due to an ampoule inserting operation, for example, that the display element is moved relative to a reading position, for example a viewing window, that the display or print on the display element becomes visible. The display element may be disposed entirely or only partially inside the ampoule.
By virtue of another aspect, the present invention relates to a method of securing a mechanism, e.g., securing a setting mechanism or a setting element of an injection device to prevent it from being operated. In one embodiment, the invention comprises an operating or anti-rotation lock to prevent the setting element from being rotated, in which case the lock can be released by inserting an ampoule in the injection device.
If an injection device is used in which an ampoule must be inserted in the injection device before it can be used, such as a 2-chamber ampoule which must be inserted and mixed directly before use, problems can occur if a user of the injection device proceeds with a setting or operating procedure before inserting the ampoule.
Thus, another object of the present invention is to provide a mechanical lock and an injection device incorporating such a mechanical lock which increases reliability during the operating sequence of an injection device in which an ampoule has to be inserted.
In one embodiment, an injection device in accordance with the present invention has a housing and an operating element mounted in the housing or connected to or coupled with the housing. For the purpose of the invention, the operating element, which might be a setting knob, a knob which has to be depressed or a rotating knob, is mounted in the housing or coupled with or connected to the housing so that the operating element is held by a first retaining connection in a first position by reference to the housing of the injection device, for example is prevented from being moved axially. This being the case, the retaining connection is designed so that it is released as or after an ampoule is fitted or inserted or pushed in so that the operating element is moved into a second retaining position which is axially offset from the first retaining position in the proximal direction, where it is retained by a second retaining connection. In some embodiments, the operating element is moved relative to the housing of the injection device when the ampoule is fitted or pushed in, in other words is pushed out of the injection device in the proximal direction. However, the injection device may be designed so that a coupling or a coupling element is provided, which is moved when the ampoule is inserted so that it moves into abutment with a proximal ampoule edge and thus releases the operating element. This being the case, the actual operating element may remain stationary relative to the injection device or may also be moved.
In some preferred embodiments, the operating element or coupling element is mounted in the injection device so that it is not moved out of the first retaining connection into the second retaining connection until after the ampoule has been fully inserted or pushed in or screwed in, which can cause the two substances contained in the ampoule to be mixed at the same time. For example, the operating or coupling element may be disposed in the injection device in such a way that an ampoule which has to be fitted or pushed in by a previously known degree or dimension, for example, does not come into contact with the coupling or operating element until the last part of the insertion distance. Thus, the ampoule can be screwed into the injection device before this last distance without contacting or moving the coupling or operating element and it is not until the ampoule makes contact with the coupling or operating element and the movement caused by fully inserting the ampoule that the coupling element releases the mechanism for operating the injection device or the operating element is released for operation and to enable a user to make a setting by extracting it out of the housing of the injection device.
The first and/or second retaining connection may be provided in the form of a catch connection, for example, in which case a catch ring may be provided, which projects radially or outwardly from a coupling or operating element and establishes a first retaining connection in conjunction with an annular groove of the injection device or housing and the second retaining connection is established by another annular groove of the injection device or the housing. The retaining element may also be provided in the form of other mechanical couplings, which can be released when a defined minimum force acts on this coupling.
The mechanical lock may be such, for example, that an anti-rotation lock is provided for the setting element by guiding grooves projecting from the setting element so that the setting element is prevented from rotating in a distal position. Once an ampoule is screwed in, the locked setting element is pushed so far in the proximal direction that the grooves used to establish the anti-rotation lock are pushed out of the elements of the injection device or housing which retain and guide these grooves, for example, thereby enabling the setting element to be rotated and thus operated. Another option is to provide a coupling element which does not enable the setting element to be rotated until after a movement in the proximal direction. For example, this coupling element may be of an annular design and may have inwardly and outwardly directed webs, which engage in grooves of the setting element and grooves of the injection device or housing, thereby preventing the setting element from being rotated relative to the housing of the injection device. When the setting element is moved in the distal direction against the force of a spring pre-tensioning the coupling element in the distal direction via an ampoule inserted in the injection device and screwed in, for example, so that the webs of the coupling element are pushed out of the grooves of the setting element and/or out of the grooves of the injection device, the coupling of the setting mechanism with the injection device is released and the injection device can then be operated, e.g., when the ampoule has been fully inserted in the injection device.
When manufacturing injection devices, e.g., injection devices designed to administer a fixed dose of a substance, their construction and the dose setting mechanism may be configured for a specific application. For example, to dispense a large quantity of substance or to produce a long stroke of the setting element, an internal thread of the injection device in which a threaded rod or setting element is guided is provided with a large pitch. If an existing injection device also has to be used for dispensing smaller doses of substances, it is necessary to come up with a new design and produce this new design to provide an internal thread with a smaller pitch, for example. Therefore, another object of the present invention is to provide an injection device which can be used universally.
In some embodiments, an injection device in accordance with the present invention has an internal thread for guiding a threaded rod or setting element, for example, and the internal thread is designed so that it has several contact faces to enable different threaded rods with an external thread of a different pitch to be guided without having to replace or modify the internal thread of the injection device. Accordingly, in some preferred embodiments, the internal thread is made up of individual thread portions. These thread portions may be offset from one another in the circumferential direction and may extend across 1/Nth of the circumference, for example, where N represents a natural number. For example, the thread portions are such that they extend across a half or a third or a quarter of the circumference on the internal face of the injection device or a housing thereof. in some embodiments, the individual thread portions have at least two contact faces on which threads of a different pitch can be guided.
In some preferred embodiments, the thread portions have at least four side faces in which a thread can be guided, in which case two side faces are disposed parallel with one another respectively. In the circumferential direction, i.e. along the course of a thread segment or thread part-element, the contact surfaces for guiding the different threads alternate indirectly or directly. For example, the contact surfaces may either contact one another directly or be used by thread portion segments or thread portion part-pieces which are used to guide other threads of a different pitch.
It may be that such a thread or thread part-piece is designed so that more than two threads of a different pitch can be guided. To this end, the thread or thread segment contact faces may have a minimum pitch and a maximum pitch predefined by the thread segments for guiding threaded rods with a variable pitch. Another option is one where the thread segments have several contact faces and are disposed in the circumferential direction so that only threads of defined pitches can be guided, for example three different predefined pitches.
Generally speaking, depending on the design of a thread segment, e.g., the design of the contact faces of the thread segment, and depending on the distribution of the thread segments in the circumferential direction, it is possible to predefine which external threads can be guided by thread segments with one or more such internal threads of differing pitch.
In accordance with the present invention, therefore, it is possible for a single injection device or a single internal thread of the invention to guide elements with an external thread of a different pitch without having to modify the structure of the internal thread or the injection device. Consequently, the same injection device can be used for different applications which, for example, require short or also long strokes to set a dose.
When a substance contained in an ampoule in an injection device has been fully or partially dispensed, for which purpose a threaded rod or plunger rod pushes on a stopper to force the substance by moving the stopper inside the ampoule, for example, it may be that this plunger rod or threaded rod is inadvertently pulled back inside the injection device, which can lead to incorrect operation of the injection device. Therefore, another object of the present invention is to provide a threaded rod and an injection device incorporating such a threaded rod, which ensures that the threaded rods can no longer be pulled out once they have been fully pushed in.
Thus, in some embodiments, a threaded rod in accordance with the present invention has an anti-rotation locking element, e.g., a claw lock, which is disposed on the threaded rod at or adjacent to its proximal end so that the anti-rotation lock or claws can be pushed into co-operating elements retaining or engaging in the locking elements or claws when the threaded rod or plunger rod has been pushed as far as a predefined distal end position of the injection device, for example. This being the case, the claws or rotation locking elements in which the claws or rotation locking elements of the threaded rod engage are permanently connected to the injection device or a part of it, for example, a part of the housing of the injection device. A threaded rod pushed into the injection device can therefore no longer be rotated once the claws or locking elements have been pushed into the co-operating locking elements of the injection device because of the engagement between the elements. The engagement might be based on webs projecting into grooves for example, and the threaded rod or plunger rod is coupled with the injection device so that it can not rotate, thereby making it impossible to turn it. A threaded rod can therefore be retained in an inserted end position because the claw lock ensures that turning is no longer possible and an axial movement is prevented by the thread coupling.
Accordingly, if using the threaded rod in accordance with the present invention, it is not absolutely necessary to provide any other retaining mechanism in the injection device for holding and securing the threaded rod in the end position. The threaded rod is already fixed by the threaded rod design in accordance with the invention and the claw lock provided or disposed on it.
In some embodiments, the rotation locking elements of the injection device may be provided in the form of indentations in or claws on the injection device or parts of the injection device, such as the rotating sleeve. Various designs of co-operating elements of the injection device are possible, and the rotation locking co-operating elements may be such that they establish a positive connection with the rotation locking elements of the threaded rod engaging in or pushed into the rotation locking co-operating elements, so that the positive connection thus prevents the threaded rod from being turned in the proximal and/or distal direction. The rotation locking elements on the threaded rod may be resiliently mounted, for example, so that they are able to snap or latch in the rotation locking co-operating elements of the injection device in the distal end position for example. The rotation locking elements of the threaded rod may also be fixedly mounted and may be at least slightly or partially deformable so that they are able to snap or latch in the rotation locking co-operating elements of the injection device in the distal end position. When the rotation locking elements snap or latch into the rotation locking co-operating elements, they are positively connected to the rotation locking co-operating elements, thereby preventing any movement or rotation of the threaded rod in the proximal and/or distal direction.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of an embodiment of an injection device in accordance with the present invention;
FIG. 2 is a perspective view of the injection device in cross-section along section A-A indicated in FIG. 1 ;
FIG. 3 is a sectional view showing an alternative embodiment along section A-A indicated in FIG. 1 together with other sections B-B and C-C indicated in the first view in section;
FIG. 4 shows the injection device illustrated in FIG. 3 after mixing and with the mechanism extracted;
FIG. 5 shows the injection device illustrated in FIG. 4 after setting the dose and tensioning the spring;
FIG. 6 shows the injection device illustrated in FIG. 5 after dispensing the dose with the mechanism blocked and the spring relaxed;
FIG. 7 is a view in cross-section showing an injection device without an ampoule inserted;
FIG. 8 shows detail A from FIG. 7 and illustrates the threaded engagement of the guide sleeve in the threaded rod;
FIG. 9 shows the thread of the guide sleeve illustrated in FIG. 8 with different contact faces for guiding different threaded rods with an external thread of a different pitch;
FIG. 10A is a perspective view illustrating an embodiment of a dose setting mechanism of an injection device in accordance with the present invention;
FIG. 10B shows the dose setting mechanism illustrated in FIG. 10A with a cross-sectional view of the proximal part;
FIGS. 11A-11C show different embodiments of a real-time or remaining quantity display;
FIGS. 12A-12B show an embodiment of a claw lock in accordance with the present invention; and
FIGS. 13A-13G show an embodiment of a mechanical lock in accordance with the present invention.
DETAILED DESCRIPTION
With regard to fastening, mounting, attaching or connecting components of the present invention, unless specifically described as otherwise, conventional mechanical fasteners and methods may be used. Other appropriate fastening or attachment methods include adhesives, welding and soldering, the latter particularly with regard to an electrical system of the invention, if any. In embodiments with electrical features or components, suitable electrical components and circuitry, wires, wireless components, chips, boards, microprocessors, inputs, outputs, displays, control components, etc. may be used. Generally, unless otherwise indicated, the materials for making the invention and/or its components may be selected from appropriate materials such as metal, metallic alloys, ceramics, plastics, etc.
FIG. 1 illustrates an embodiment of a fixed-dose injection device, i.e., an injection pen, in which the dose to be dispensed is set using the dose setting knob 1 .
The pen has a threaded rod 5 , which is designed in the shape of a star with four points 5 b , as illustrated by the sections shown in FIGS. 3 to 6 , thereby providing a simple and robust means of setting the fixed dose.
In principle, the threaded rod 5 may have a star-shaped cross-section (Swiss cross) but the star may also have more or less points 5 b than the Swiss cross.
FIG. 2 illustrates the pen shown in a perspective view in FIG. 1 but in section along line A-A.
The guide sleeve 3 may be connected to the housing 10 and is mounted or carried so that it can not rotate relative to the housing 10 . Inside the guide sleeve 3 is a rotating sleeve 2 mounted with a snapper bead 2 a so that it can be rotated but can not be moved axially. Mounted on the external face of the guide sleeve 3 is the dose setting knob 1 which can likewise be rotated by virtue of a snapper bead 3 a but can not be moved axially. Disposed at the proximal end of the rotating sleeve 2 and connected to the guide sleeve 3 and rotating sleeve 2 is a spring element 4 , which, in one preferred embodiment, is provided in the form of a two to three-times coiled spring wire or spring strip. A rotation of the rotating sleeve 2 relative to the guide sleeve 3 tenses the spring 4 , which is attached by bends 4 a at the opposite ends to the guide sleeve 3 on the one hand and to the rotating sleeve 2 on the other hand, thereby producing a return force opposing the setting rotating movement.
In some preferred embodiments, the dose setting knob 1 is not pulled out axially but rotated. Disposed on the internal face of the dose setting knob 1 pointing in the axial direction are four webs. The webs engage in matching grooves of the rotating sleeve 2 and couple the dose setting knob 1 with the rotating sleeve 2 . Thus, a rotating movement of the dose setting knob 1 can be transmitted to produce a rotating movement of the rotating sleeve 2 . In principle, the dose setting knob 1 and rotating sleeve 2 could be of an integral design or provided as one element.
The rotating sleeve 2 has snapper elements 2 b pre-tensioned radially inwardly and, in the embodiment illustrated as an example in section C-C in FIG. 5 and shown in FIG. 5C , has two oppositely lying snapper elements 2 b pre-tensioned radially inwardly. These snapper elements 2 b engage in the grooves 5 a of the threaded rod 5 during the priming movement or are rotated past the points 5 b . During the priming operation, the threaded rod 5 is mounted so that it can not rotate because it is retained by a snapper element 3 b of the guide sleeve 3 . The rotating sleeve 2 has a snapper element 2 c pre-tensioned radially outwardly, which is rotated into a window or orifice 3 g of the guide sleeve 3 illustrated in the section B-B shown in FIG. 5 , and detail D in FIGS. 5B and D. Element 2 c latches in the window 3 g so that it is not possible for the rotating sleeve 2 to be turned back relative to and inside the guide sleeve 3 due to the force of the spring 4 tensioned by the setting operation. When the release button 11 of the pen lying above the window 3 g of the guide sleeve 3 is depressed, the snapper element 2 c of the rotating sleeve 2 is pushed out of the window 3 c of the guide sleeve 3 and thus releases the rotating sleeve 2 from the guide sleeve 3 so that it can be turned back by the setting distance due to the force of the pre-tensioned torsion spring 4 .
Provided on the distal end of the rotating sleeve 2 lying opposite one another in the circumferential direction are two stops, webs or cams 20 a , 20 b projecting in the axial direction, which permit a maximum rotation of the rotating sleeve 2 of approximately 110° because these cams move into abutment with cams 3 c of the guide sleeve 3 which are also in the radial direction but oriented in the proximal direction.
When rotated back in the dispensing direction indicated by arrow A in the section C-C shown in FIG. 5 , the snapper elements 2 b of the rotating sleeve 2 pre-tensioned radially inwardly latch in the grooves 5 a of the threaded rod 5 extending in the axial direction so that the threaded rod 5 is driven by the backward rotating movement of the rotating sleeve 2 and is thus screwed into the pen in the distal direction guided by an internal thread 3 d of the guide sleeve 3 . This causes a forward movement of the stopper or stoppers 13 a , 13 b of the ampoule 13 due to the ram 8 provided on the distal end of the threaded rod 5 or an extension element 5 v connected to it into the ampoule 13 , thereby dispensing the substance 13 c contained in the ampoule 13 . After dispensing, the pen can be primed again by rotating the dose setting knob 1 and the same dose can then be dispensed.
The threaded rod 5 can be made by an injection moulding process with two mould halves if the threaded rod 5 is based on a cross-section in the form of a simple cross. In the axial direction of the threaded rod 5 , the grooves 5 a in which the snappers 2 b of the guide sleeve 2 engage may be continuous and thus interrupt the thread 5 c on the external face of the threaded rod 5 . This enables high or steep faces to be produced for the snapper 2 b.
The outer or peripheral regions of the threaded rod 5 have a ramp 5 d so that the snappers 2 b can slide over and away more easily during priming. This also results in a higher face 5 e on the side of the groove 5 a of the threaded rod 5 extending in the axial direction, in which the snapper 2 b engages, reliably preventing the rotating sleeve 2 from being turned back relative to the threaded rod 5 .
In principle, with such a design of the threaded rod 5 , it is easily possible to vary the thread pitch during the manufacturing process so that different quantities of dose to be dispensed can be set by the same setting rotating movement of 110° for example, depending on the respective pitch specifically available. In this respect, the internal thread 3 d of the guide sleeve 3 can be changed so that it matches the modified pitch of the external thread 5 c of the threaded rod 5 . Alternatively, another option would be for the internal thread 3 d of the guide sleeve 3 to be designed to guide different pitches of the external thread 5 c of the rod 5 within a range of a minimum pitch predefined by the internal thread 3 d up to a maximum pitch predefined by the internal thread 3 d . FIG. 9 shows a single thread of the internal thread 3 d of the guide sleeve 3 opened out with a minimum and a maximum pitch resulting from contact edges 3 e and 3 f of the internal thread 3 d.
To ensure that the pen can not be primed again once the last dose has been dispensed, a claw lock is provided on the threaded rod 5 . It has a wider region 5 f at the proximal end of the threaded rod 5 from which four webs 5 g project pointing distally in the axial direction, which move or are pushed into matching co-operating stops 2 g of the rotating sleeve 2 after the last dose has been dispensed. As result, the threaded rod 5 is moved axially so far into the rotating sleeve 2 that the claws or webs 5 g of the threaded rod 5 lie against matching co-operating stops 2 g of the rotating sleeve 2 . The webs of the claw lock are able to move into the corresponding co-operating stops 2 g because when the injection device is operated, they are lightly or partially mechanically deformed or compressed and relax on reaching the end position, for example, and move into the co-operating stops provided in the form of recesses. The claws of the claw lock may also be resiliently mounted. When the injection device is operated, the resiliently mounted claws 5 g slide along the co-operating stop 2 g as illustrated in FIG. 12A and are deflected out in the direction indicated by the arrow. Once the dose has been dispensed, the claws 5 g snap into the co-operating stop 2 g as illustrated in FIG. 12B , so that the injection device can no longer be primed. Irrespective of the design of the claw lock 5 g and the co-operating stops 2 g , the system of the claw lock 5 g and co-operating stops 2 g in accordance with the present invention means that when the last dose has been dispensed, the pen can no longer be primed because the threaded rod is retained by the positive connection between the claw lock 5 g and co-operating stops 21 g so that it can not rotate. It is no longer possible to set another dose on the pen because the threaded rod 5 is mounted so that it can not rotate in the guide sleeve 3 , and the dose setting knob 1 and the rotating sleeve 2 are prevented from rotating by the claw coupling 2 g , 5 g.
In some embodiments, a two-chamber ampoule 13 may be inserted or screwed into the injection device. For mixing purposes, the ampoule 13 is screwed into the pen, and once the ampoule 13 has been screwed far enough into the pen, it moves into abutment with the guide sleeve 3 and pushes it together with the dose setting knob 1 in the proximal direction of the pen. This causes the dose setting knob 1 to be pushed out of the pen and it is not until then that the pen can actually be set or primed.
As illustrated in FIGS. 13B and 13C and the detailed view of FIG. 13D , a catch ring 40 or locking ring may be provided, for example, the two fork-shaped catch pawls 40 a of which project into co-operating recesses of the rotating sleeve 2 and prevent the rotating sleeve 2 from rotating. Since the injection device is charged by rotating the rotating sleeve 2 , the injection device is prevented from being primed or charged due to the engagement of the catch ring 40 in the rotating sleeve 2 .
To release the catch ring 40 and the rotating sleeve 2 , the ampoule sleeve which is screwed into the pen to mix the two-chamber ampoule is screwed in. In the last millimetres of movement, such as the last 1 to 3 mm, for example approximately the last 2 millimetres, the catch ring 40 is moved by the ampoule sleeve from the locked position into a released position in which the catch ring 40 is no longer latched to the rotating sleeve 2 . Once the ampoule 13 has been screwed in far enough, the two catch pawls 40 of the catch ring or locking ring 40 are pushed out, as illustrated in FIGS. 13E to 13G , whereby oblique surfaces 40 b or sliding surfaces disposed on the internal faces of the two fork-shaped catch pawls 40 a slide relative to and along oblique surfaces 30 or sliding surfaces formed on the guide sleeve 3 . Thus, the catch ring 40 is moved out of engagement with the rotating sleeve 2 and the rotating sleeve 2 is released so that it can effect rotating movements, for example to enable a dose to be set.
A display sleeve 6 is also provided on or associated with the threaded rod 5 , which is fixedly connected to the threaded rod, i.e. fixed in rotation and axially displaceable. On the external face of the display sleeve 6 , the dose quantities still to be dispensed are displayed in the circumferential direction. A viewing window 12 made from transparent materials or orifices 12 . 3 , 12 . 9 , 12 . 7 may be provided in the guide sleeve 3 , ampoule holder 9 and threaded sleeve 7 (from the inside towards the outside).
When the ampoule 13 has been mixed, the display sleeve 6 is pushed into it (but not before). In principle, the display sleeve 6 could also be mounted on the rear stopper 13 a so that it can rotate, in which case the display sleeve 6 is initially uncoupled from the mechanical system of the pen and is provided in the ampoule part.
Since there is a direct coupling between the display sleeve 6 and the threaded rod 5 , the display sleeve 6 is not able to slip. This means that an incorrect display is not possible, even if the pen is dropped and subjected to a strong impact, for example.
The guide sleeve 3 is also used as a visual screen because the window 12 . 3 in the guide sleeve 3 is offset from the window 12 . 7 in the threaded sleeve 7 before the ampoule 13 is screwed in. Only after screwing in and mixing the ampoule 13 is the window 12 . 3 of the guide sleeve 3 moved to a position congruent with the window 12 . 7 of the threaded sleeve 7 so that the display sleeve 6 mounted on the threaded rod 5 becomes visible as a result and can be read.
The release button 11 is positioned in a hole in the housing 10 and has two resilient arms 11 a in the circumferential direction, which push the releaser button 11 radially outwardly away from the guide sleeve 3 . The resilient arms 11 a describe a radius which is smaller than the external radius of the guide sleeve 3 to enable the release button 11 to be pre-tensioned radially outwardly.
The display 6 is directly coupled with the plunger rod or threaded rod 5 in the embodiments illustrated in FIGS. 11A and 11B and can be rotated about it without being retained by friction.
The plunger rod 5 has a thread or threaded part on the external face, in which the display 6 or, if a transmission is used for the display 6 , transmission element coupled with the display 6 , for example a gear or a gear with an internal thread as illustrated in FIG. 11C , can engage. If a transmission is used, a gap is formed between the gear directly coupled with the toothed rack and the display, through which the guide sleeve 3 can be inserted, for example.
If, instead of the toothed rack, a rotating mechanism is used with a plunger rod, the remaining quantity display can also be used. To this end, the remaining quantity display element 6 could be mounted so that it can not rotate on the plunger rod 5 so that, when dispensing, the plunger rod 5 is moved by the remaining quantity display 6 which is in turn mounted in the pen so that it is not able to move axially.
A remaining quantity display 6 which is not retained by friction can be achieved by using an appropriate thread pitch, which is dependent on the material and is approximately 45° in the embodiment illustrated as an example here.
The coupling between the remaining quantity display element 6 and toothed rack 5 is designed so that when the toothed rack 5 is fully inserted, the remaining quantity display element has effected a full rotation of 360°. In the event of a rotation of >360°, the display element 6 may be designed so that it can be moved farther by the external thread.
It would also be conceivable to use an axially displaceable remaining quantity display 6 , which moves axially relative to the injection device as the toothed rack 5 is moved, for example by a thread engagement on the external face of the remaining quantity display 6 in an internal thread in the housing of the device. For example, an injection pen with a constant, pre-set dose may be used and the remaining quantity display shows 14 maximum possible units to be dispensed, which can be counted back to 0 starting from an initial state.
Embodiments of the present invention, including preferred embodiments, have been presented for the purpose of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms and steps disclosed. The embodiments were chosen and described to provide the best illustration of the principles of the invention and the practical application thereof, and to enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth they are fairly, legally, and equitably entitled. | An injection device for injecting a substance from an ampoule inserted in the device, the device including one or more of the following components: an internal thread for engaging a threaded rod, the internal thread including several contact faces enabling the use of a different threaded rods, a real-time display for displaying a quantity of a substance, e.g., the quantity to be injected or dispensed, the quantity available for dispensing or the quantity dispensed, a mechanical lock for locking the device prior to inserting the ampoule, and a claw lock for preventing use of the injection device. | 0 |
FIELD OF THE INVENTION
The present invention is directed to a method, to techniques for applying the method and to apparatus which will permit the rapid attainment and the maintenance of a substantially constant concentration in the arterial blood plasma of an intravenously administered drug. In one preferred form, the method and apparatus are applied to the intravenous administration of drugs which produce sedation, anaesthesia, analgesia or muscle paralysis, in association with anaesthetic practice.
BACKGROUND OF THE INVENTION
At the present time there is a major problem in establishing and maintaining a constant concentration of drugs that are administered intravenously to maintain anaesthesia. It is known in general terms that to achieve a constant concentration of a drug in the arterial blood plasma it is necessary to administer a bolus dose of the drug to establish an initial level, followed by an infusion of the drug to maintain the level over a period of time. Methods used to date to implement this general idea are based on conventional pharmacokinetic analysis where predictions are made from studies based on the administration of single doses of a drug.
To use such methods it is first necessary to mathematically describe the loss from the body of a single dose of the particular drug. The single dose of the drug is administered to a subject and then samples of blood are drawn over a number of days in order to define the decay in the concentration of the drug in the blood plasma. Then, using the mathematical process of residuals or by nonlinear least-square regression analysis, one or more pairs of exponential coefficients are derived to describe the decay of the curve to the zero point at infinite time (see FIG. 1). A description of this method is provided in detail by Gibaldi, M. and Perrier, D., "Pharmacokinetics" Marcel Dekker Inc., New York, 1982, pp 433 and 475)
Also, from the elimination profile the clearance (Cl) of the drug by metabolism or excretion from the body may be obtained by:
Cl =dose/AUC
where the plasma concentration/time curve is integrated (AUC) for up to three days following the administration of the dose of the drug, again see Gibaldi and Perrier, p. 321.
Once the coefficients of the decay curve and the clearance of the drug have been determined, it then becomes possible using mathematical transforms to create a mathematical model which simulates the distribution and elimination of the single dose of the drug. The model consists of compartments described in terms of their volume (eg. V1, V2 and V3) and rate constants (eg. k12, k21, k13, k31 and k10) for the movement of drug to and fro between the compartments (see (FIG. 2). The loss of drug from the system by detoxification or excretion is described either by an elimination rate constant or by the clearance of the drug from the particular patient. Such methods are fully described in many tests, particularly by Gibaldi and Perrier at pp 45-111.
Once such a mathematical model of the subject has been created it then becomes possible to design infusion patterns in an attempt to achieve a steady concentration.
Earliest methods of infusion have involved the injection of a single dose of the drug followed by a constant rate infusion. The infusion is used to counteract loss of drug by elimination while the single dose, based on the amount of drug required either, to reach the desired concentration in the initial volume of distribution (V1 in FIG. 2) or in the steady state volume of distribution (V1 +V2+V3 in FIG. 2), is used to establish an initial concentration. Both these methods however ignore the time related movement of drug between the compartments and have proved unsatisfactory for many drugs, particularly anaesthetic drugs which are lost rapidly from the circulation. The situation is compounded further for many anaesthetic drugs as they have very narrow ranges of safety making it highly desirably to hold concentrations close to that desired by the operator.
Various approaches have been described in an attempt to overcome the problem of rapid loss of drug to the tissues and the consequent, highly undesirable, fluctuations in blood concentration. Some involve either substitution of a short term loading infusion for the initial bolus or alternatively the addition of a smaller loading infusion to the bolus and maintenance doses.
The most popular methods of infusion, however, utilize the coefficients of the compartmental model (FIG. 2) derived using the methods outlined above and averaged for a number of patients to derive exponential infusions. The parameters of the model are used as a basis for calculating an infusion profile which will keep the concentration constant in the central compartment of the model on the assumption that the patient will behave as the model. Such a method results in a mono- or polyexponentially decaying infusion profile asymptoting to a constant rate which relates to the anticipated constant rate of elimination of the drug at a steady plasma concentration. The constant rate (assymptote) varies considerably between drugs, being determined by the ability of the patient to detoxify or excrete the drug. Such methods combining bolus, exponential decaying infusion and maintenance rate infusion have been described in theory by Kruger-Thiemer, E. in "Continuous intravenous infusion and multicompartment accumulation" in European Journal of Pharmacology, pp 317-324, Volume 4, (1968) and by Vaughan, D. P. and Tucker, G. T. in "General derivation of the ideal intravenous drug input required to achieve and maintain a constant plasma drug concentration. Theoretical application to lignocaine therapy." in European Journal of Clinical Pharmacology, pp 433-440, Volume 10, 1976.
A practical use of the exponential method, in particular the use of a computer to perform the required transforms and control the rate of a drug delivery device, has been described by Schwilden H., Schuttler J., Stoeckel H. G. and Lauven P. M. in "Strategies of Infusion for Intravenous Anaesthesia" in Pharmacological Basis of Anesthesiology, eds Tiengo M. and Cousins M. J., Raven Press, 1983. These authors describe a method where it is necessary to store in the memory of a computer averaged kinetic data, ie. the compartmental parameters shown in FIG. 2, for each drug as well as appropriate programs to perform the considerable mathematical operations required. Then, prior to an infusion, the operator nominates the concentration required in the plasma of the subject. Then by a method, of the type described by Kruger-Theimer, an infusion pattern is computed as time passes, the magnitude of which is used to control the rate of a drug delivery device.
Various other approaches to the generation of exponential infusions have been described which use pneumatic or electrical means. One such method is described by Stoffregen (German Patent Application DE No. 3227518 A1 - 24 July, 1981) which produces a mono-exponential decay. This method while apparently novel in electronic technique uses the well known exponential method and further does not appear to offer any means of generating a polyexponential decay. Also the method does not describe any means of adapting the infusion rate to achieve a nominated arterial plasma concentration of the drug or to vary the base rate of infusion in accordance with rate of elimination of the particular drug in use.
SUMMARY OF THE INVENTION
The present invention recognizes:
(i) that conditions following a single dose, by comparison with those during an infusion may well be different, particularly for drugs that have a significant effect on the rate of flow of blood through the heart and to the various organs of the body.
(ii) that conditions of drug distribution and elimination are unlikely to be the same during an infusion at therapeutic levels as they are during the hours and days following a single dose,
(iii) that therapeutic levels of a drug may affect the distribution of a drug to the various tissues, particularly those where detoxification occurs.
(iv) that single dose drug elimination curves may be quite inaccurate at the extreme ends so that the early part suffers because of extrapolation and the later part because of the extremely low drug levels involved which lead to errors in the assay.
(v) that time related changes in the circulation may occur resulting in corresponding changes with time of the parameters of the kinetic model.
(vi) that drugs which produce unconsciousness cause falling levels of adrenaline and other substances which in turn alter circulatory and metabolic function, and
(vii) that for an infusion to be applicable to a wide variety of subjects and to be able to achieve a nominated level of the drug in a subject, some formal method is required to relate drug delivery to a measurable physical parameter which is widely applicable to subjects of varying age and morphology.
Central to the approach used in this method is the development of a new concept in pharmacokinetics, the Plasma Drug Efflux. This concept simply stated is that at any instant, if the plasma concentration of a drug is neither rising nor falling, the rate of delivery of the drug to the circulation ie. the infusion rate, must equate to the rate at which the drug is being lost form the circulation, it being unimportant whether the loss, is by distribution, metabolism or excretion.
If, by way of illustration, the blood plasma is represented as a single compartment of undetermined volume the infusion scheme may be represented as shown in FIG. 3. Then if drug is administered by some arbitrary infusion scheme Q(t), the plasma concentration is C(t) and the rate of drug loss from the plasma may be called the Plasma Drug Efflux, E p (t).
If the plasma drug concentration is constant so that the amount of drug is not changing then the instantaneous rate of drug influx to the plasma (the infusion rate), and the instantaneous concentration in the plasma may be used as an estimate of drug efflux from the plasma, as an estimate of i.e.:
E.sub.p ≈Q.sub.I /C.sub.I
The efflux estimate may then be plotted against time, and will essentially describe a dosing-rate/concentration profile as a function of time which will result in a plateau concentration for all time.
In practice in applying this method it is not possible at first to achieve a constant plasma concentration as this is, of course, the goal of the method. But it is possible by the use of very few iterations to closely approach this goal.
Thus, according to the first aspects, the present invention provides a method of determining a generalised infusion rate profile for the delivery of drugs into the circulation comprising the steps of:
(a) infusing a drug at arbitrary but known rates into a group of patients for each of whom the Lean Body Mass has been determined;
(b) determining the plasma arterial concentration of the drug in each patient at a number of specific time intervals throughout each infusion period;
(c) for each patient, estimating the rates of loss of drug from the circulation at a number of specific time instants by dividing the known infusion rates per Lean Body Mass at these instants by the plasma arterial concentrations of the drug at each of these instants.
(d) calculating the average of the estimated rates of loss of drug from the circulation per Lean Body Mass unit at each specific time interval for the group of patients;
(e) interpolating the successive average points between the specific time intervals to produce an infusion profile;
(f) infusing said drug in accordance with said infusion profile determined from said interpolations into a group of patients for each of whom the Lean Body Mass has been determined, said infusion rate being scaled according to said Lean Body Mass of each patient, and
(g) repeating steps (b) to (f) until a desired steady plasma arterial content of the drug is substantially maintained throughout the infusion period. It must be emphasized that the shape of each infusion profile, except for the first in the series, can be determined entirely by the results obtained from the previous infusion group and that no mathematical function is assigned or required by the method.
The invention also provides a method of infusion of a drug into a patient comprising the steps of:
(i) determining the Lean Body Mass of the patient:
(ii) selecting a predetermined profile for the rate of delivery of drug, which rate varies with time and is configured to maintain a selected substantially steady plasma arterial content of the drug in the patient throughout an infusion period;
(iii) scaling said predetermined profile by the determined Lean Body Mass of the patient and by the desired substantially level arterial plasma concentration of drug to be maintained in the system of the patient, and
(iv) administering the drug to the patient in accordance with said scaled profile by means of an infusion device which is controlled to deliver said drug at said scaled infusion rate profile.
Still further the invention provides a system for achieving the method of infusion comprising an infusion system for regulating the delivery of a drug to a patient, including control means for controlling the operation of an infusion pump, said control means including pre-programmed means for varying the invusion rate with respect to elapsed time, said pre-programmed means varying the infusion rate in accordance with a profile which varies with time and which is adapted to maintain a desired substantially steady plasma arterial content of the drug throughout the infusion period, and operator adjustable scaling means for setting the desired concentration of said drug in the patient and for setting the Lean Body Mass of the patient, said scaling means causing modification of the pre-programmed infusion rate by a fixed proportion over each time period of operation of said infusion pump.
The invention also provides an infusion apparatus by means of which the method and system may be realized, comprising an infusion pump comprising means for receiving a syringe containing a fluid to be administered, syringe actuator means and means for driving said actuator means to move the plunger of said syringe to deliver fluid therefrom, characterised in that said drive means includes a permanently maintained connection between said drive means and a position sensing device by means of which the position of said actuator means is monitored at all times.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred embodiment of each aspect of the invention will now be described with reference to the accompanying drawings in which:
FIG. 1 is a graph showing the basis of prior art methods of infusion;
FIG. 2 is a diagram showing the basis of the compartmental model of drug distribution and elimination;
FIG. 3 is a diagram illustrating one model explaining the basis of the method of the present invention;
FIG. 4 is a graph showing the Plasma Drug Efflux data of a first group of patients to the drug thiopentone (thiopental);
FIG. 4 is a graph showing the average of the data point in FIG. 4 interpolated to produce an Efflux profile;
FIG. 6 is a graph showing the Efflux profile (b) after two iterations and the profile (a) based on the Kruger-Thiemer method;
FIGS. 7 and 8 are graphs showing the infusion rates required for patients of indicated Lean Body Mass (LBM) and for different desired plasma concentrations for a single LBM;
FIG. 9 is the Plasma Efflux profile for methohexitone (methohexital) after three iterations;
FIG. 10 is a graph of the arterial plasma concentration of methohexitone in a patient showing a substantially constant level at the desired concentration for the whole period;
FIG. 11 is a perspective view of a preferred infusion pump;
FIG. 12 is a plan view of the control panel of the pump of FIG. 11;
FIG. 13 is a block diagram of the control circuitry for the pump of FIG. 11;
FIG. 14 is a section front elevation of the pump of FIG. 11 taken along the line 14--14 in FIG. 11;
FIG. 15 is a sectional elevation taken along the line 15--15 in FIG. 14;
FIG. 16 is a sectional plan view taken along the line 16--16 in FIG. 15; and
FIG. 17 is a sectional end elevation taken along the line 17--17 in FIG. 14.
DESCRIPTION OF PREFERRED EMBODIMENTS
Describing first the preferred method of defining a generalised infusion rate profile as applied to anaesthetic drugs, the method comprises the steps of:
(a) first determining the lean body mass (LBM) of a group of subjects. A convenient way of doing this in human subjects is to use the method described by Hallynck T.H. et al in "Should clearance be normalized to body surface of to lean body mass?" in British Journal of Clinical Pharmacology, pp 523-526, Volume 11, (1981), who presented the following formulae:
Males: LBM=1.10×weight-128×(weight.sup.2 /height.sup.2)
Females: LBM=1.07×weight-148×(weight.sup.2 / height.sup.2)
(b) Following administration of a suitable bolus dose of a desired drug to achieve unconsciousness, the drug is infused at an arbitrary but known rate throughout the infusion. This arbitrary infusion can be a constant rate infusion, a stepped rate infusion, an infusion pattern derived using the compartmental (Kruger-Thiemer) technique described above or an infusion pattern derived by the present method for a different drug which is known to have similar properties to the drug under test.
(c) From this inital set of results and by knowing the rate of infusion throughout, whatever the pattern, as well as the sex, height and weight of each patient a set of data points can be obtained relating the infusion rate to the plasma arterial concentration at various times (FIG. 4).
(d) By averaging the amplitude of the data points within specific time periods and interpolating the resulting points (FIG. 5) an estimate of the Plasma Drug Efflux profile is thus obtained.
This estimate of the Efflux, expressed in terms of millilitres of blood cleared of drug per minute per kilogram lean body mass thus becomes the prescription for the infusion profile for the next group of subjects.
(e) Then by using the same method of dosing but now applying the dosage in terms of the estimated Efflux of the drug and the LBM, plasma concentrations will approach a constant and desired level without any intervention on the part of the operator.
(f) Iterations of this method may then be repeated three of four times if further precision is needed.
This is thus a new infusion profile which completely bypasses the conventional, single dose derived compartmental model described earlier in this specification. In doing this, a definition of the error for infusion dosing based on the conventional approach is also achieved. The rate profile is now derived under actual infusion dosing conditions, and is clearly a more valid approximation to the ideal infusion function.
FIG. 6 presents a comparison between the curve of anaesthetic agent thiopentone (thiopental) for a conventional infusion rate function, based on the method of Kruger-Thiemer labelled (a), with the derived Plasma Efflux profile after two iterations normalized for plasma level, and based on actual infusion data, labelled (b).
A comparison of the curves shown in FIG. 6 reveals:
(i) the rate of the new profile is much higher than the previous curve as time progresses,
(ii) the new profile is 10 to 20% higher in the early phases than the previous curve,
(iii) the new profile is around 50-100% higher than the old curve from about 30 minutes onwards.
The initial high level of the new profile indicates that a much higher initial infusion rate is required, quickly forcing the plasma concentration to the required level, then a rate which is about twice the conventional rate, thus holding the plasma concentration at the desired level and indicating the marked difference in the circulation during this period from that predicted by the Kruger-Theimer method.
It must be appreciated that an infusion rate that is half that actually required to achieve the desired level will result in approximately half the arterial plasma concentration during that period of the infusion.
As stated above, some drugs, particularly those used in anaesthesia, must be used within a narrow range of concentrations. If, for example, the concentration of methohexitone (FIG. 10) moves from a normally desired level of 4 to 6 mg/l to 10 mg/l the severe depression of the heart and breathing may occur while a fall to below 3 mg/l is likely to result in wakening of the patient.
As described above the plasma drug efflux profile presented in FIG. 6 is normalized to unit plasma concentration and unit patient lean body mass.
In order to apply the data presented in FIG. 6 to a practical infusion device, it is necessary to multiply the amplitude of the plasma drug efflux curve first by a numerical value representing the size of the patient (Lean Body Mass), and secondly, by a numerical value representing the actual plasma concentration of the drug required by the operator.
FIG. 7 shows the actual infusion rate required for applying the curve of FIG. 6 curve (b) to patients of 20, 40, 60 and 80 kg LBM in order to achieve a steady plasma concentration of 1 mg/l of thiopentone. It can be seen that the shape of the generalized profile for plasma drug efflux remains the same as presented in FIG. 6 curve (b) but that the magnitude is altered throughout the profile in direct proportion to the Lean Body Mass of the patient.
FIG. 8, demonstrates a further scaling operation of the curve of FIG. 6 curve (b) where the actual infusion rates required for a 50 kg LBM patient, in order to achieve steady plasma concentrations of 1, 5, 10 and 20 mg/l are presented.
It is of interest to note that in a further application of the technique of the invention to the anaesthetic agent methohexitone (methohexital) (FIG. 9) that the Plasma Drug Efflux profile, derived from actual infusion data for this drug after three iterations bears little relationship to an exponential function, having two distinct humps. It is of further interest to note that an application of the Efflux profile of FIG. 9 to generate an infusion in a typical patient (FIG. 10) has resulted in constant and desired arterial plasma drug concentrations over a period of five hours. The broken line in the Figure indicates the concentration desired by the operator. Similar results have been achieved on many patients with no material departures from the desired level in any patient.
It will be appreciated that the above method may be used to derive similar Plasma Drug Efflux profiles for other anaesthic agents and for other drugs where a desired level of the drug in the system of the patient is to be maintained over an extended period of time.
While the most commonly used intravenous anaesthetic agents, thiopentone and methohexitone, have been used as examples, the methods, and the apparatus to be described below, are equally applicable to the administration of all intravenous anaesthetic agents including propofol, diazepam, midazolam and etomidate, as well as narcotic analgesics including morphine, pethidine, alfentanil, sufentanil, fentanyl and phenoperidine.
It will be appreciated from the above that the Efflux profile may be used to control a programmable infusion pump so that a selected drug may be delivered to a patient in accordance with the profile, as scaled by the Lean Body Mass of the patient and level of the drug desired by the operator to be maintained in the system of the patient. The profile is most suitably programmed into a device capable of controlling the infusion pump and since a different profile is required for each drug, this is most suitably achieved by the use of a programmed module which is inserted by the operator into the infusion pump controller circuit. One preferred embodiment of such an infusion pump will now be described.
By using the average rate of loss of the drug among different subjects against time an infusion pattern is produced which approaches the optimal pattern. This new pattern may then be applied to the next group of patients so that an iterative process results whereby an optimized curve is produced.
Referring now to FIGS. 11 to 17, a preferred embodiment of the infusion pump for performing the drug infusion method and its control circuitry is shown. The infusion pump will be seen to comprise a casing 100 within which the syringe drive and other mechanisms described below are located, the casing 100 including a syringe cradle 101 having a central groove 102 for locating the body of a syringe and a slot 103 for receiving and locating the syringe flange. A vertically moveable syringe holder and sizer 104 is positioned over the groove 102 and a syringe actuator 105, which is driven by the syringe drive in a manner further described below, is positioned to engage the syringe plunger to deliver fluid from the syringe at the rate determined by the syringe drive under the influence of its control circuitry.
The casing is also provided with a front panel 106 including the required input keys and displays. The casing further includes a window 107 through which the name of the program drug appearing on a program module 108 which is inserted into a receiving cavity in the casing 100 in the direction of the arrow, may be read.
Referring now to FIG. 12, the front panel 106 will be seen to include 4 four digit LCD displays 109, 110, 111 and 112. The first display 109 is associated with a first sector 113 of the panel 106 and includes illuminatable message displays for syringe concentration, patient concentration and dose given as well as the alternative measurement displays mg. mg/ml or mg/l. Thus when the relevant displays are illuminated, the four digit display indicates the level of the illuminated parameter.
The second display 110 is associated with a second sector 114 of the panel 106 which relates to the syringe and the rate of infusion therefrom. The infusion rate may be displayed in ml/min or ml/h by actuating an option switch inside the casing 100. The volume in the syringe is displayed in ml.
The third display 111 is associated with a third sector 115 which displays patient data including illuminatable displays which prompt the selection of male or female and prompt the inputting of the patients height and weight. A further option select switch is available to indicate the height of the patient in inches rather than in centimeters.
The fourth display 112 is associated with a fourth sector 116 which relates to elapsed time and also includes illuminatable displays indicating the status of the battery, occlusion, malfunction and operator error.
To the right of sector 116 a fifth panel 117 includes a key pad 118 for numeric entry including a cancelled button and an enter button. The panel 117 also includes five selection buttons selecting the functions: battery power, run, pause, reset and bolus. A battery charge level indicator 119 is also provided in the front panel 106.
Numeric entry into any one of the displays 109 to 112 is achieved by scrolling through the data displays using the set button associated with the relevant panel sector 113 to 116 followed by entry of the value by means of the key pad 118. Once the desired value is displayed, the operator may press the enter button so that the value is entered into the memory of the control circuitry to be described below.
The infusion pump is capable of operating at three levels:
Level 1--The rate of infusion is entered directly on the front panel and the pump will deliver any solution at this rate only--or until the rate is manually changed.
Level 2--The rate can be set by a remote device such as a computer. The Infusion Pump will communicate with the remote device by means of an isolated serial port.
Level 3--The rate of delivery of certain anaesthetic drugs is determined by the EPROM module 108 which is plugged into the infusion pump casing 100. This module will vary the rate with time and the relationship between these two factors will depend on the type of drug. Consequently, a separate module will be required for each drug type.
The rate as read from the EPROM module 108 is normalised, and the control unit will scale this to the patients sex, weight and height, and to the desired concentration entered by the operator. These factors are entered on a front panel keyboard as described below. A serial port (Serial I/O option--FIG. 13) is an `add-on` option capable of operating with or without an EPROM module plugged into the unit. Once appropriate control codes are sensed at the port, the unit will assume Level 2 operation. The serial port will also be capable of acting as a printer output for Level 1 or Level 3 operation.
Referring now to FIG. 13 of the drawings, the control circuitry for the infusion pump will now be described. Central to the control circuitry is a micro computer 120, which in the present embodiment is a type 80C39, which operates in accordance with an operating program stored in EPROM 121. The EPROM 121 my form part of the micro processor 120, and such a micro processor is available in the form of an 80C48. The micro processor 120 controls the speed of the motor in the syringe drive to be described below via a MOSFET driver circuit 122. The voltage applied to the motor via the circuit 122 is sensed by the line 123 which is connected to an analog to digital convertor 124 which also receives signals from feedback potentiometers 125 and 126 which respectively monitor the position of the syringe actuator 105 in FIG. 14, and indicate the syringe size via movement of the syringe sizing arm 104. Each feedback potentiometer 125, 126 is preferably a ten turn 50k ohm wire wound potentiometer since such potentiometers are accurate, reliable and inexpensive. An optical encoder 127, which forms part of the motor monitors the speed of the motor and feeds this data to the micro processor 120 so that the speed of the motor is accurately controlled by the micro processor 120.
A 6 MHz crystal clock signal generator 128 is connected to the micro processor 120 to enable the necessary timing functions to be performed. The micro processor 120 and the motor are powered by means of a battery 129 which is connected to the micro processor 120 and to the motor drive circuit 122 via a DC-DC convertor 130 which removes any unwanted variations in the battery supply voltage. A charger 131 is provided to enable the battery 129 to be recharged.
The micro processor 120 is also connected to a switch 132 positioned on the syringe actuator 105 with closure of the switch 132 indicating that the contact between the syringe actuator 105 and the syringe plunger has occurred. The switch 132 is preferably a single pole double toggle switch which indicates not only when contact between the syringe actuator 105 and the syringe plunger has occurred but also when disengagement between the syringe actuator 105 and the syringe plunger has occurred. Although this arrangement is presently preferred, it is also possible for the micro processor 120 to sense when the current drawn by the motor increases and decreases, via line 123, so that the engagement and disengagement between the syringe actuator 105 and the syringe plunger may be detected.
The LCD displays 109 to 112 are connected to LCD driver circuits 133 while the remaining indicator lamps and LED battery charge indicator 119 are connected to lamp driver circuits 134. A warning buzzer 135 is also provided for the purpose to be described further below.
The operating program stored in EPROM 121 causes the infusion pump to function in the following manner.
At "power on" all displays are illuminated for one second and then turned off. An internal test sequence is performed in which the presence of the drug specific EPROM module is detected and any malfunction in the displays is noted and, if so, the malfunction display illuminated. Thereafter, the initialisation sequence commences in which the "syringe concentration" display is illuminated and the units in mg/ml is displayed via the display 109 taking the usual concentration of the drug read from the module 108, for example, thiopentone--25 mg/ml, methohexitone--10 mg/ml, fentanyl--0.050 mg/ml. The operator may then press the set button in sector 113 or perform the numeric entry sequence for a desired syringe concentration value. The resulting syringe value, whether it remains as read from the EPROM or is altered by the operator, is stored in memory to be used to scale delivery of the drug containing fluid. After entry of this data or after the set button is pressed, the "patient concentration" display is illuminated and an average value as read from the module 108 is displayed at 109, for example, thiopentone 10.0 mg/l or methohexitone 5.0 mg/l. The displayed value may be modified by the numeric entry sequence described above. The EPROM module 108 stores an acceptable range of patient concentrations for each drug, for example, thiopentone 5-20 mg/l and methohexitone 2-12 mg/l. If values outside these ranges are entered then the `patient concentration` display is flashed in all modes of operation until the value is brought within the range. On pressing the set button or the enter button, entry to this sector is complete and the first display on the syringe sector 114 ("load empty") is illuminated.
The operator raises the syringe holder and sizer 104 and loads an empty syringe into the syringe cradle 101 and presses the set button in sector 114. The motor is activated and the syringe drive to be described further below moves the syringe actuator 105 towards the empty syringe until closure of the switch 132 indicates contact and the position of the syringe actuator 105 is stored in the memory of the micro processor 120. This is the zero position (plunger length) of that particular syringe. The syringe diameter as detected by the syringe holder and sizer 104 through feedback potentiometer 126 is also stored in the memory. If no syringe is loaded, the previously stored zero position and syringe diameter are assumed and the syringe actuator 105 is driven fully to the left to await the loading of a filled syringe.
The "load filled" display is then illuminated and the operator loads a syringe and presses the set button. At this point, a comparison is made between the previous diameter and the new diameter and if a discrepancy of greater than ±2.5% is noted, the "load empty" display is illuminated in order to calibrate for a new syringe. If the new diameter matches the old then the "volume" display is illuminated and the volume of the syringe computed from the diameter of the syringe and the displacement of the syringe actuator 105 from the zero position is displayed at 110 and stored in the memory of the infusion device in order to adapt plunger movement to deliver the required volume as determined by other calculations. As an optional safety feature, the operator may be required to enter the loaded volume of the new syringe and if the entered value differs by more than ±10% of the previously computed value, the calibration procedure is recommenced from "load empty".
It has been found that the variation in wall thickness of commerically available syringes of similar internal diameters is insignificant when regard is had to the error tolerance in the volume of drug which may be infused into a patient as well as the acceptable error in the formulation of the drug solution. Accordingly, the diameter measurement which is made by the syringe holder and sizer 104 is sufficiently accurate to provide the necessary volume measurement during the infusion process.
After the filled syringe is loaded and the syringe actuator 105 is in contact with the syringe plunger, the "sex M=0 F=1" display is illuminated followed by the "height" and "weight" displays in sequence for numeric entry of the values relating to the particular patient to be treated. If the operator wishes to enter the patient height in inches, the internal switch is actuated. The operator enters these patient parameters, the Lean Body Mass is calculated, displayed on display 111 and stored in the memory of the device for use in adapting infusion rates to the particular patient. Once the patient data entry is completed, the set button is pressed and the display 112 will scroll through the values entered in sector 116, at which time any value may be changed by the numeric entry procedure.
After the patient data has been entered, all displays should be blanked except for the time which will show 00:00. At this stage, the elapsed time may be preset using the numeric entry sequence in the event that the pump needs to be restarted within an infusion sequence. The zero elapsed time or the operator preset time is indicated on display 112 and stored in the memory of the device for use in determining the point to start reading the infusion pattern.
When the patient is ready for treatment, the run button is pressed with the elapsed time incrementing, except during activation of the pause button, and shown on display 112. The syringe display 110 will show the delivery rate in ml/min or ml/h if the option switch has been actuated. The patient display 111 indicates the Lean Body Mass of the patient in kg calculated by the formula referred to above. The drug display 109 indicates the accumulated dose of drug administered to the patient.
Whenever the pause button is pressed, the time clock stops operation and the syringe display 110 indicates the total volume delivered since commencement of operation and the volume display is illuminated. The patient display remains unaltered while the drug display 109 indicates the dose given since the previous reset or commencement, the dose given display being illuminated at the same time.
It should be emphasized that by virtue of the syringe sizing mechanism and the plunger sensing switch of the device the accumulated volume and doses displayed will represent the sum of all syringes loaded whatever the volume or size of syringe used. Change of any display can occur at this point by pressing the appropriate set button and if the syringe holder and sizer 104 is lifted or the syringe actuator 105 is moved, the syringe sequence recommences at the "load filled" point.
If the bolus button is pressed at any time, the syringe and drug displays are immediately zeroed and drug delivery commences at a rate of the order of 1 ml/sec for a 50 ml syringe, the display "dose given" is illuminated and the progressive volume delivered is displayed at 110 in ml. On release of the bolus button, the syringe display reverts to a display of the running rate, the drug display 109 shows the sum of the bolus and the previous dose while the time display reverts to the previous mode.
Pressing the BAT button causes illumination of the LED display 119 to indicate the condition of the battery.
If either the syringe switch 132 or the syringe holder and sizer 104 is moved to a new position for more than two seconds, the syringe actuator 105 is driven to the left and the syringe set sequence is recommenced at the "load filled" point. If an occlusion is detected by a sudden increase in the drive current to the motor, via line 123, the syringe actuator 105 is driven to the left until the switch 132 is disengaged, whereupon the "occlusion" display is illuminated and the buzzer 135 actuated. The detection of occlusion is related to a diameter of the syringe, detected by the syringe sizing mechanism so that the larger drive current required for larger syringes will not cause a false occlusion alarm. One way of achieving this is to store data relating to the maximum force required to move a syringe at various rates in use and to scale this force in accordance with the detected diameter.
Occlusion of the drug delivering conduit by a tap represents considerable danger to a patient if a highly potent drug is contained in the syringe and the tap is suddenly opened while under pressure. The three features of adjusting occlusion pressure detection to the measured syringe diameter, backing of the drive once overpressure is detected and sounding the alarm after the pressure is removed are specifically designed to lessen this risk.
Illumination of the "malfunction" display occurs whenever any form of malfunction is identified and the buzzer 135 is actuated. Similarly, the "operator error" display will be illuminated in the event of an operator error being detected, such as, pushing forward manually on the drive mechanism when the drive mechanism is connected or the entry of incompatible syringe sizes for a given LBM. Syringe to patient incompatibility is determined by calculating the ratio of the Lean Body Mass of the patient to the sensed diameter of the syringe and relating this ratio to the rate fluid is to be delivered. It is recognized that considerable inaccuracy will result if a very large syringe is used with a very small patient.
As mentioned above, three levels of operation may be selected and the level of operation determines the rate at which the fluid in the syringe is delivered and this rate continues, as programmed, unless any one of the following occur:
the bolus key is depressed.
an occlusion occurs.
a system malfunction occurs.
the plunger is manually pushed forward to administer more fluid (as sensed by the plunger position potentiometer 125). The switch 132 shows the plunger is disengaged.
the syringe size potentiometer 126 indicates a change in reading, or
the pause key is pressed.
In Level 3 operation, an infusion pattern stored in the EPROM 108 is followed by the infusion pump. The pattern is drug dependent and a separate module 108 is used for each type of drug. Typical infusion patterns for thiopentone and methohexitone are shown in FIGS. 6 and 9 of the drawings and are described in greater detail above. The rate drug delivery stored in the module 108 is scaled by the Lean Body Mass data entered in the manner described above as well as by the desired concentration data entered by the operator. The effect of this scaling is clearly shown in FIGS. 7 and 8 of the drawings which indicate drug delivery rate in terms of the dose delivered per minute. The volume of drug containing fluid which must be delivered is further scaled in accordance with usual concentration of the particular drug in the syringe which is read from the drug specific EPROM 108 or entered by the operator during the initialization sequence. Then using the result of these previous calculations the actual movement of the syringe actuator is scaled in proportion to the syringe diameter as determined by the syringe sizing mechanism.
During Level 3 operation, a bolus is automatically administered at time 00:00 unless the operator indicates, via keyboard input, that a bolus has been previously administered.
This starting bolus is administered at a rate determined by data stored in the EPROM module 108, the volume administered being scaled according to the entered Lean Body Mass desired concentration and the concentration of drug in the syringe. The amount delivered is displayed at 109 with the "dose given" display illuminated.
During normal operation additional drug may be administered by pressing the bolus key and will continue at the rate described above for as long as the key is depressed.
Referring now to FIGS. 14 to 17 of the drawings, the syringe drive mechanism will now be described in greater detail.
The drive motor M is preferably an ESCAP DC gear motor type MA1616 C11 with 243:1 gear ratio and B type optical encoder. The output shaft of motor M is fitted with a toothed or knurled drive wheel 300 and the motor is mounted on a pivoted arm 301 (FIG. 16) which is pivoted towards its "drive engaged" position under the influence of a spring 302. The drive wheel 300 engages a polyurethane drive ring 303 which encircles a driven wheel 304 which transmits drive through a shaft 305 to a toothed drive head 306. A toothed drive belt 307 engages the drive head 306 and also passes around a similar toothed drive head 308 spaced from the drive head 306 at the opposite end of the casing 100. Both drive heads 306, 308 are mounted in bearings on a frame 309 and the drive head 308 is drivingly connected to the position feedback potentiometer 125 which is supported below the frame 309 in the manner shown (FIG. 14). It should be appreciated that the belt drive may be replaced by a chain or similar flexible drive although the belt drive is preferred for practical reasons.
A permanent driving connection is effected between the drive belt 307 and the syringe actuator 105 by means of belt clamp 310 having a connector plate 311 which is in turn attached to a slider 312 which is connected to the syringe actuator 105 by means of tubes 313, 314 surrounding a pair of spaced parallel guide rods 315, 316 which extend longitudinally of the casing 100 and into the syringe cradle 101. Both the slider 312 and the syringe actuator 105 are provided with bearings 317, 318 which engage the guide rods 315, 316 to facilitate sliding movement of the slider 312 and the syringe actuator 105. The tubes 313, 314 engage seals 319 in the syringe cradle 101 to prevent ingress of foreign matter into the casing 100.
It will be appreciated from the above that a permanent driving connection is maintained between the belt 307 and the syringe actuator 105 so that the position potentiometer 125 is at all times able to accurately sense the position of the syringe actuator 105. In other words, there is not in the present embodiment of the invention, as in some prior art infusion pumps, the ability to disconnect the drive between the syringe actuator and the driving mechanism. However, it is possible to disengage the drive wheel 300 from the driven wheel 304 to enable easy manual movement of the syringe actuator 105 during loading and unloading of a syringe.
In the present embodiment, drive release is achieved by manually depressing push buttons 320, 321 mounted in the syringe actuator 105. The buttons 320, 321 extend from the ends of arms 322, 323 which in turn extend from mounting sleeves 324, 325 which surround the tubes 313, 314 and are fixed to impart rotation thereto by means of grub screws 326 when the buttons 320, 321 are depressed. It will be appreciated from the above that the tubes 313, 314 are free to rotate in both the syringe actuator 105 and the slider 312.
Drive release actuating cams 327, 328 are attached to tubes 313, 314 by means of grub screws 329 and are located within the slider 312. The cams 327, 328 are positioned to contact a motor release bar 330 (FIGS. 15 and 17 which is in the form of a bell-crank lever having its pivot extending longitudinally of the casing 100. The other arm 331 of the bell-crank lever is attached by a link 332 (FIGS. 15 and 16) to the pivoted motor mounting plate 301. Thus by depressing the buttons 320, 321, with one hand, the tubes 313, 314 are rotated to bring the cams 327, 328 into contact with the motor release bar 330 which pivots the plate 301 to the left in FIG. 16 to move the drive wheel 300 out of engagment with the rim 303 of the driven wheel 304. When thus released, the syringe actuator 105 may be freely moved along the guide rods 315, 316 although by virtue of the permanent connection to the drive belt 307, the position sensing potentiometer 125 continues to register the position of the syringe actuator 105 at all times.
It will be appreciated that motor release may be achieved with only one button and associated tube and cam mechanism.
Referring now to FIGS. 14 and 17, the syringe holder and sizer 104 will be seen to comprise a clamping arm 340 mounted on a vertically extending shaft 341 supported for vertical sliding movement by frame members 342, 343 and biased towards a clamping position by means of compression spring 344 engaging a flange retainer 345 attached to the shaft 341. At its lowermost end, the shaft 341 has an element of toothed drive belt 346 attached thereto and a light biasing spring 347 is attached to the other end of the belt 346 to maintain it in engagement with a gear wheel 348 keyed to th shaft of the syringe sizing potentiometer 126. In this way the syringe holder and sizer 104 operates to clamp the syringe in the syringe cradle 101 and causes the sizing potentiometer 126 to transmit a syringe size signal to the micro processor 120 via the analog to digital convertor 124.
The rating of the spring 302 is selected so that the driving gear 300 will slip on the rim 303 of the driven wheel 304 in the event that a severe occlusion occurs and the syringe plunger does not move into the syringe. Of course in most instances, the micro processor 120 will sense an excessive increase in motor current and will stop the motor M. | A method of determining a generalised infusion rate profile for the delivery of drugs into the circulation comprising the steps of:
(a) infusing a drug at arbitrary but known rates into a group of patients for each of whom the Lean Body Mass has been determined;
(b) determining the plasma arterial concentration of the drug in each patient at a number of specific time intervals throughout each infusion period;
(c) for each patient, estimating the rates of loss of drug from the circulation at a number of specific time instants by dividing the known infusion rates per Lean Body Mass of these instants by the plasma arterial concentrations of the drug at each of these instants;
(d) calculating the average of the estimated rates of loss of drug from the circulation per Lean Body Mass unit at each specific time interval for the group of patients;
(e) interpolating the successive average points between the specific time intervals to produce an infusion profile;
(f) infusing said drug in accordance with said infusion profile determined from said interpolations into a group of patients for each of whom the Lean Body Mass has been determined, said infusion rate being scaled according to said Lean Body Mass of each patient, and
(g) repeating steps (b) to (f) until a desired steady plasma arterial content of the drug is substantially maintained throughout the infusion period. | 0 |
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