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FIELD OF THE INVENTION
[0001] The present invention relates to the field of detecting micro-organisms, in particular detection of bacteria. The methods of the invention are highly sensitive and have numerous applications. Methods and kits are described which rely upon a novel indicator of bacterial viability.
BACKGROUND TO THE INVENTION
[0002] Measuring the presence and levels of certain molecules which are associated with cell viability is important in a number of contexts. For example, measuring levels of ATP is useful in mammalian cells for growth analysis and toxicology purposes.
[0003] Culture approaches can be used to detect small numbers of bacteria but such techniques require several days to complete, especially when attempting to detect small numbers of bacteria and also when detecting slower growing micro organisms.
[0004] Alternatively, tests may be carried out based upon measuring the presence of a molecule which can be linked to the presence in the sample of a contaminant cell or organism. The most commonly detected molecule is Adenosine Triphosphate (ATP). Detection of DNA and RNA has also been proposed, although the correlation between the presence of DNA and RNA and viability is not clear-cut due to the variable persistence of nucleic acids in cells post death (Keer & Birch, Journal of Microbiological Methods 53 (2003) 175-183). Detection of adenylate kinase as an indicator of viability has also been proposed (Squirrell D J, Murphy M J, Leslie R L, Green J C D: A comparison of ATP and adenylate kinase as bacterial cell markers: correlation with agar plate counts. In Bioluminescence and chemiluminescence progress and current applications. Edited by: Stanley R A, Kricka L J. John Wiley and Sons; 2002 and WO 96/02665)
[0005] A routinely employed method for determining ATP levels involves the use of bioluminescence. The method uses the ATP dependency of the reaction in which light emitting luciferase catalyzes oxidation of luciferin. The method may be used to measure relatively low concentrations of ATP. Kits useful for detecting ATP using bioluminescence are commercially available from Roche, New Horizons Diagnostics Corp, Celsis etc.
[0006] A number of problems exist with respect to bioluminescence detection. For example, detection of microbial ATP only, in the presence of ATP from non-microbial sources can be a problem. This problem has been solved to a certain degree by use of filters which can separate bacteria from non-bacterial sources of ATP, thus providing a more accurate signal.
[0007] In addition, chemicals and/or metals in a sample can interfere with the bioluminescence reaction. This is of particular relevance, for example, where surface contamination is being measured following cleaning of a surface using cleaning agents. The chemical cleaning agents interfere with the luciferase catalysed reaction, and thus in some cases lead to false negative results, where microbial or other contaminant ATP is present but the bioluminescence reaction is not effective.
[0008] Ligases are enzymes which catalyze ligation of nucleic acid molecules. The ligation reaction requires either ATP or NAD+ as co-factor depending upon the ligase concerned.
SUMMARY OF THE INVENTION
[0009] The present invention identifies ligases, in particular NAD-dependent ligases, as a useful indicator of the presence of a (viable) micro-organism or microbe.
[0010] Accordingly, the invention provides for the use of NAD-dependent ligase activity as an indicator of the presence of a (viable) micro-organism in a sample. The link between NAD-dependent ligase activity and viability is central to the invention (Korycka-Machala et al., Antimicrobial Agents and Chemotherapy, August 2007, p 2888-2897) since it allows the activity of this enzyme to be used as an indicator of viable microbial cells, in particular of bacterial origin, in the sample.
[0011] Similarly, the invention provides a method of detecting an NAD-dependent ligase as an indicator of the presence of a micro-organism in a sample comprising:
[0012] (a) contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample,
[0013] (b) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and
[0014] (c) specifically determining the presence (and/or the amount) of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the micro-organism.
[0015] Thus, the methods of the invention are useful for identifying all micro-organisms in which an NAD-dependent ligase is (or has been) expressed. The methods may therefore be coined as a method of detecting an NAD-dependent ligase expressing micro-organism in a sample. In certain embodiments, the methods of the invention are applied to the detection of viable micro-organisms and thus may be considered as a method for detecting a viable micro-organism in a sample. In particular, the methods may be useful for identifying bacteria or micro-organisms in which the NAD-dependent ligase gene is essential for viability. However, micro-organisms, such as bacteria, recently rendered non-viable (for example through treatment with an anti-bacterial as discussed herein) may retain detectable NAD-dependent ligase activity until the enzyme is degraded. Thus, reference to micro-organisms may include recently viable micro-organisms, up until the point where NAD-dependent ligase has been degraded, as appropriate. If a distinction between viable and recently viable micro-organisms is required, a simple time course or comparison of NAD-dependent ligase activity between two or more time points, under appropriate conditions, should be sufficient to determine whether NAD-dependent ligase activity increases, persists or diminishes over time. If the NAD-dependent ligase activity persists for, or increases over, an extended period or at (a) later time point(s) (compared to the initial measurement), this may indicate that the micro-organisms are viable. If NAD-dependent ligase activity diminishes at (a) later time point(s), this may indicate that the detected activity was from recently viable micro-organisms. Detection methods are discussed in detail herein. In specific embodiments, the micro-organism is a bacterium. All (eu)bacteria are believed to contain at least one gene encoding an NAD-dependent (DNA) ligase. In a more specific embodiment, the bacterium is a eubacterium. However, NAD-dependent ligases have also been found in thermophillic and cold-resistant bacteria and accordingly, the methods of the invention may be more generally applicable (Wilkinson et al., Molecular Microbiology (2001) 40(6), 1241-1248). Thus, the bacteria may be mesophillic and/or thermophillic bacteria for example.
[0016] A “sample” in the context of the present invention is defined to include any sample in which it is desirable to test for the presence of a micro-organism, in particular a bacterium, expressing an NAD-dependent ligase. Thus the sample may comprise, consist essentially of or consist of a clinical sample, or an in vitro assay system for example. Samples may comprise, consist essentially of or consist of beverage or food samples or preparations thereof, or pharmaceutical or cosmetic products such as personal care products including shampoos, conditioners, moisturisers etc., all of which are tested for microbial contamination as a matter of routine. The sample may comprise, consist essentially of or consist of tissue or cells and may comprise, consist essentially of or consist of a sputum or a blood sample or a platelet sample for example. In addition, the methods and kits of the invention may be used to monitor contamination of surfaces, such as for example in locations where food is being prepared. Contamination is indicated by the presence of NAD-dependent ligase activity. The contamination may be from any microbial source, in particular bacterial contamination. Furthermore, the invention is also useful in monitoring environmental conditions such as water supplies, wastewater, marine environments etc. The invention is also useful in monitoring bacterial growth in fermentation procedures and in air sampling where bacteria or spore content can be assessed in hospital, industrial facilities or in biodefence applications.
[0017] By “NAD-dependent ligase” is meant a DNA ligase which depends upon the nicotinamide adenine dinucleotide (NAD+) cofactor for activity. NAD-dependent ligases can be distinguished from ATP-dependent ligases which rely upon the cofactor ATP for activity. The activity of the NAD-dependent ligase is the formation of a phosphodiester bond between the 5′ end of a nucleic acid molecule and the 3′ end of a nucleic acid molecule.
[0018] The methods of the invention rely on the fact that if there are one or more (viable) micro-organisms, in particular bacteria, present in the sample, the NAD-dependent ligase will be present. This enzyme can thus, under appropriate conditions, catalyse a ligation reaction to generate a novel detectable nucleic acid molecule (in a subsequent process). The novel nucleic acid molecule may be detected by any suitable means, thereby allowing a determination of the presence of the micro-organisms in the sample under test.
[0019] Thus, if the micro-organism is not present in the sample, there will be no NAD-dependent ligase activity in the sample and thus the novel detectable nucleic acid molecule will not be generated.
[0020] The methods of the present invention provide significant technical advantages, due in large part to the fact that a novel nucleic acid molecule is generated as part of the method. In the methods of the present invention, unreacted nucleic acid molecule will not contribute to the signal, and as a result no false positive signals should be produced when the methods are carried out.
[0021] Furthermore, the method is highly sensitive providing detection of the NAD-dependent ligase present in the sample down to femtogram and possibly even attogram levels. The sensitivity is derived from the fact that every bacterial cell contains thousands of enzyme molecules, and thus each can catalyse multiple ligation events under suitable conditions. Every bacterial cell must produce ligase activity to repair ongoing genomic damage and this essential activity contributes to its usefulness as a marker for the presence of viable microbial cells. Thus unlike PCR approaches, which must target one or a few copies of a gene per cell or use additional steps or reagents to detect ribosomal or messenger RNA, the approach described herein targets the detection of multiple copies of the NAD-dependent ligase per cell in a simple assay format. The sensitivity is further enhanced compared to other approaches in that each copy of the ligase is able to modify multiple (hundreds or thousands) substrate nucleic acid molecules which can each then be detected.
[0022] A further advantage over ATP detection techniques is that ATP is common to bacterial, fungi and mammalian cells and it is necessary to differentiate between human and bacterial ATP, for example, when performing a bacterial detection or viability test. By targeting a bacterial specific enzyme, NAD-dependent ligase, there is specificity for the detection of bacteria. Unlike bacterial ligases which require NAD+ as a cofactor, mammalian and fungi ligases have a requirement for ATP. As NAD+ may be provided in the assay, in particular in large molar excess, interference by mammalian and fungal ligases can be avoided.
[0023] As stated herein, the first step in the method comprises, consists essentially of or consists of contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample. Any suitable ligatable molecule which can be specifically detected once ligated may be utilised in the methods of the invention.
[0024] For the avoidance of doubt, it is hereby stated that the ligated nucleic acid molecule is generally a novel detectable nucleic acid molecule which has a different overall structure to that of the original (substrate) nucleic acid molecule. Thus, the novel detectable nucleic acid molecule may contain additional nucleotides such that the novel nucleic acid molecule may be uniquely identified, for example by amplification utilising primers which can only bind and produce an amplification product using the ligated nucleic acid molecule as a template. However, it may be that only one strand is extended as compared to the (original) substrate nucleic acid molecule, for example the ligase may seal a nick in one strand of a double stranded substrate molecule.
[0025] The substrate nucleic acid molecules for use in the methods, and inclusion in the kits, of the invention, must be of sequence and structure such that the NAD-dependent ligase can act on the molecule to produce a detectable ligated (novel) nucleic acid molecule.
[0026] Suitable substrate nucleic acid molecules for use in the invention are set forth as SEQ ID Nos 1 to 4, 7 and 8 and described in more detail in the experimental section below. It is noted that variants of these sequences may be utilised in the present invention. For example, additional flanking sequences may be added. Variant sequences may have at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% nucleotide sequence identity with the nucleotide sequences of the substrate nucleic acid molecules set forth as SEQ ID NOs 1 to 4, 7 and 8. The nucleic acid molecules may incorporate synthetic nucleotide analogues as appropriate or may be RNA or PNA based for example, or mixtures thereof. They may be labelled, such as usin a fluorescent label, or FRET pair, in certain embodiments to facilitate detection. Suitable detection methods are described herein.
[0027] “Nucleic acid” is defined herein to include any natural nucleic acid and natural or synthetic analogues that are capable of being ligated by an NAD-dependent ligase in order to generate a ligated (novel detectable) nucleic acid molecule. The ligation reaction may involve either joining of two DNA molecules or sealing a nick in a nucleic acid molecule to produce a detectable ligated nucleic acid molecule for example. Suitable nucleic acid molecules may be composed of, for example, double or single-stranded DNA and double or single-stranded RNA. Nucleic acid molecules which are partially double-stranded and partially single-stranded are also contemplated in certain embodiments of the invention. In certain embodiments the substrate nucleic acid molecule comprises, consists essentially of or consists of dsDNA, to include nicked dsDNA. The term “nucleic acid” encompasses synthetic analogues which are capable of being ligated by NAD-dependent ligase in a sample in an analogous manner to natural nucleic acids, for example nucleic acid analogues incorporating non-natural or derivatized bases, or nucleic acid analogues having a modified backbone. In particular, the term “double-stranded DNA” or “dsDNA” is to be interpreted as encompassing dsDNA containing non-natural bases.
[0028] Though the nucleic acid substrate may comprise, consist essentially of or consist of a blunt-ended double-stranded DNA molecule, in a separate embodiment the nucleic acid substrate for the NAD-dependent ligase comprises, consists essentially of or consists of two double stranded DNA molecules with a complementary overhang and 5′ phosphate groups at the ends to be joined. In one specific embodiment, the complementary overhang is between 2 and 10, such as 3 or 5 base pairs. In an alternative embodiment, the nucleic acid substrate comprises, consists essentially of or consists of a partially double-stranded DNA molecule with a nick containing a 5′ phosphate. Synthesized nucleic acid molecules are commercially available and can be made to order with a terminal 5′ phosphate group attached. This has the technical advantage that 100% of the nucleic acid molecules used in the methods of the invention will be labelled with a 5′ phosphate group. Furthermore, the nucleic acid substrates can be designed to specification, for example to include biotin molecules for subsequent post-ligation capture if so desired, as described herein.
[0029] Thus, in embodiments of the invention, the novel nucleic acid molecule that is detected is generated by ligation of the 3′ end of the nucleic acid molecule to the 5′ end of a further nucleic acid molecule. In these embodiments, if the ligase is present in the sample, it will catalyse the ligation and a ligated nucleic acid molecule (incorporating an overall novel sequence) will be formed which can be detected by a subsequent process, as detailed herein (such as a nucleic acid amplification process for example).
[0030] Thus, the substrate nucleic acid molecule may, in fact, comprise, consist essentially of or consist of two or more nucleic acid molecules as appropriate. This applies generally to the methods and kits of the invention.
[0031] In certain embodiments, the nucleic acid substrate comprises, consists essentially of or consists of two double stranded nucleic acid molecules with single-stranded complementary overhangs.
[0032] The 3′ end of nucleic acid substrate molecules that are not productively joined in terms of producing a ligated product which is then detected (desired to be joined) may be blocked with a suitable blocking group in order to ensure that they cannot participate in a ligation reaction. Any appropriate blocking group may be utilised.
[0033] In specific embodiments, the nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample comprises, consists essentially of or consists of a nicked double stranded nucleic acid molecule. In specific embodiments, the overall substrate may be made up of three specific single stranded DNA (ssDNA) molecules. Two or more of the ssDNA molecules may be of identical sequence. One ssDNA molecule may hybridize to the other two nucleic acid molecules in a manner such that a double stranded region is formed that contains a nick. NAD-dependent ligase activity, if present in the sample, may seal the nick thus producing a double stranded DNA molecule which can be detected according to the methods described herein. Suitable examples of such an arrangement include the nucleic acid molecules set forth as SEQ ID No:7 and 8 (two copies), as discussed herein.
[0034] In further specific embodiments, the nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample comprises, consists essentially of or consists of two nucleic acid molecules which can be ligated together.
[0035] Preferably, the nucleic acid substrate is present in excess, and in particular in large molar excess, over the ligase in the sample. This is an important technical distinction over prior art methods. Because a novel ligated nucleic acid molecule is detected, only the presence of this molecule in the sample is essential for the detection methods to work effectively. Thus, it is not detrimental to the methods of the invention if other nucleic acid molecules are present in the sample such as from the bacteria to be detected or from mammalian or fungal sources which may be found in the sample to be tested for example.
[0036] Preferably, the substrate nucleic acid molecules are designed such that they do not have high levels of homology with the genome of the one or more bacteria or other micro-organisms which produce the NAD-dependent ligase which is to be detected in the sample. This means that, even in the presence of contaminating nucleic acid molecules, only the novel ligated nucleic acid molecule may be detected. Thus, the substrate should have sufficiently low levels of sequence identity with the genomic DNA of the bacteria to be detected to prevent non-specific amplification of genomic DNA producing a false positive result. The sequence of the substrate may thus be designed with the target bacteria in mind. In particular, the primers for amplifying specifically the novel ligated nucleic acid molecule are designed such that they do not produce an amplification product from the bacterial genomic DNA. For example, the substrate and primers may incorporate complementary non-naturally occurring molecules which can base pair with each other, and allow specific amplification of bacterial genomic DNA. As an example, pyDAD and puADA may be incorporated into primers and substrate molecules as appropriate (Sismour et al., Nucleic Acids Research, 2004, Vol. 32, No. 2: 728-735).
[0037] Preferably, the homology is less than about 5%, less than about 10%, less than about 12.5%, less than about 15%,less than about 20%, less than about 30%, less than about 40%, 50%, 60%, 70% or 80% sequence identity with the corresponding nucleotide sequence from the one or more bacteria or other micro-organisms which produce the NAD-dependent ligase which is to be detected in the sample. In one embodiment, there is no sequence identity with the corresponding nucleotide sequence from the one or more bacteria or other micro-organisms which produce the NAD-dependent ligase which is to be detected in the sample over approximately 10, 20, 30, 40 or 50 contiguous nucleotides. In another embodiment, there is less than about 10% or less than about 12.5%, 15%, 20%, 30%, 40%, 50% or 60% sequence identity over approximately 10, 20, 30, 40 or 50 contiguous nucleotides with the corresponding nucleotide sequence from the one or more bacteria or other micro-organisms which produce the NAD-dependent ligase which is to be detected in the sample.
[0038] The second step of the methods of the invention comprises, consists essentially of or consists of incubating the sample under conditions suitable for NAD-dependent ligase activity. Any suitable conditions may be employed, as would be readily determined by one of skill in the art. For example ligation may occur at any temperature between around 4 and 80° C. depending upon the ligase concerned (thermophilic bacteria may be detected using reactions incubated at higher temperatures than mesophilic bacteria for example). Preferred incubation temperatures are between around 4 and 40° C., more preferably between around 20 and 37° C. and most preferably at room temperature for general (viable) bacterial detection. Suitable incubation times may be between approximately 10 minutes and 10 hours, such as between around 30 minutes, 1 hour or 2 hours and 5, 6, 7, 8 or 9 hours. Incubation may occur in a suitable buffer. Commercially available ligase buffers include E. coli ligase buffer available from NEB. Suitable incubation conditions for use of a ligase are well known in the art and are recommended with commercially available ligases.
[0039] In specific embodiments, the conditions suitable for NAD-dependent ligase activity include supplying the sample with additional NAD+. The rationale behind this approach of adding NAD+ is that it presents optimal conditions for NAD-dependent ligase activity. Accordingly, NAD-dependent ligase activity in the sample is heavily favoured over any other enzyme activity, such as ATP-dependent ligase activity, in the sample. This is particularly relevant in situations where the sample may contain additional enzyme activity, such as ATP-dependent ligase activity, which could lead to production of a ligated nucleic acid molecule even in the absence of viable bacteria in the sample (i.e. a false positive result). Thus, by actively promoting NAD-dependent ligase activity in the sample, if present, it is possible to identify the presence of viable micro-organisms, in particular bacteria, in the sample even in the presence of potential competing enzyme activity. As is shown in the experimental section below, addition of NAD+ to the sample improves the sensitivity of detection.
[0040] In alternative embodiments, no additional NAD+ is added to the sample. Accordingly, here the methods rely upon endogenous NAD+ to support NAD-dependent ligase activity. In the absence of (viable) bacterial cells, there may be no detectable NAD-dependent ligase activity. If bacterial cells are present in the sample, the endogenous NAD+ allows the NAD-dependent ligase to act on the substrate nucleic acid molecule to produce a ligated nucleic acid molecule which is then detected. As shown in the experimental section of the description herein, such methods may permit greater discrimination in signal, since non-viable cells have lower levels of NAD+.
[0041] Depending upon the sample type utilised and the particular applications of the methods of the invention, it may be desirable to inhibit any ATP-dependent ligase activity in the sample. In particular, the sample may include eukaryotic cells and/or prokaryotic cells in which an ATP dependent ligase is expressed. Such ATP-dependent ligases may have the ability to act on the substrate nucleic acid molecules to produce a ligated nucleic acid molecule and thus lead to production of false positive results. Accordingly, the methods of the invention may comprise the step of inhibiting ATP-dependent ligase activity in the sample. Inhibition of ATP-dependent ligase activity may be achieved by any suitable means. In one embodiment, ATP-dependent ligase activity is inhibited by depletion of (its cofactor) ATP from the sample. This may be achieved by burning off the ATP in the sample, for example using an enzyme such as luciferase prior to adding the substrate nucleic acid to the sample. ATP-dependent ligase activity may be directly inhibited, for example by adding a competitive substrate. A suitable competitive substrate may comprise, consist essentially of or consist of dATP (Wood W B et al. (1978) J. Biol. Chem. 253, 2437). Incubation conditions may also be altered in order to inhibit ATP-dependent ligase activity without adversely affecting NAD-dependent ligase activity in the sample. For example, use of high concentration of monovalent cations, such as greater than around 200 mM may allow selective inhibition of ATP-dependent ligase activity (Okazaki, R. et al. (1968) Proc. Natl. Acad. Sci USA 59, 598 and Edwards, J B et al. (1991) Nucl Acids Res. 19, 5227).
[0042] In further embodiments, the methods of the invention involve capture of any ATP-dependent ligase from the sample prior to determining NAD-dependent ligase activity. This is another way of preventing ATP-dependent activity from influencing the results obtained. The ATP-dependent ligase may be captured from the sample by any suitable means. For example, the ATP-dependent ligase may be captured using a specific reagent, or capture agent, which binds to the ATP-dependent ligase. The binding may be selective for ATP-dependent ligases and/or ATP-dependent ligases from a specific source as appropriate. In a specific embodiment, the ATP-dependent ligase is captured from the sample using an immobilized nucleic acid molecule. Alternative capture agents include antibodies (and derivatives and variants thereof as defined herein), lectins, receptors etc.
[0043] Reagents for capture of a ligase (ATP or NAD-dependent, as appropriate) may be immobilised on a solid support in one embodiment. Any suitable solid support may be employed. The nature of the solid support is not critical to the performance of the invention provided that the ligase may be effectively immobilized thereon (without adversely affecting enzyme activity in the case of NAD-dependent forms). Non-limiting examples of solid supports include any of beads, such as polystyrene beads and derivatives thereof and paramagnetic beads, affinity columns, microtitre plates etc. Biotin and streptavidin may be utilised to facilitate immobilisation as required. Methods of immobilization are well known in the art and discussed herein.
[0044] In specific embodiments, the methods of the invention further comprise lysis of micro-organisms/bacteria in the sample to release NAD-dependent ligase. The lysis is preferably selective and thus leaves non micro-organism and in particular non-bacterial cells intact. This facilitates detection of NAD-dependent ligase activity in the sample. This step is preferably carried out before the sample is contacted with the nucleic acid substrate, although this is not essential. Suitable agents for lysing bacterial cells selectively are known in the art and include bacterial protein extraction reagents such as B-PER(Pierce) for example. Other conditions may include sonication or French Press for example. However, lysis may not be essential in all embodiments of the invention. In particular, increasing the permeability of the bacterial cell wall and/or membrane may in certain embodiments be sufficient to enable detection of NAD-dependent ligase activity according to the methods of the invention. Suitable agents and techniques for achieving this increase in permeability are known in the art.
[0045] A further agent useful in various applications of the present invention is lysostaphin (AMBI). Lysostaphin is an endopeptidase specific for the cell wall peptidoglycan of staphylococci and thus can be used to specifically lyse staphylococcal cells.
[0046] The lysostaphin gene has been cloned and can be produced recombinantly. However, the recombinant form commercially available (under the trade name AMBICIN® L) has been found to contain a number of significant impurities relevant to the present invention. In particular, commercially available recombinant lysostaphin includes both nuclease and ligase activity. This is detrimental to the performance of the present invention which relies upon detection of NAD-dependent ligase activity on a nucleic acid based substrate.
[0047] In order to overcome the problems with the commercially available lysostaphin, the inventors have devised a process which deactivates the ligase and/or nuclease activity in the preparation whilst retaining the endopeptidase activity of the lysostaphin. Accordingly, the invention provides a lysostaphin preparation which is substantially free from nuclease and/or ligase contaminants (and which retains endopeptidase activity). The invention also provides a method for producing a lysostaphin preparation which is substantially free from nuclease and/or ligase contaminants comprising heating a lysostaphin preparation which contains nuclease and/or ligase contaminants under conditions whereby nuclease and/or ligase activity is inhibited and/or reduced whereas (endopeptidase) activity of the lysostaphin is substantially unaffected. Accordingly, in a further aspect the invention provides a lysostaphin preparation which is substantially free from nuclease and/or ligase contaminants produced by heating a lysostaphin preparation which contains nuclease and/or ligase contaminants under conditions whereby nuclease and/or ligase activity is inhibited and/or reduced whereas (endopeptidase) activity of the lysostaphin is substantially unaffected.
[0048] The heating may be to a temperature of between around 50 and 60° C. In specific embodiments, the lysostaphin preparation is heated to a temperature of around 55° C. since this temperature has been shown to be particularly effective in terms of removing contaminant ligase and/or nuclease activity, whilst retaining (endopeptidase) activity of the lysostaphin.
[0049] The preparation may be heated for a suitable period of time. For example, the preparation may be heated for a period of between 1 and 30 minutes such as between 5 and 20 minutes. Longer treatment times may be desirable where lower heating temperatures are employed and vice versa. A particularly suitable treatment is carried out for around 5 minutes. This may be at around 55° C. in specific embodiments.
[0050] Lysostaphin may be included in a suitable ligase buffer in certain embodiments. Such a ligase buffer is particularly useful in the methods of the invention and may include standard components such as salts, detergents, proteins etc. One specific example is described in the experimental section herein and includes MgCl 2 , DTT, BSA, NAD+ and Tris (pH8). Thus, in one aspect the invention provides a buffer containing NAD+ and lysostaphin, in particular a lysostaphin of the invention. Supplementing the buffer with NAD+ has benefits in terms of promoting NAD-dependent ligase activity as discussed herein.
[0051] In further embodiments, the methods of the invention involve capture of any NAD-dependent ligase from the sample. This allows concentration of NAD-dependent ligase activity from the sample and may also allow removal of any inhibitors of enzyme activity which may be found in the sample (through washing for example). The NAD-dependent ligase may be captured from the sample by any suitable means. It is preferred that the NAD-dependent ligase is captured using a specific reagent which binds to the NAD-dependent ligase. The binding may be selective for NAD-dependent ligases and/or NAD-dependent ligases from a specific source as appropriate. In specific embodiments, the NAD-dependent ligase is captured from the sample using an immobilized nucleic acid molecule. More specifically, the immobilized nucleic acid molecule may be the nucleic acid molecule which acts as substrate for NAD-dependent ligase activity in the sample.
[0052] In further embodiments the bacterial ligase can be captured from the sample using the nucleic acid substrate immobilized onto a solid surface. For example, in one method the DNA substrate could be immobilized to streptavidin beads through a biotin at the 3′ end of one or more of the DNA strands forming the nucleic acid substrate. Any bacterial ligase in a given solution can covalently bind to the 3′ hydroxyl of the immobilized DNA substrate and can be captured for subsequent ligation. The advantage of this embodiment is that the ligase can be captured and concentrated from a large volume of solution which can enhance sensitivity of detection. Thus, the methods of the invention may advantageously be utilised to identify or detect bacteria in large volume and/or diluted samples. In addition, the ligase is purified from the bacterial extract which may enhance the activity of the enzyme. Where the substrate nucleic acid molecule comprises of two or more nucleic acid molecules, each of the molecules may be immobilized as appropriate. Each may be immobilized on the same or a separate solid surface as desired.
[0053] In other embodiments, the NAD-dependent ligase may be captured using a reagent which may be protein and/or nucleic acid based for example. The reagent may be an antibody, a lectin, a receptor and/or a nucleic acid based molecule. The term “antibody” incorporates all derivatives and variants thereof which retain antigen (NAD-dependent ligase) binding capabilities. Both monoclonal and polyclonal antibodies may be utilised. Derivatised versions, which may be humanized versions of non-human antibodies for example, are also contemplated. Derivatives include, but are not limited to, heavy chain antibodies, single domain antibodies, nanobodies, Fab fragments, scFv etc.
[0054] Due to the fact that NAD-dependent ligases share high levels of homology with one another whilst being dissimilar to ATP-dependent ligases (Wilkinson et al., Molecular Microbiology (2001) 40(6), 1241-1248), use of an NAD-dependent ligase specific reagent to capture NAD-dependent ligase represents one useful way of accounting for any ATP-dependent ligase activity which could feasibly be present in the original sample. Moreover, due to the high homology levels, it should also be possible to utilise a generic reagent which can capture NAD-dependent ligase generally. This may be any kind of reagent as discussed above, but is preferably a nucleic acid based reagent, such as a ligatable substrate, or an antibody or derivative thereof. For example, the antibody may be specifically raised against antigens incorporating the conserved motifs from NAD-dependent ligase amino acid sequences (see FIG. 2 of Wilkinson et al., Molecular Microbiology (2001) 40(6), 1241-1248 for example).
[0055] In further embodiments, depending upon the application to which the methods of the invention are put, it may be desirable to distinguish the source of the NAD-dependent ligase. According to such embodiments, a reagent of sufficient specificity is utilised to capture the NAD-dependent ligase of interest. Any specific reagent, which may be protein or nucleic acid based may be utilised. Examples include lectins, receptors, antibodies, DNA and RNA. For example, antibodies may be raised against antigens taken from the non-conserved regions of the NAD-dependent ligase of interest—especially since the amino acid sequence of many ligases are in the public domain (see FIG. 2 of Wilkinson et al., Molecular Microbiology (2001) 40(6), 1241-1248 for example).
[0056] Reagents for capture of an NAD-dependent ligase may be immobilised on a solid support in one embodiment. Any suitable solid support may be employed. The nature of the solid support is not critical to the performance of the invention provided that the NAD-dependent ligase may be immobilized thereon without adversely affecting enzyme activity. Non-limiting examples of solid supports include any of beads, such as polystyrene beads and derivatives thereof and paramagnetic beads, affinity columns, microtitre plates etc. Biotin and streptavidin may be utilised to facilitate immobilisation as required.
[0057] Similarly, immobilization chemistry is routinely carried out by those skilled in the art. Any means of immobilization may be utilised provided that it does not have an adverse effect on the methods of the invention, especially in terms of specificity and sensitivity of detection of the ligated nucleic acid molecule produced as an indicator of the presence of a viable micro-organism in the sample.
[0058] Once the NAD-dependent ligase has been captured, the immobilised enzyme may be washed to remove inhibitory materials that may affect the subsequent detection process. Thus, in certain embodiments, the method further comprises, consists essentially of or consists of a washing step prior to detection of the novel (ligated) nucleic acid molecule. Washing may utilise any suitable buffer or wash solution, and may include components such as EDTA and Tris-HCl. Suitable wash solutions are well known to those of skill in the art.
[0059] In other embodiments, the methods of the invention comprise, as a preliminary step, specific capture of the micro-organism, and in particular bacterium, from a starting sample to produce a test sample in which only the specific bacterium of interest is present. In certain embodiments, the invention provides for a method in which the sample is initially filtered in order to concentrate the one or more bacterial cells or other micro-organisms (as described above). More specific detection of certain bacterial cells or micro-organisms may require specific filtration in order to separate these cells from other (NAD-dependent or ATP dependent) ligase producing cells. Such filters and filtration systems and methods are well known in the art and commercially available (for example from New Horizons Diagnostics Inc.). Specific capture may also be achieved via a suitable reagent. Any specific reagent, which may be protein or nucleic acid based may be utilised. Examples include lectins, receptors, antibodies (and derivatives thereof), DNA and RNA, as discussed herein, which discussion applies mutatis mutandis.
[0060] The methods of the invention may involve purification of the (novel) ligated nucleic acid molecule prior to detection. Any suitable purification technique may be employed, as are well known in the art. For example nucleic acid may be isolated and run on a gel and the product of the expected size purified prior to detection. Immobilisation of the substrate nucleic acid molecule as described herein may also facilitate purification of the ligated nucleic acid molecule since the ligated nucleic acid molecule will also be immobilized.
[0061] In certain embodiments, unligated substrate molecules are selectively removed from the sample or otherwise modified (to prevent their detection) prior to the detection of the ligated nucleic acid molecule. This may be carried out to prevent unligated substrate influencing the sensitivity and/or specificity of detection of the ligated nucleic acid molecules. In specific embodiments, this is achieved by a treatment step employing selective nucleases. In particular, one or more exonucleases may be employed to remove unligated substrate molecules. In specific embodiments, 3′-5′ exonucleases such as ExoIII, ExoI and/or ExoT are employed to digest unligated substrate molecules.
[0062] By controlling the incubation conditions, in particular the temperature and time period of incubation, unligated substrates may be digested but ligated nucleic acid molecules (combining two or more ligated substrates) remain in tact so that they may be detected, especially at the ligation boundary as discuss herein. A combination of dsDNA specific 3′-5′ exonucleases, such as ExoIII and one or more ssDNA specific 3′-5′ exonucleases such as ExoI and/or ExoT may advantageously be employed where the ligated nucleic acid molecule is formed from at least three substrate nucleic acid molecules which together form a double stranded region including a nick which is ligated by NAD-dependent ligase activity in the sample. The dsDNA 3′-5′ exonuclease may act to digest the dsDNA portion to produce ssDNA. If the nick has not been sealed by NAD-dependent ligase, the ssDNA 3′-5′ exonuclease may then begin digestion at the ligation site thus removing unligated substrate that could potentially influence the detection reaction. ExoIII may be particularly useful since it does not initiate efficiently at 3′ overhangs (see molecular Cloning—A Laboratory Manual, Third Edition, Sambrook and Russell (2001) (Cold Spring Harbour Laboratory Press). By appropriate substrate design, such as using the substrates described herein, such as those comprising, consisting essentially or consisting of the nucleotide sequences set forth as SEQ ID Nos 7 and 8, efficient and specific removal of unligated substrate molecules may be achieved.
[0063] Nuclease treatment may be carried out for a suitable period of time such as between 10 minutes and 1 hour, in particular for 30 minutes, and at a suitable temperature such as between 20 and 40° C., in particular at 37° C. The nucleases may then be inactivated to prevent digestion of ligated nucleic acid molecules. Any suitable conditions may be employed. For example, nucleases may be inactivated by treatment at an elevated temperature, such as over 60° C. or between 50° C. and 100° C., in particular at 95° C. This may be carried out for any appropriate amount of time, such as for 2 to 10 minutes, in particular around 5 minutes.
[0064] The methods of the invention may incorporate suitable controls. This may be useful in conjunction with certain sensitive detection techniques, such as nucleic acid amplification techniques (as described herein) to ensure that accurate results have been obtained. For example, the controls may incorporate testing a sample in which NAD-dependent ligase activity is known to be present. If no ligated nucleic acid molecule is produced when the substrate is added to this sample, it is clear there is a problem for example with the reagents used in the methods or with the detection technique. A suitable negative control may be a sample in which there is known to be no NAD-dependent ligase activity. Again, a positive result/detection of similar levels of product as are found in the test sample is an indication that there is a problem. A control in which no nucleic acid based substrate molecule is added may also be employed to ensure the methods are not detecting an unrelated ligation event. All combinations and permutations of appropriate controls are envisaged in the present invention. Suitable controls for use in nucleic acid amplification reactions are employed in specific embodiments of the invention, as described herein.
[0065] In preferred embodiments of the invention, the novel nucleic acid molecule, produced according to the presence of NAD-dependent ligase activity in the sample (as an indicator of the presence of one or more (viable) micro-organisms, in particular bacteria in the sample), is detected using nucleic acid amplification techniques.
[0066] This serves to make the methods of the invention maximally sensitive. Such amplification techniques are well known in the art, and include methods such as PCR, NASBA (Compton, 1991), 3SR (Fahy et al., 1991), Rolling circle replication, Transcription Mediated Amplification (TMA), strand displacement amplification (SDA) Clinical Chemistry 45: 777-784, 1999, the DNA oligomer self-assembly processes described in U.S. Pat. No. 6,261,846 (incorporated herein by reference), ligase chain reaction (LCR) (Barringer et al., 1990), selective amplification of target polynucleotide sequences (U.S. Pat. No. 6,410,276), arbitrarily primed PCR (WO 90/06995), consensus sequence primed PCR (U.S. Pat. No. 4,437,975), invader technology, strand displacement technology and nick displacement amplification (WO 2004/067726). The list above is not intended to be exhaustive. Any nucleic acid amplification technique may be used provided the appropriate nucleic acid product is specifically amplified.
[0067] Amplification is achieved with the use of amplification primers specific for the sequence of the novel/ligated nucleic acid molecule which is to be detected. In order to provide specificity for the nucleic acid molecules primer binding sites corresponding to a suitable region of the sequence may be selected. The skilled reader will appreciate that the nucleic acid molecules may also include sequences other than primer binding sites which are required for detection of the novel nucleic acid molecule produced by the NAD-dependent ligase activity in the sample, for example RNA Polymerase binding sites or promoter sequences may be required for isothermal amplification technologies, such as NASBA, 3SR and TMA.
[0068] One or more primer binding sites may bridge the ligation boundary of the substrate nucleic acid molecule such that an amplification product is only generated if ligation has occurred, for example. Alternatively, primers may bind either side of the ligation boundary and direct amplification across the boundary such that an amplification product is only generated (exponentially) if the ligated nucleic acid molecule is formed. As discussed above, primers and the substrate nucleic acid molecule(s) may be designed to avoid non-specific amplification of bacterial genomic DNA.
[0069] Suitable primers for use in the methods of the invention are set forth as SEQ ID Nos 5 and 6 or 9 and 10 respectively and described in more detail in the experimental section below. These primers form a separate aspect of the invention. It is noted that variants of these sequences may be utilised in the present invention. In particular, additional sequence specific flanking sequences may be added, for example to improve binding specificity, as required. Variant sequences may have at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% nucleotide sequence identity with the nucleotide sequences of the primers set forth in SEQ ID NOs 5 and 6 or 9 and 10. The primers may incorporate synthetic nucleotide analogues as appropriate or may be RNA or PNA based for example, or mixtures thereof. The primers may be labelled, such as with fluorescent labels and/or FRET pairs, depending upon the mode of detection employed.
[0070] Probes may be utilised, again which may be labelled, as desired.
[0071] Thus, in certain aspects, the methods of the invention are carried out using nucleic acid amplification techniques in order to detect the novel nucleic acid molecule produced as a direct result of the action of NAD-dependent ligase activity on the substrate nucleic acid molecule which indicates the presence of a bacterial cell or other NAD-dependent ligase expressing micro-organism in the sample. In certain embodiments the technique used is selected from PCR, NASBA, 3SR, TMA, SDA and DNA oligomer self-assembly. Detection of the amplification products may be by routine methods, such as, for example, gel electrophoresis but is preferably carried out using real-time or end-point detection methods.
[0072] A number of techniques for real-time or end-point detection of the products of an amplification reaction are known in the art. These include use of intercalating fluorescent dyes such as SYBR Green I (Sambrook and Russell, Molecular Cloning—A Laboratory Manual, Third edition), which allows the yield of amplified DNA to be estimated based upon the amount of fluorescence produced. Many of the real-time detection methods produce a fluorescent read-out that may be continuously monitored; specific examples including molecular beacons and fluorescent resonance energy transfer probes. Real-time and end-point techniques are advantageous because they keep the reaction in a “single tube”. This means there is no need for downstream analysis in order to obtain results, leading to more rapidly obtained results. Furthermore keeping the reaction in a “single tube” environment reduces the risk of cross contamination and allows a quantitative output from the methods of the invention. This may be particularly important in the context of the present invention where health and safety concerns may be of paramount importance (such as in detecting potential bacterial contamination of platelet samples for example).
[0073] Real-time and end-point quantitation of PCR reactions may be accomplished using the TaqMan® system (Applied Biosystems), see Holland et al; Detection of specific polymerase chain reaction product by utilising the 5′-3′ exonuclease activity of Thermus aquaticus DNA polymerase; Proc. Natl. Acad. Sci. USA 88, 7276-7280 (1991), Gelmini et al. Quantitative polymerase chain reaction-based homogeneous assay with flurogenic probes to measure C-Erb-2 oncogene amplification. Clin. Chem. 43, 752-758 (1997) and Livak et al. Towards fully automated genome wide polymorphism screening. Nat. Genet. 9, 341-342 (19995) (incorporated herein by reference). This type of probe may be generically referred to as a hydrolytic probe. Suitable hydrolytic/Taqman probes for use in real time or end point detection are also provided. They may comprise, consist essentially of or consist of the nucleotide sequence set forth as SEQ ID NO: 11. The probe is suitably labelled, for example using the labels detailed below.
[0074] In the Molecular Beacon system, see Tyagi & Kramer. Molecular beacons—probes that fluoresce upon hybridization. Nat. Biotechnol. 14, 303-308 (1996) and Tyagi et al. Multicolor molecular beacons for allele discrimination. Nat. Biotechnol. 16, 49-53 (1998) (incorporated herein by reference), the beacons are hairpin-shaped probes with an internally quenched fluorophore whose fluorescence is restored when bound to its target. These probes may be referred to as hairpin probes.
[0075] A further real-time fluorescence based system which may be incorporated in the methods of the invention is Zeneca's Scorpion system, see Detection of PCR products using self-probing amplicons and fluorescence by Whitcombe et al. Nature Biotechnology 17, 804-807 (1 Aug. 1999). Additional real-time or end-point detection techniques which are well known to those skilled in the art and which are commercially available include Lightcycler® technology, Amplifluour® primer technology, DzyNA primers (Todd et al., Clinical Chemistry 46:5, 625-630 (2000)), or the Plexor™ qPCR and qRT-PCR Systems.
[0076] Thus, in further aspects of the invention the products of nucleic acid amplification are detected using real-time or end point techniques. In specific embodiments of the invention the real-time technique consists of using any one of hydrolytic probes (the Taqman® system), FRET probes (Lightcycler® system), hairpin primers (Amplifluour® system), hairpin probes (the Molecular beacons system), hairpin probes incorporated into a primer (the Scorpion® probe system), primers incorporating the complementary sequence of a DNAzyme and a cleavable fluorescent DNAzyme substrate (DzYNA), Plexor qPCR and oligonucleotide blocking systems.
[0077] In certain embodiments, the reaction mixture will contain all of; the sample under test, the substrate nucleic acid molecule(s), reagents, buffers and enzymes required for amplification of the novel (ligated) nucleic acid molecule optionally in addition to the reagents required to allow real time or end-point detection of amplification products. Thus the entire detection method for the NAD-dependent ligase (from the one or more bacterial cells or micro-organisms of interest) may occur in a single reaction, with a quantitative output, and without the need for any intermediate washing steps. Use of a “single tube” reaction is advantageous because there is no need for downstream analysis in order to obtain results, leading to more rapidly obtained results. Furthermore keeping the reaction in a “single tube” environment reduces the risk of cross contamination and allows a quantitative output from the methods of the invention. Also, single tube reactions are more amenable to automation, for example in a high throughput context.
[0078] Alternatively, the methods of the invention may be carried out in step-wise fashion. Thus, in a first step it may first be necessary to prepare the sample in a form suitable for use in the method of the invention. For example, as discussed herein, selective cell lysis or increasing cellular permeability may be required. Capture of NAD-dependent ligase may also be desirable again as described herein. ATP dependent ligase activity may be inhibited etc.
[0079] The methods of the present invention have a number of applications. For example, they have utility in the important field of microbial resistance to existing treatments. Many bacteria are now resistant to a large number of currently available antimicrobial treatments, and certain strains, such as Methicillin Resistant Staphylococcus aureus (MRSA) pose dangerous health risks particularly in a clinical context.
[0080] There is, therefore, a requirement for techniques and assay kits which allow resistance to anti-microbial agents to be readily determined.
[0081] Therefore, according to a further aspect, the invention provides a method of screening for resistance of a bacterial cell or other micro-organism to an agent directed against said cell, bacterium or other micro-organism, the method comprising, consisting essentially of or consisting of the steps of, in a sample:
(a) exposing the bacterial cell or micro-organism to the agent; (b) contacting the sample with a nucleic acid molecule which acts as substrate for NAD-dependent ligase activity in the sample, (c) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and (d) specifically detecting whether there is present (and/or the amount of) a (novel) ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule wherein if there is resistance, the (novel) ligated nucleic acid molecule will be detected (or will be detected at higher levels).
[0086] The same method may also be used as a compound screening method to determine if a new compound, agent or molecule has effect against a particular one or more target bacterial cells or other micro-organisms expressing NAD-dependent ligase as an essential enzyme.
[0087] Thus, in a still further aspect the invention provides a method of screening for agents which are capable of killing or preventing growth of one or more bacterial cells or other appropriate micro-organisms, the method comprising, consisting essentially of or consisting of the steps of, in a sample:
(a) exposing the bacterial cell or micro-organism to the agent; (b) contacting the sample with a nucleic acid molecule which acts as substrate for NAD-dependent ligase activity in the sample, (c) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and (d) specifically detecting whether there is present (and/or the amount of) a (novel) ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule, wherein if the agent is capable of killing or preventing growth of the bacterium or micro-organism the novel nucleic acid molecule will not be detected (or will be detected at lower levels).
[0092] This aspect of the invention may also be utilised as a rapid viability test in compound screening. Thus, a compound, agent or molecule may be screened according to the method to determine whether it is toxic to appropriate cells. Thus, a positive result in the method in terms of detecting the novel nucleic acid molecule would indicate that the compound is of low toxicity to the cells. The method of the invention may also prove to have diagnostic utility, whereby an infection may be specifically and sensitively detected in the early stages when only minimal levels of the infecting bacterial cell or other micro-organism expressing an NAD-dependent ligase are present.
[0093] Therefore, in a further aspect there is provided a method of diagnosing an infection, or a disease associated with the presence of a bacterial cell or other micro-organism in a subject, comprising, consisting essentially of or consisting of the steps of, in a sample obtained from the subject:
(a) contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample, (b) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and (c) specifically determining the presence (and/or the amount of) of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the (viable) bacterium or other micro-organism as an indication of infection or disease.
[0097] In this context the “sample” will generally be a clinical sample. The sample being used will depend on the condition that is being tested for. Typical samples which may be used, but which are not intended to limit the invention, include whole blood, serum, plasma, platelet and urine samples etc. taken from a patient, most preferably a human patient.
[0098] In a preferred embodiment, the test will be an in vitro test carried out on a sample removed from a subject.
[0099] In a further embodiment, the above-described diagnostic methods may additionally include the step of obtaining the sample from a subject. Methods of obtaining a suitable sample from a subject are well known in the art. Alternatively, the method may be carried out beginning with a sample that has already been isolated from the patient in a separate procedure. The diagnostic methods will most preferably be carried out on a sample from a human, but the method of the invention may have diagnostic utility for many animals.
[0100] The diagnostic methods of the invention may be used to complement any already available diagnostic techniques, potentially as a method of confirming an initial diagnosis. Alternatively, the methods may be used as a preliminary diagnosis method in their own right, since the methods provide a quick and convenient means of diagnosis. Furthermore, due to their inherent sensitivity, the diagnostic methods of the invention require only a minimal sample, thus preventing unnecessary invasive surgery. Also, a large but non-concentrated sample may also be tested effectively according to the methods of the invention.
[0101] Thus, the methods of the invention have multiple applications beyond detection of contaminating organisms in a sample. The description provided above with respect to the first aspect of the invention applies mutatis mutandis to the further aspects of the invention and is not repeated for reasons of conciseness. For example, suitable controls may be incorporated for these methods of the invention.
[0102] In specific embodiments the NAD-dependent ligase is derived from a pathogenic micro-organism, in particular a pathogenic bacterium.
[0103] The bacterium may be any bacterium which is capable of causing infection or disease in a subject, preferably a human subject. In one embodiment, the bacteria comprises or consists essentially of or consists of any one or more of Staphylococcus species, in particular Staphylococcus aureus and preferably methicillin resistant strains, Enterococcus species, Streptococcus species, Mycobacterium species, in particular Mycobacterium tuberculosis, Vibrio species, in particular Vibrio cholerae, Salmonella and/or Escherichia coli etc. The bacteria may comprise, consist essentially of or consist of Clostridium species and in particular C. difficile in certain embodiments. C. difficile is the major cause of antibiotic-associated diarrhoea and colitis, a healthcare associated intestinal infection that mostly affects elderly patients with other underlying diseases.
[0104] In certain embodiments, according to these further aspects of the invention, the molecule which is being tested in the method (either for resistance or ability to treat an infection or toxicity to cells) is an antimicrobial compound. In the compound screening methods, any molecule may be tested. Examples include antimicrobial agents, nucleic acid molecules including siRNA (dsRNA) molecules and antisense molecules, small molecules, antibodies and all derivatives thereof including Fab fragments, variable region fragments and single domain antibodies for example provided they retain binding affinity etc. The method may be carried out in a high throughput context to screen large numbers of molecules in a short period of time.
[0105] The antimicrobial agent, in one embodiment, may be taken from the two main types of antimicrobial agents, antibiotics (natural substances produced by micro-organisms) and chemotherapeutic agents (chemically synthesized), or may be a hybrid of the two such as semi-synthetic antibiotics (a subsequently modified naturally produced antibiotic) or synthetic antibiotics (synthesised versions of natural antibiotics).
[0106] Suitable candidate antimicrobial agents may, following a positive result in the methods of the invention in terms of ability to kill or prevent growth of a bacterium or bacterial cell or other suitable micro-organism be tested for at least one or more of the following properties:
(1) the agent should be non-toxic to the subject and without adverse side effects, (2) the agent should be non-allergenic to the subject, (3) the agent should not eliminate the natural flora of the subject, (4) the agent should be stable, (5) the agent should preferably be cheap and readily available/easy to manufacture; and (6) the agent should be sufficiently potent that pathogen resistance does not develop (to any appreciable degree). This feature may be tested according to the methods described above.
[0113] In one embodiment, a combination of multiple suitable antimicrobial agents may be tested for ability to treat an infection and/or for resistance thereto.
[0114] Antibiotics or derivatives thereof which may be tested for resistance and perhaps also for their novel ability to treat certain infections may be selected from the following groups, provided by way of example and not limitation; beta-lactams such as penicillin, in particular penicillin G or V, and cephalosporins such as cephalothin, semi-synthetic penicillins such as ampicillin, methicillin and amoxicillin, clavulanic acid preferably used in conjunction with a semi-synthetic penicillin preparation (such as clavamox or augmentin for example), monobactams such as aztreonam, carboxypenems such as imipenem, aminoglycosides such as streptomycin, kanamycin, tobramycin and gentamicin, glycopeptides such as vancomycin, lincomycin and clindamycin, macrolides such as erythromycin and oleandomycin, polypeptides such as polymyxin and bacitracin, polyenes such as amphotericin and nystatin, rifamycins such as rifampicin, tetracyclines such as tetracycline, semi-synthetic tetracyclines such as doxycycline, chlor tetracycline, chloramphenicol, quinolones such as nalidixic acid and fluoroquinolone and competitive inhibitors such as sulfonamides, for example gantrisin and trimethoprim. Ceftriaxone and/or nitroflurazone may also be utilised.
[0115] The methods of the invention may also be applied to determining the presence of bacteria of interest which are resistant to a designated or specific anti-bacterial agent. Accordingly, the present invention provides a method for determining the presence of bacteria of interest, which are resistant to a specific anti-bacterial agent, in a sample comprising, consisting essentially of or consisting of (the following steps, in particular in the order specified):
[0116] (a) capturing, prior to culture, the bacteria of interest using a specific capture reagent,
[0117] (b) incubating the thus captured bacteria of interest in an incubating medium including the specific anti-bacterial agent,
[0118] (c) exposing the incubated bacteria of interest to an agent capable of causing lysis of the bacteria or of increasing the permeability of the bacterial cell wall to a degree such that the presence of intracellular material from the bacteria can be determined, and
[0119] (d) determining the presence of intracellular material from the bacteria of interest (whose permeability has been increased or which have been lysed).
[0120] The bacteria of interest may be any bacteria which are known to be resistant to a specific anti-bacterial agent. Typically, the bacteria may be infection or disease causing bacteria which are known to have resistance to one or more specific anti-bacterial agents. In certain embodiments, the bacteria comprises or consists essentially of or consists of any one or more of Staphylococcus species, in particular Staphylococcus aureus and most particularly methicillin resistant strains, Enterococcus species, Streptococcus species, Mycobacterium species, in particular Mycobacterium tuberculosis, Vibrio species, in particular Vibrio cholerae, Salmonella and/or Escherichia coli etc. The bacteria may comprise, consist essentially of or consist of Clostridium species and in particular C. difficile in certain embodiments.
[0121] The specific anti-bacterial agent to which the bacteria of interest are resistant may be any specific anti-bacterial agent. The agent is advantageously utilised in step (b) to prevent, inhibit or restrict sensitive bacteria which may have been captured in step (a) from growing. The agent may cause lysis of sensitive bacteria, although that is not essential. The agent may be an antibiotic or a chemotherapeutic agent or may be a hybrid of the two (semi-synthetic or synthesised antibiotic), as discussed herein. Antibiotics or derivatives thereof to which certain bacteria are resistant and which may therefore be employed in the methods of the invention may be selected from those listed herein, which list applies mutatis mutandis.
[0122] In certain embodiments, beta-lactam antibiotics such as ampicillin, methicillin and amoxicillin and in particular methicillin are utilised in the methods. Here, the bacteria may be Staphylococcus aureus, in particular the method may be used to detect MRSA in a sample.
[0123] In this context the “sample” will generally be a clinical sample. The sample being used may depend on the type of resistant bacteria that is being tested for. Typical samples which may be used, but which are not intended to limit the invention, include nasal, groin and armpit swabs etc. taken from a patient, in particular from a human patient. Generally, the methods of this aspect of the invention will be an in vitro test carried out on a sample removed from a subject.
[0124] In further embodiments, the above-described methods may additionally include the step, of obtaining the sample from a subject. Methods of obtaining a suitable sample from a subject are well known in the art. Alternatively, the method may be carried out beginning with a sample that has already been isolated from the patient in a separate procedure. The methods will generally be carried out on a sample from a human, but the method of the invention may have diagnostic utility for many animals.
[0125] Step (a) is designed to capture the bacteria of interest from the general (clinical) sample, which may include other cell types, such as mammalian cells and other bacterial cells. Any suitable specific capture reagent may be employed for this purpose. In certain embodiments the specific capture reagent may be specific only to a particular species of bacteria. In other embodiments the specific capture reagent may be specific to a particular strain of bacteria. For example, the specific capture reagent may allow capture of Staphylococci generally or it may allow capture of S. aureus more specifically, or even only antibiotic resistant strains, such as MRSA, of S. aureus only. The specific capture reagent may be protein and/or nucleic acid based for example. The reagent may be an antibody, a lectin, a receptor and/or a nucleic acid based molecule for example. The term “antibody” incorporates all derivatives and variants thereof which retain antigen binding capabilities. Both monoclonal and polyclonal antibodies may be utilised. Derivatised versions, which may be humanized versions of non-human antibodies for example, are also contemplated. Derivatives include, but are not limited to, heavy chain antibodies, single domain antibodies, nanobodies, Fab fragments, scFv etc.
[0126] In specific embodiments, the specific capture reagent is immobilized on a solid support. Any suitable solid support may be employed. The nature of the solid support is not critical to the performance of the invention provided that the bacteria of interest may be immobilized thereon without adversely affecting growth in the subsequent step. Non-limiting examples of solid supports include any of beads, such as polystyrene beads and derivatives thereof and paramagnetic beads, affinity columns, microtitre plates etc. Biotin and streptavidin may be utilised to facilitate immobilisation as required.
[0127] Similarly, immobilization chemistry is routinely carried out by those skilled in the art. Any means of immobilization may be utilised provided that it does not have an adverse effect on the methods of the invention, especially in terms of specificity and sensitivity of detection of the bacteria of interest.
[0128] Step (b) is important to prevent, inhibit or otherwise restrict growth of any captured bacteria which are susceptible to the specific anti-bacterial agent but which were captured in step (a). This step effectively ensures that resistant bacteria of interest can be easily detected and discriminated from bacteria which are captured but are susceptible to the specific anti-bacterial agent. Any suitable incubating medium may be employed. In specific embodiments, a liquid medium is used. Suitable media for permitting bacterial growth are well known in the art and commercially available. As discussed, the incubating medium contains the specific anti-bacterial agent to control growth of any susceptible bacteria captured in step (a). This ensures background in the methods of the invention is kept low and helps to improve the sensitivity and specificity of detection of bacteria of interest which are resistant to the specific anti-bacterial agent. Of course, since the bacteria of interest are resistant to the agent they will continue to grow, thus allowing their sensitive and specific detection following lysis or an increase in cellular permeability, in steps (c) and (d).
[0129] Step (c) allows the intracellular content of the bacteria of interest to be released, thus permitting the detection of the bacteria of interest in step (d). Any agent capable of causing cell lysis may be utilised. In specific embodiments of the present invention the agent capable of causing cell lysis is selective towards the bacteria of interest. This is not essential, however, due to step (a) which leads to specific capture and step (b) which prevents growth of susceptible bacteria. In certain embodiments, the agent is selective to Staphylococcus aureus. In more specific embodiments, the agent capable of causing cell lysis is lysostaphin. The lysostaphin may be a commercially available lysostaphin or may be a lysostaphin of the present invention, which discussion applies mutatis mutandis.
[0130] In other embodiments, the agent capable of causing cell lysis is a bacteriophage. The bacteriophage may be selective to the bacteria of interest. In alternative embodiments, the agent may be a bacteriocin, such as a colicin or a microcin as appropriate. However, lysis may not be essential in all embodiments of the invention. In particular, increasing the permeability of the bacterial cell wall and/or membrane may in certain embodiments be sufficient to enable detection of intracellular material, such as NAD-dependent ligase activity, according to the methods of the invention. Suitable agents and techniques for achieving this increase in permeability are known in the art.
[0131] Step (d) involves determining the presence of intracellular material from the bacteria of interest (caused by lysis of the bacterial cells or an increase in cellular permeability). This step may comprise, consist essentially of or consist of any appropriate assay known in the art. Examples include bioluminesence assays, such as those based on adenylate kinase (AK) as described, for example, in International Pulication Numbers WO 94/17202 and WO 96/02665. However, the assay may alternatively comprise a colourimetric or fluorimetric assay based on intracellular enzyme markerssuch as phosphatase or peroxidase. However, in preferred embodiments, step (d) incorporates the detection methods of the invention involving use of NAD-dependent ligase as an indicator of the presence of the bacteria of interest. Thus, a suitable nucleic acid molecule substrate can be added to the intracellular material. If resistant bacteria of interest are present in the sample, NAD-dependent ligase activity will be present and the substrate will be ligated to produce a ligated nucleic acid molecule. Specific detection of this ligated nucleic acid molecule provides an indication of the presence of the resistant bacteria of interest in the starting sample. Accordingly, all embodiments of the methods of the invention, as described herein, may be applied to this aspect of the invention. Thus, step (d) may incorporate the steps of:
[0132] (a) contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample,
[0133] (b) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and
[0134] (c) specifically determining the presence of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the NAD-dependent ligase expressing micro-organism.
[0135] In specific embodiments, a measurement of intracellular material and in particular embodiments NAD-dependent ligase activity is made at the end of step (a)/beginning of step (b). This measurement provides a background signal against which the test signal can be compared to reach a conclusion regarding the significance of the results. It indicates the basal level of the intracellular material, in particular NAD-dependent ligase activity, in the sample prior to the incubation step which is designed to selectively permit growth of bacteria which are resistant to the specific anti-bacterial agent. A marked or significant increase in the measurement, such as NAD-dependent ligase activity, made in step (d) as compared to that made at the end of step (a)/beginning of step (b) is a reliable indicator of the presence of the bacteria of interest which are resistant to the specific anti-bacterial agent. If there is no increase (or indeed a decrease) as compared to the background signal following the incubation (step (b)) and treatment to increase permeability or cause cell lysis (step (c)), this is an indication of an absence of bacteria which are resistant to the specific anti-bacterial agent.
[0136] In certain embodiments of the present invention the method further comprises, consists essentially of or consists of a washing step following step (a) to remove any cells or other materials non-specifically associated with the capture reagent. Such steps would be routine for one skilled in the art when dealing with a specific capture procedure.
[0137] In the preferred embodiments where step (d) incorporates the detection methods of the invention involving use of NAD-dependent ligase as an indicator of the presence of the bacteria of interest, the steps of the method are not necessarily restricted to the order specified. In particular, step (a) of capturing the bacteria of interest using a specific capture reagent may be carried out following an initial step (b), namely incubating the bacteria of interest in an incubating medium including the specific anti-bacterial agent. Thus, the invention provides a method for determining the presence of bacteria of interest, which are resistant to a specific anti-bacterial agent, in a sample comprising, consisting essentially of or consisting of (the following steps, in particular in the order specified):
[0138] (a) incubating the bacteria of interest in an incubating medium including the specific anti-bacterial agent,
[0139] (b) capturing the incubated bacteria of interest using a specific capture reagent,
[0140] (c) exposing the captured bacteria of interest to an agent capable of causing lysis of the bacteria or of increasing the permeability of the bacterial cell wall to a degree such that the presence of NAD-dependent ligase from the bacteria can be determined, and
[0141] (d) determining the presence of the (resistant) bacteria of interest in the sample by:
(i) contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample, (ii) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and (iii) specifically determining the presence of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the NAD-dependent ligase expressing micro-organism.
[0145] Of course, all description of the various steps of the method provided herein apply to these particular aspects. The order of capture follow by culture is generally preferable since this only requires a single culture step in specific embodiments. Where culture is carried out before capture, it has been found in practice that an additional culture step post capture may be required to ensure sufficient sensitivity in the tests.
[0146] The methods of the present invention may include an additional intervening step or steps so as to enable the presence of more than one target bacteria to be determined. Typically, these steps may comprise capturing multiple different bacteria of interest using one or more appropriate capture agents. Similarly, the methods of the invention may include a number of such steps so that the presence of other target bacteria may be determined.
[0147] Also provided are test kits for performing these methods of the invention. The test kit may be a disposable test kit in certain embodiments. Each component of the test kit may be supplied in a separate compartment or carrier, or one or more of the components may be combined—provided that the components can be stably stored together. The test kit incorporates a specific capture agent for capturing the bacteria of interest resistant to a specific anti-bacterial agent. Suitable capture agents are discussed above, which discussion applies mutatis mutandis. In certain embodiments, a solid support for the specific capture agent is provided in the kit. In further embodiments, the specific capture agent is supplied pre-loaded onto the solid support. Suitable solid supports and means of immobilization are described herein, which description applies mutatis mutandis to these aspects of the invention.
[0148] The kit may also incorporate the incubating medium for the bacteria of interest. In specific embodiments, the medium incorporates the specific anti-bacterial agent to which the bacteria of interest is resistant. Alternatively, the agent may be supplied separately and added to the medium only when the methods are carried out. Suitable media and specific anti-bacterial agents are described herein (with respect to the corresponding methods), which discussion applies mutatis mutandis. The medium may be supplied in any suitable form, such as in freeze dried form for example.
[0149] The kit may also incorporate a suitable agent capable of causing cell lysis of the bacteria of interest or of increasing the permeability of the bacterial cell wall and/or membrane sufficiently to enable detection of intracellular material (in particular NAD-dependent ligase activity) according to the methods of the invention. Suitable agents are discussed above, which discussion applies mutatis mutandis. In specific embodiments, the agent is a lysostaphin such as a (functional) lysostaphin provided by the present invention, in particular a lysostaphin preparation which is substantially free from nuclease and/or ligase contaminants (produced by inactivating these components—as discussed herein).
[0150] The kit may also further incorporate means for determining the presence of intracellular material from the lysed cells of the bacteria of interest or cells which have been treated so as to increase their permeability. Any suitable components may be included depending upon the particular detection technique to be employed. In specific embodiments, the kit includes components allowing detection of NAD-dependent ligase activity in the sample. Thus, the kits of the invention described herein may be combined with the present kits to provide an NAD-dependent ligase linked detection kit for determining the presence of a bacteria of interest resistant to a specific anti-bacterial agent in a sample. In certain embodiments, the kits incorporate at least one nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample. Suitable substrate nucleic acid molecules, which may comprise two or more ligatable nucleic acid molecules, are discussed herein which discussion applies mutatis mutandis. Thus, the substrate nucleic acid molecules may be immobilized on a solid support or may be supplied together with a solid support to allow immobilization thereon in certain embodiments.
[0151] The kit may, in certain embodiments, also incorporate reagents necessary for nucleic acid amplification. Employment of nucleic acid amplification techniques allows sensitive detection of the presence of a novel ligated nucleic acid molecule. Suitable techniques and the necessary reagents would be immediately apparent to one skilled in the art. Thus, the kits may in particular incorporate suitable primers for specific detection of the ligated nucleic acid molecule—as discussed in greater detail herein. The kits may also incorporate suitable reagents for real-time detection of amplification products.
[0152] The kits may incorporate a suitable carrier in which the reactions take place. Advantageously, such a carrier may comprise a multi-well plate, such as a 48 or 96 well plate for example. Such a carrier allows the detection methods to be carried out in relatively small volumes—thus facilitating scale up and minimising the sample volume required.
[0153] The kits will typically incorporate suitable instructions. These instructions permit the methods of the invention to be carried out reliably using the kits of the invention.
[0154] In one specific aspect, the methods of the invention are utilised in order to detect bacterial contamination of a platelet sample.
[0155] Thus, there is provided a method of detecting an NAD-dependent ligase as an indicator of the presence of bacterial contamination in a platelet (containing) sample comprising:
[0156] (a) contacting the platelet sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample,
[0157] (b) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and
[0158] (c) specifically determining the presence of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the bacterial contamination in the platelet (containing) sample.
[0159] In specific embodiments, the method for detection of bacterial contamination of platelets comprises, consists essentially of or consists of additional substeps. These substeps may include, for example:
[0160] (i) lysis of the platelets under conditions that leave the bacterial cells intact. This principally allows selective concentration of bacterial cells prior to testing for the presence of NAD-dependent ligase activity. Thus, any ATP dependent ligase activity provided by mammalian cells can be removed prior to testing
[0161] (ii) concentration of the bacteria (for example by centrifugation to produce a bacterial cell containing pellet)
[0162] (iii) lysis of the bacteria or a treatment to increase the permeability of the bacteria to release the NAD-dependent ligase
[0163] The description of the various embodiments of the methods of the invention apply mutatis mutandis to this specific application and are not repeated for reasons of conciseness.
[0164] The invention also provides kits which enable and are suitable for carrying out the various methods of the invention.
[0165] Therefore, in a further aspect, the invention provides a kit for carrying out one of the methods of the invention comprising, consisting essentially of or consisting of:
[0166] (a) at least one nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample,
[0167] (b) means for immobilizing the substrate nucleic acid molecule and/or
[0168] a reagent for specific capture of an NAD-dependent ligase and/or
[0169] means for selective lysis of bacterial cells or other micro-organisms containing NAD-dependent ligase activity in the sample or for increasing the permeability of the bacterial cells or other micro-organisms to allow detection of NAD-dependent ligase activity and/or
[0170] means for selective lysis of any cells in the sample which do not contain NAD-dependent ligase activity (such as mammalian cells etc, in particular platelets in platelet samples) and/or
[0171] means for inhibiting ATP dependent ligase activity in the sample and/or
[0172] means for selective removal of unligated substrate molecules (to prevent unligated substrate influencing the sensitivity and/or specificity of detection of the ligated nucleic acid molecules)
[0173] The embodiments presented in respect of the methods (and other kits) of the invention apply mutatis mutandis and are not repeated here for reasons of conciseness. Thus, all necessary components and reagents required to carry out the methods of the invention may be incorporated into the kits of the invention. In particular, the substrate nucleic acid molecule includes a dsDNA component which can be ligated by an NAD-dependent ligase. Specific examples may be selected from the nucleic acid substrates comprising the nucleotide sequences set forth as SEQ ID NO: 1 to 4 and/or 7 and 8 respectively (as shown in the detailed description herein). The four nucleic acid molecules comprising the nucleotide sequences set forth as SEQ ID NOs 1-4 respectively can form a substrate molecule with a ligatable complementary 5 nucleotide overlap in one aspect of the invention. In a further aspect, the nucleic acid molecules comprising the nucleotide sequences set forth as SEQ ID NOs 7 and 8 can hybridize to form a substrate molecule which contains a double stranded section with a nick.
[0174] The kits of the invention may also include appropriate filters in order to separate the bacterial cells or other micro-organisms to be detected from other (ligase producing) cells. Such filters and filtration systems and methods are well known in the art and commercially available (for example from New Horizons Diagnostics Inc.). The kits of the invention may also incorporate a suitable filter or filtration mechanism or system in order to be able to isolate target cells or organisms prior to determining whether the NAD-dependent ligase activity is present.
[0175] Additionally, specific bacterial cells or other micro-organisms may also be selected and/or isolated by utilising specific reagents which can bind to the cells or micro-organisms. Suitable reagents include both protein and nucleic acid based reagents. Examples include antibodies, lectins, receptors, DNA, RNA etc. Thus, the kits of the invention may additionally comprise, consist essentially of or consist of a suitable reagent for isolating the bacterium or bacteria of interest. Antibodies and all derivatives thereof (such as Fab fragments, single domain antibodies and variable region fragments) which retain specific binding affinity are included in the definition of the term “antibody”.
[0176] As discussed herein, the substrate nucleic acid molecule may be immobilized on a solid support. The immobilization of the substrate nucleic acid molecule on a solid support allows effective capture of the NAD-dependent ligase from the sample. The interaction of the immobilized substrate nucleic acid molecule with the NAD-dependent ligase results in the generation of a novel, ligated nucleic acid molecule. Thus, the kits of the invention may further comprise a solid support. The substrate may or may not be provided pre-loaded on the solid support. If it is not pre-immobilized on the solid support, suitable reagents to allow immobilization may be provided in the kit, optionally together with suitable instructions. Reagents to allow immobilization would be well known to one of skill in the art. Any means of immobilization may be utilised provided that it does not have an adverse effect on the implementation of the methods of the invention, especially in terms of specificity and sensitivity of detection of the NAD-dependent ligase from the one or more target bacterial cells or micro-organisms.
[0177] Any suitable solid support may be included in the kits of the invention. The nature of the solid support is not critical to the performance of the invention provided that the substrate nucleic acid molecule may be immobilized thereon without adversely affecting NAD-dependent ligase activity, including the ability of the enzyme to interact with the nucleic acid molecule. Non-limiting examples of solid supports include any of beads, such as polystyrene beads and paramagnetic beads and derivatives thereof, affinity columns, microtitre plates etc. Where the substrate nucleic acid molecule is in fact two (or more) nucleic acid molecules which are ligated together, either one or both of the substrate nucleic acid molecules may be immobilized on a solid support. In specific embodiments, the separate substrate nucleic acid molecules may be immobilized on the same support as one another. This allows the molecules to be in proximity to ensure that ligation is efficient if the NAD-dependent ligase is present in the sample under test. Biotin and/or the streptavidin reagents may be incorporated in the kits to facilitate immobilisation for example.
[0178] In further embodiments, the kits of the invention further comprise, consist essentially of or consist of reagents necessary for nucleic acid amplification. Preferably, the reagents are for carrying out any one of the amplification techniques discussed herein. Reagents for carrying out nucleic acid amplification are commercially available and well characterised in the art. Examples of suitable reagents include suitable primers designed to amplify the novel ligated nucleic acid molecule. The discussion of primer design in respect of the methods of the invention applies mutatis mutandis here. Thus, suitable primers of the invention may be incorporate into suitable kits for detecting ligated nucleic acid molecules (e.g. as set forth in SEQ ID NOs: 5 and 6 or 9 and 10 respectively). Polymerases, such as Taq polymerase of which several variants (including hot start variants) are available and buffers such as KCl and (NH 4 ) 2 SO 4 may also be included.
[0179] In related embodiment, the kit further comprises, consists essentially of or consists of reagents for detecting the products of nucleic acid amplification in real time or at end point. The kit may include reagents for carrying out real-time or end point amplification and detection utilising any of the fluorescence based systems disclosed herein. Suitable reagents for use in these methods are well known in the art and are commercially available.
[0180] Examples of suitable reagents include sequence specific probes. These probes may bind in between the primers used to amplify the novel nucleic acid molecule, and thus may bind to amplified nucleic acid molecules to provide a direct indicator of the levels of product being formed during amplification. The design of such probes is routine for one of skill in the art. Alternatively, appropriate primers may need to be designed, for example in the Amplifluour and Scorpion systems which allow real time or end point detection of amplification products. Thus, the kits of the invention may incorporate hairpin primers (Amplifluor), hairpin probes (Molecular Beacons), hydrolytic probes (Taqman), FRET probe pairs (Lightcycler), primers incorporating a hairpin probe (Scorpion), fluorescent dyes (SYBR Green etc.), primers incorporating the complementary sequence of a DNAzyme and a cleavable fluorescent DNAzyme substrate (DzYNA) or oligonucleotide blockers for example. A suitable hydrolytic probe is set forth as SEQ ID NO: 11.
[0181] Any suitable fluorophore is included within the scope of the invention for labelling, or as part of, the relevant primers or probes. Fluorophores that may possibly be included in the kits of the invention include, by way of example, FAM, HEX™, NED™, ROX™, Texas Red™ etc. Similarly the kits of the invention are not limited to a single quencher. Quenchers, for example Dabcyl and TAMRA are well known quencher molecules that may be used in the method of the invention and included in the kits of the invention.
[0182] Kits of the invention may also include further components necessary for the generation and detection of PCR products other than those described above, such as microarrays, which may be used for detection of amplification products, or may be used to amplify (amplification on a chip) and detect the amplification product. Other components may further include “micro fluid cards” as described by Applied Biosystems, Reversed hybridization strips such as those described by LIPA technology (Innogenetics, Zwijnaarde, Belgium, or those described by Ulysis and ULS technology (Kreatech Biotechnologies, Amsterdam, The Netherlands)). Such components are known in the art and are listed by way of example and not limitation for inclusion in the kits of the invention.
[0183] The sample for testing with the kits of the invention may be any suitable sample, as defined above.
[0184] Additionally lysis reagents, which lyse other cells which are not target bacterial cells or micro-organisms but which may otherwise contribute ligase activity to the assay system may be included in the kits of the invention. Suitable reagents, which preferably do not lyse the cells of the bacteria or other micro-organisms which are to be detected include, by way of example and not limitation alcohols, salts etc and possibly also reagents such as proteinase K and chloroform depending upon which bacteria or other micro-organisms are being detected. In the specific application to detecting bacterial contamination of platelets, sodium carbonate and zwittergent may be utilised at an appropriate concentration to lyse platelets selectively and leave any bacterial cells in tact. Thus, the kits may incorporate these components.
[0185] The kits of the invention may further comprise, consist essentially of or consist of an enzyme for removing or exhausting from the sample ATP, to thus prevent any ATP dependent ligase activity in the sample influencing the bacterial detection. In a specific embodiment, the enzyme comprises any one or more of luciferase, phosphatase and pyrophosphatase, since all of these enzymes may be used to exhaust the ATP signal derived from non-target cells or organisms in the sample which may otherwise give rise to false positive results. Suitable reagents for these enzymes, such as an appropriate (storage) buffer may be included in the kits.
[0186] The kits of the invention may further comprise, consist essentially of or consist of reagents for lysis of the cells of the bacteria or other micro-organisms being detected in order to release the NAD-dependent ligase. Suitable reagents include by way of example and not limitation phenol, chloroform, proteinase K and lysostaphin, in particular lysotaphins of the present invention. Agents for increasing cellular permeability, in order to permit detection of NAD-dependent ligase activity, may similarly be incorporated as discussed herein.
[0187] The kits of the invention may further comprise, consist essentially of or consist of one or more nucleases in order to degrade nucleic acid molecules associated with the bacteria or other micro-organisms which provide the NAD-dependent ligase activity which is detected in the sample. This may be beneficial to prevent non-specific ligation events for example. This may not be an absolute requirement however, since the substrate nucleic acid molecule may be designed such that they are not homologous to the nucleic acid molecules of the bacteria or other micro-organisms organism (whose viability is) being detected. Thus, specific detection of the novel ligated nucleic acid molecule can be achieved in the presence of “contaminating” endogenous nucleic acid. This is discussed in detail above, which discussion and embodiments apply mutatis mutandis to the kits of the invention.
[0188] As stated above, the kits may include means for selective removal of unligated substrate molecules. This helps to prevent unligated substrate influencing the sensitivity and/or specificity of detection of the ligated nucleic acid molecules. In specific embodiments, the means for selective removal of unligated substrate molecules comprises one or more selective nucleases. In particular, one or more exonucleases may be employed to remove unligated substrate molecules. In specific embodiments, 3′-5′ exonucleases such as ExoIII, ExoI and/or ExoT are employed to digest unligated substrate molecules. A combination of dsDNA specific 3′-5′ exonucleases, such as ExoIII and one or more ssDNA specific 3′-5′ exonucleases such as ExoI and/or ExoT may advantageously be incorporated into the kits, in particular where the ligated nucleic acid molecule is formed from at least three substrate nucleic acid molecules which together form a double stranded region including a nick which is ligated by NAD-dependent ligase activity in the sample.
[0189] In specific embodiments, the kit is provided with suitable buffers that allow all of the components to be provided in the same compartment or storage vessel. Thus, the complete kit is essentially provided as a complete (homogeneous) reaction mix. Thus, the methods of the invention may be carried out in a single reaction step which reduces the possibility of cross contamination of samples and also provides rapid results. Especially preferred is a reaction mix which provides results in real time or at end point. Preferably, such a reaction mix is an aqueous composition, but may be provided as a dry powder for reconstitution using sterile or distilled water for example.
[0190] Preferably, the reagents included allow an isothermal amplification technique to be utilised, such as TMA. The reagents may allow the isothermal amplification technique (such as TMA) to be carried out in real-time or at end point.
[0191] All kits of the invention may be provided with suitable instructions for use in any one of the methods of the invention. The instructions may be provided as an insert, for example as a booklet provided inside the packaging of the kit and/or may be printed on the packaging of the kit for example.
[0192] Thus, according to a still further aspect, the invention provides a spray device for administering the reaction mix which contains all components necessary to carry out the methods of the invention to a surface. Any suitable spray device may be utilised, which may be a pump spray or an aerosolized device for example. Such a device may find application in a number of settings where microbial detection, or detection of any contaminating micro-organisms from any source, on a surface is required. For example, where food is being prepared it would be advantageous to be able to ensure that, following cleaning of surfaces after food preparation, no potentially harmful bacterial cells or micro-organisms remain on the surface. This ensures that the surface is then “clean” and may be utilised for further food preparation. A spray device can also be used to detect bacterial contamination on surfaces in a hygiene monitoring application, by detecting NAD-dependent ligase activity. Thus, the presence of this enzyme as a marker of (viable) bacteria indicates that some form of contamination is present on the surface. Use of an isothermal DNA amplification method is preferred for the detection of NAD-dependent ligase activity on a surface. Suitable examples such as TMA are referred to above.
[0193] The invention will be further defined by and understood with respect to the detailed description, incorporating the accompanying figures and examples in which:
DETAILED DESCRIPTION OF THE INVENTION
BRIEF DESCRIPTION OF THE FIGURES
[0194] FIG. 1 is a schematic of the Ligase Mediated Assay of the invention that detects the bacterial enzyme, NAD-dependent ligase. NAD-dependent ligase is found exclusively in eubacteria (2) and has not been reported in mammals. Hence this technology is ideal for use in the rapid and sensitive detection of bacteria in clinical samples where background from the host would otherwise be a problem. An additional advantage of the methods of the invention is that there is a further amplification step in the system since NAD-dependent ligase generates many molecules of the DNA primer prior to NAT amplification. So this assay is a sensitive approach; currently the detection limit for E. coli and S. aureus is in the range 100 to 1000 cells in culture samples.
[0195] FIG. 2 shows a plot of relative amplification versus time for various reaction conditions (with or without additional NAD+ and with or without gentamicin treatment).
[0196] FIG. 3 is a flow chart showing the protocol for detection of Staph. aureus using the methods of the present invention.
[0197] FIG. 4 . Dilution of Staph. aureus cells. Detection using methods of the present invention (referred to as LiMA-2) and real time PCR (Taq-Man). From left to right the curves represent: 10 6 , 10 5 , 10 4 , 10 3 , 10 2 , 10, 0 cells and the PCR blank.
[0198] FIG. 5 . Sensitivity of Staph. aureus cells to antibiotic. 10 4 cells were added to culture medium, PCR traces are shown, from left to right: T=5 hours culture (no oxacillin), T=0 hours and T=5 hours culture (plus oxacillin)
EXAMPLE 1
Detection of Platelet Contamination
[0199] Rationale.
[0200] Bacterial contamination of platelets can be detected by selective lysis of the platelets followed by bacterial cell lysis and detection of the bacterial ligase. Any contaminating mammalian ligase will not be detected efficiently by the assay because mammalian ligases use ATP as a cofactor whereas bacterial ligases use NAD+. The ligase buffer in this case is supplemented with the bacterial specific NAD+ cofactor. The bacterial ligase is detected by ligation of two synthetic DNA duplexes with a complementary 5 base overhang. Once ligated, ligated molecules are detected by PCR across the ligation junction.
[0201] Method
[0202] 1. 0.5 ml platelets (collected by apherisis) were spiked with known numbers of Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa bacteria (assess by prior culture and enumeration).
[0203] 2. The spiked samples were made 50 mM sodium carbonate and 1% (w/v) Zwittergent in a final volume of 1 ml.
[0204] 3. After incubation for 5 min to allow platelet lysis 100 μl M Tris pH 7.5 was added.
[0205] 4. The bacteria were pelleted by centrifugation at 6,000×g for 5 min and the supernatant removed.
[0206] 5. 20 μl BPer (Pierce) was added and incubated 5 min to allow bacterial cell lysis.
[0207] 6. 2 μl of the bacterial lysate was then added to a ligase reaction containing 2 μl 10× E. coli ligase buffer (NEB), 2 μl (20 ng) each of the DNA substrate S1/AS1 and S2/AS2 in a total volume of 20 μl. The DNA substrate is formed from 4 synthetic oligos which have a ligatable complementary 5 base overlap:
[0000]
S1
(SEQ ID NO: 1)
5′ GCCGATATCGGACAACGGCCGAACTGGGAAGGCGCACGGAGAGA 3′
AS1
(SEQ ID NO: 2)
3′ TATAGCCTGTTGCCGGCTTGACCCTTCCGCGTGCCTCTCTGGTGC
5′, PHOSPHORYLATED AT THE 5′ END
S2
(SEQ ID NO: 3)
5′ CCACGAAGTACTAGCTGGCCGTTTGTCACCGACGCCTA 3′,
PHOSPHORYLATED AT THE 5′ END
AS2
(SEQ ID NO: 4)
3′ TTCATGATCGACCGGCAAACAGTGGCTGCGGAT 5′
[0208] The substrate was formed by mixing equimolar concentrations of S1 and AS1 at 93° C. and allowing to cool to room temperature. Similarly, S2 and AS2 were formed in the same way.
[0209] 7. After 30 min at room temperature 2 μl of the ligated product was investigated by PCR.
[0210] 8. The real time PCR (Eurogentec) contained SYBR Green and the forward primer, 5′ GGACAACGGCCGAACTGGGAAGG 3′ (SEQ ID NO: 5) and reverse primer, 3′ CGACCGGCAAACAGTGGCTGCGGAT 5′ (SEQ ID NO: 6) with dentauration at 94° C. for 10 sec, annealing at 65° C. for 15 sec and extension at 72° C. for 15 sec.
[0211] Results
[0000]
Cycle at which PCR
was positive
Number of E. coli
10 6
14.5
10 5
18.44
10 4
20.82
10 3
23.88
10 2
25.55
10 1
27.95
Number of S. aureus
10 6
14.2
10 5
17.55
10 4
20.16
10 3
22.65
10 2
25.74
10 1
28.55
Number of P. aeruginosa
10 6
15.42
10 5
18.65
10 4
21.18
10 3
23.68
10 2
26.93
10 1
29.83
no bact ctrl
30.58
No platelet ctrl
30.48
PCR ctrl
34.26
[0212] Discussion
[0213] Spiking with 10-fold dilutions of bacteria gave a corresponding titration of PCR signal. From the PCR results it can be seen that as few as 10 bacteria can be detected spiked into 0.5 ml of platelets. Similar results were achieved with replacing the sodium carbonate with ammonium sulphate for platelet lysis.
EXAMPLE 2
Drug Susceptibility Testing
[0214] Rationale.
[0215] The PCR signal generated is related to the number of ligated molecules of the DNA substrate which in turn is related to the number of ligase molecules present. In turn, the number of molecules of ligase present is dependent on the viability of the bacterium. Upon culture of a given bacterium, if the bacteria are healthy, growing and increasing in number there will be progressively more ligase present which will generate more ligation and more PCR signal. If the bacteria are unhealthy and non-viable or dying there will be no increase in ligase on culture and the number of ligase molecules might even be expected to decrease which will be reflected in the amount of ligation and PCR signal generated. In this example we have tested the susceptibility of the organism to an antibiotic. By culturing in the presence and absence of antibiotic we can compare the signal generated from the bacterial ligase at different time points. Additionally, the experiment can be performed with and without the addition of the NAD+ cofactor. In the presence of added cofactor the ligase can cycle through many ligation steps. In the absence of added cofactor the ligase must depend on endogenous bacterial NAD+ for ligation. These two conditions, therefore are two different measures of the health of the bacterial cell
[0216] Method
[0217] 1. 10 ml of media (LB broth) containing 50 μg/ml gentamicin was inoculated with 104 E. coli bacteria/ml and incubated for 3 hours. At 30 min time points 1 ml of the culture was removed and placed on ice until completion of the time course.
[0218] 2. The bacteria were then pelleted by centrifugation at 6,000×g for 5 min and the supernatant removed.
[0219] 3. The protocol from this stage was identical to steps 3 to 8 in example 1 except that the ligase reaction was performed with and without added NAD+.
[0220] Results
[0000]
Cycle at which PCR was positive
With added NAD+
Without added NAD+
Plus
Minus
Plus
Minus
gentamicin
gentamicin
gentamicin
gentamicin
Time
(min)
0
26.2
24.5
29.5
29.85
30
25.1
25
29.4
29.95
60
25.7
23.6
31.6
31.64
90
26.2
22.7
30.1
28.52
120
27.2
21
30.3
25.53
150
26.8
20.1
29.4
24.35
180
26.3
18.2
30.1
22.71
No
29.3
30.6
bacterial
control
[0221] The results can be presented as a graph in which the amplification factor at each time point and for each condition is plotted compared to the time 0 time point (see FIG. 2 ).
[0222] Discussion
[0223] The assay works well as an antibiotic susceptibility test. In the presence of gentamicin the signal from the bacterial ligase does not increase with incubation. However, in the absence of gentamicin there is progressively more ligation and associated PCR signal at each time point. This reflects the growth and viability of the E. coli. In this example, only 104 E. coli was used as the original inoculum which demonstrates the high sensitivity of this approach. Inclusion of NAD+ in the ligation buffer allows the ligase enzyme to cycle through many molecules of DNA substrate and so the sensitivity of detection is increased. However, in the absence of exogenous NAD+, the bacterial enzyme must utilise bacterial NAD+ and although the signal is delayed there is a greater difference in signal between time 0 and the later time points. This reflects the fact that non-viable bacteria will have decreased levels of available NAD+.
EXAMPLE 3
Detection of Bacterial Ligase After Nucleic Acid Capture
[0224] This example demonstrates that the bacterial ligase can be captured from solution using immobilised nucleic acid substrate. This example was essentially similar to example 1 but the nucleic acid substrate was immobilised onto streptavin beads through the synthesis of AS1 biotinylated at the 3′ end.
[0225] Method
[0226] 1. Initially, the method was the same as steps 1-5 of example 1 using 0.5 ml platelets (collected by apherisis) and spiking with known numbers of Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa bacteria (assess by prior culture and enumeration).
[0227] 2. After bacterial cell lysis using 20 μl BPer the solution was made up to 100 μl with 1× ligase buffer which did not contain NAD+.
[0228] 3. The nucleic acid duplex S1/AS1 was formed as described previously except that AS1 was biotinylated at the 3′ end and the duplex bound to streptavidin beads (Sigma) at a concentration of 20 ng of duplex per 20 μl beads. 20 μl beads with immobilised S1/AS1 was added to the lysate from step 2 above and incubated for 10 min.
[0229] 4. The beads with attached ligase were collected using a magnet and placed into a 20p1 ligation reaction including 1× ligase buffer with NAD+ and 20 ng of the nucleic acid duplex S2/AS2.
[0230] 5. After ligation for 30 min, the reaction was heated at 95° C. for 5 min and 2 μl placed into a PCR as described in example 1, step 8.
[0231] Results
[0000]
Cycle at which PCR
was positive
Number of E. coli
10 6
12.3
10 5
15.36
10 4
17.22
10 3
20.15
10 2
22.89
10 1
25.67
Number of S. aureus
10 6
12.4
10 5
14.57
10 4
18.16
10 3
21.35
10 2
23.99
10 1
26.15
Number of P. aeruginosa
10 6
12.92
10 5
15.23
10 4
18.64
10 3
21.21
10 2
23.94
10 1
26.76
no bact ctrl
30.52
No platelet ctrl
30.39
PCR ctrl
34.10
[0232] Discussion
[0233] This example shows that the ligase released from the bacteria can be captured onto an immobilised nucleic acid substrate prior to subsequent ligation. This approach concentrates the ligase and allows analysis of a greater proportion of the released ligase. This results in a more sensitive detection which is reflected in the PCR analysis for a given number of organisms becoming positive at an earlier cycle number.
EXAMPLE 4
NAD-Dependent Ligase Detection: from Stap. aureus
[0234] Media Wash Step:
[0235] Take 1 ml fresh Staph. aureus culture (10 6 cells/μl), spin 8000 rpm 5 min, resuspend pellet in 1 ml deionised water Dilute in a series of 10 fold dilutions down to 10 2 cells/μl
[0236] Lysis/Ligation Mix
[0000]
Add 2 μl “10x ligase buffer” (4 mM MgC12, 1 mM
DTT, 50 μg/ml BSA, 26 μM NAD + , 30 mM Tris pH 8)
DNA substrate** (“anchor and template”) 1 μl
(annealed to 100 ng/μl final concentration)
Heat treated lysostaphin 2 μl*
1% Triton X-100 2 μl
Non specific DNA 100 μM 0.2 μl (single
stranded oligomer)
Deionised water 12.8 μl
Add 1 μl of relevant Staph. aureus culture dilution
Incubate at room temperature for 30 mins
*Take stock lysostaphin, 10 mg/ml, dilute 10x in
1x final ligase buffer without added NAD + , heat at
55° C. 5 min, then dilute 10x again. Note that
heat treating the lysostaphin eliminates
contaminating nucleases and ligases from the
solution, so reducing background and loss of
signal problems in the subsequent NAD-dependent
ligase assay.
** Two components, which when hybridized generate
a double stranded section with a nick.
Anchor:
(SEQ ID NO: 7)
5′-CCCCGGATCCCTTAGAATTCCCCTCAGAGGCACTGGAGCTGGAGACG
TA-3′
Template:
(SEQ ID NO: 8)
5′P-GTGCCTCTGAGCCAGGGGAGCAGTTCGGCGTAGTGATGACGAGTCT
ACGAGTCTACGAGTTCTACGTCTCCAGCTCCA-3′
[0237] Treating Unligated Substrate
[0238] After ligation step above add 2 μl of following nuclease mix to each tube:
[0239] 10× dilution ExoIII 2 μl
[0240] ExoI 2 μl
[0241] ExoT 2 μl
[0242] 100× dilution of the “10× ligase buffer” (without NAD + ) 14 μl
[0243] Incubate at 37° C. for 30 mins
[0244] Heat to 95° C. for 5 mins (to inactivate the Exonucleases)
[0245] PCR Step
[0246] Add 2 μl to PCR mastermix, cycles were:
[0247] 90° C. 10 min 1×, followed by:
[0248] 90° C. 5 sec 40×
[0249] 60° C. 10 sec 40×
[0250] Using:
[0251] Primer1 5′-GAGTCTACGAGTCTACGAGTTCT-3′(SEQ ID NO:9)
[0252] Primer2 5′-TCATCACTACGCCGAACTGC-3′ (SEQ ID NO:10)
[0253] Taqman Probe 5′FAM-CTCAGAGGCACTGGAGCTGGAGAC-3′TAM (SEQ ID NO:11) Dual Labeled HPL (5′ fluorescein and 3′ TAMRA quencher)
[0254] Results
[0255] FIG. 3 shows the assay protocol for the detection of Staph. aureus using the LIMA-2 technology. FIG. 4 shows typical data from a serial dilution of Staph. aureus obtained with a ‘real-time’ PCR assay using the Taq-Man approach. The detection limit in this experiment was estimated to be between 10 and 100 cells. FIG. 5 shows the effect of adding an antibiotic to the culture medium, the NAD-dependent ligase content falls by >2×10 3 fold after 4 hours in the presence of antibiotic.
[0256] Conclusion
[0257] We have shown that NAD-dependent ligase is a useful marker for viable bacterial cells and can be detected very sensitively with a nucleic acid template based technique. The very low detection limit for Staph. aureus indicates that the LiMA-2 technique is one of the most sensitive methods currently available for bacterial detection.
REFERENCES
[0258] Barringer K J, Orgel L, Wahl G, Gingeras T R. Blunt-end and single-strand ligations by Escherichia coli ligase: influence on an in vitro amplification scheme. Gene. 1990 Apr. 30; 89(1):117-22.
[0259] Compton J. Nucleic acid sequence-based amplification. Nature. 1991 Mar. 7; 350(6313):91-2.
[0260] Fahy E, Kwoh D Y, Gingeras T R. Self-sustained sequence replication (3SR): an isothermal transcription-based amplification system alternative to PCR. PCR Methods Appl. 1991 August; 1(1):25-33. Review.
[0261] The LiMA Technology: Measurement of ATP on a Nucleic Acid Testing Platform. Banin S, Wilson S M and Stanley C J (2007). Clinical Chemistry 53, 2034-2036
[0262] Recent developments in ligase-mediated amplification and detection. Cao W (2004). Trends in Biotechnology 22(1), 38-44
[0263] The present invention is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description and accompanying figures. Such modifications are intended to fall within the scope of the appended claims. Moreover, all embodiments described herein are considered to be broadly applicable and combinable with any and all other consistent embodiments, as appropriate.
[0264] Various publications are cited herein, the disclosures of which are incorporated by reference in their entireties. | NAD-dependent ligase is identified as an indicator of micro-organisms in a sample. A method of detecting the presence of an NAD-dependent ligase expressing micro-organism in a sample comprises the steps of: (a) contacting the sample with a nucleic acid molecule which acts as a substrate for NAD-dependent ligase activity in the sample, (b) incubating the thus contacted sample under conditions suitable for NAD-dependent ligase activity; and (c) specifically determining the presence of a ligated nucleic acid molecule resulting from the action of the NAD-dependent ligase on the substrate nucleic acid molecule to indicate the presence of the NAD-dependent ligase expressing micro-organism. The method has a number of applications and kits for carrying out the methods are also provided. Lysostaphin preparations substantially free from nuclease and/or ligase contaminants are produced by heating a lysostaphin preparation which contains nuclease and/or ligase contaminants under conditions whereby nuclease and/or ligase activity is reduced whereas endopeptidase activity of the lysostaphin is substantially unaffected. | 2 |
PRIORITY
[0001] This application claims priority to U.S. Provisional Application 61/224,644 filed Jul. 10, 2009, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] 1. Field of the Invention
[0003] This invention is related to the field of blinds (e.g., hunting blinds) and other camouflaging devices.
[0004] 2. Related Art
[0005] Hunting blinds help hunters immerse themselves into the local environment of wildlife by, for example, helping hide the hunter from a field of view of an animal to limit the amount of fear or suspicion experienced by that animal. In general, hunting blinds may help obscure, alter, mask, or hide the visual appearance, heat, sound, and/or smell of the hunter. Additionally, blinds and the like may be used by non-hunters to, for example, help a bird watcher get closer to a flock of birds without startling the birds, or help a nature photographer approach or be approached by animals in their natural environment.
[0006] Traditional hunting blinds are often camouflaged to look like or otherwise blend into a part of the local environment. For example, traditional hunting blinds may be decorated or adorned with a fabric pattern that looks like a collection of sticks and/or leaves. These patterns help hide (e.g., obscure) any edges and/or sharp angles of the camouflaged object that may be used to differentiate the object from natural objects of the local environment.
[0007] Hunting blinds may also help hide, trap, or obscure smells, sounds, heat, or other identifiers from an animal. Likewise, hunting blinds may provide protection to a hunter. For example, hunting blinds may help shelter a hunter from weather (e.g., wind, rain, uncomfortable temperatures, solar exposure, etc.) and/or may protect the hunter from being harmed by animals (e.g., by avoiding recognition by the animals and/or by providing a barrier between the hunter and the animals).
SUMMARY
[0008] An exemplary embodiment relates to a hunting blind comprising a frame comprising one or more rib members and a barrier layer, a fibrous covering, and a camouflage layer.
[0009] Another exemplary embodiment relates to a method of assembling a hunting blind comprising providing a generally rectangular frame base, providing one or more frame panels comprising at least one rib and a barrier layer, attaching two frame panels to opposite sides of the frame base, forming a canopy from two or more joined frame panels, and covering the canopy with a fibrous covering.
[0010] Another exemplary embodiment relates to a method of assembling a hunting blind comprising providing a generally rectangular frame base, attaching one or more ribs to the frame, attaching one or more barriers layers to the ribs with a clip, attaching a fibrous covering to the ribs or barrier layers, and attaching a covering to the ends of the blind.
[0011] These and other features and advantages of various embodiments of systems and methods according to this invention are described in, or are apparent from, the following detailed description of various exemplary embodiments of various devices, structures, and/or methods according to this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Various exemplary embodiments of the systems and methods according to the present disclosure will be described in detail, with reference to the following figures, wherein:
[0013] FIG. 1 is a perspective view of a first exemplary embodiment of a hunting blind;
[0014] FIG. 2 is a another perspective view of the hunting blind embodiment FIG. 1 showing a portion of an internal framework;
[0015] FIG. 3 is a perspective view of a base portion of the framework of the embodiment of FIG. 1 ;
[0016] FIG. 4 is a perspective view of a side panel portion of the framework embodiment of FIG. 3 ;
[0017] FIG. 5 is a partial perspective view of the framework embodiment of FIG. 3 ;
[0018] FIG. 6 is a partial perspective view of the framework embodiment of FIG. 1 ;
[0019] FIG. 7 is a perspective view of a top panel portion of the framework embodiment of FIG. 3 ;
[0020] FIG. 8 is a perspective view of the framework of the framework embodiment of FIG. 3 ;
[0021] FIG. 9 is a perspective view of a portion of a second exemplary embodiment of a framework for a hunting blind;
[0022] FIG. 10 is a perspective view of the framework embodiment of FIG. 9 ;
[0023] FIG. 11 is a perspective view of a screw and a bracket or clip usable to secure a barrier to a framework of a hunting blind according to an exemplary embodiment;
[0024] FIG. 12 is a perspective view of the clip of FIG. 11 coupling a barrier to a frame;
[0025] FIG. 13 is a perspective view of an exemplary embodiment of a window cover with the window covered; and
[0026] FIG. 14 is a perspective view of the window cover embodiment of FIG. 13 with the window uncovered.
[0027] It should be understood that the drawings are not necessarily to scale. In certain instances, details that are not necessary to the understanding of the invention or render other details difficult to perceive may have been omitted. It should be understood, of course, that the invention is not necessarily limited to the particular embodiments illustrated herein.
DETAILED DESCRIPTION
[0028] It should be appreciated that the following description of a hunting blind is in relation to use by a hunter for hunting animals. However, any individual could use the described blind for any desired purpose. As such, the following description (e.g., with regard to use by hunters) should be appreciated to include use by any user(s) who may use the blind for any desired purpose.
[0029] While traditional hunting blinds may help obscure the edges and/or angles of the blind and/or the hunter, traditional hunting blinds may still appear to be foreign or suspicious objects and may be avoided by animals. For example, a traditional hunting blind may not be specifically recognized as a threat by an animal, however, that animal may still recognize that the hunting blind is not a natural and/or expected object (e.g., a tree) and may still avoid the hunting blind.
[0030] Additionally, many traditional hunting blinds (e.g., so-called tree stands or blinds) require natural objects of similar shape and/or size to the object being camouflaged in order for the hunting blind to appear as part of that environment. Likewise, traditional camouflaged blinds require certain foliage, trees, branches, and/or the like to be able to appear as part of the local environment. These traditional hunting blinds may be predominantly useful in wooded areas where the traditional hunting blind may be camouflaged as part of the trees or undergrowth.
[0031] However, hunters often hunt in locations or environments that are without large natural objects, such as trees, and/or without substantial foliage (e.g., background foliage). For example, hunters may utilize a feed field or food plot, in which vegetation (e.g., corn, sorghum, winter wheat, rye, triticale, alfalfa, clover, soybeans, brassicas, etc.) is planted that is particularly preferred by a desired animal (e.g., deer). In such feed fields or food plots, there may not be sufficient natural objects, foliage, or the like to optimally blend into using traditional camouflaged hunting blinds.
[0032] However, hay bales (e.g., hay or straw) are common appearances in fields of many types, including feed fields, food plots, and the like. Animals appear to show little or no fear or suspicion when approaching hay bales, perhaps because the animals have become conditioned to seeing hay bales in fields. Additionally, some animals may have become conditioned to the tendency for hay bales to appear rapidly. For example, a field may be clear one day and include several hay bales the next. The abrupt appearance of these hay bales does not appear to be feared by animals or raise their suspicions. It should be appreciated that, in general, animals are often fearful or otherwise cautious around objects that appear foreign to a local known environment, either by shape and design or by abrupt appearance.
[0033] Earlier attempts to make a hay bale style hunting blind have not been successful for several reasons. Earlier hay bale blinds have been too heavy, too permanent, too expensive, and/or required frequent repair and/or replacement. For example, earlier hay bale blinds have used solid steel bars in large dimensions, welded frames, and elaborate assembly. These blinds often require full frame preconstruction and thus create challenges related to shipping (e.g., by requiring freight shipping) and placement in the field. Once assembled, these earlier hay bale blinds are difficult to disassemble and/or move.
[0034] Likewise, earlier hay bale blinds have typically used a layer of straw between two layers of fencing and a plastic interior layer to provide a camouflaged outer surface. The straw in these earlier hay bale blinds is not securely fastened to the blind and, as such, is rapidly lost from the blind due, at least in part, to weather conditions and natural settling. That is, the straw layer of previous blinds may be lost due to wind, rainfall, and/or natural settling of the material due to gravity. Many prior hay bale blinds require replacement or significant maintenance every year. The straw layer used in these previous blinds may also be particularly prone to igniting or catching fire in the presence of an ignition source such as, for example, a gas (e.g., propane or natural gas) or electric space heater.
[0035] By replacing the straw layer with a more resilient fibrous material, the life of the blind can be extended. The replacement fibrous material may also be less prone to igniting or catching fire than the previous straw layer. Likewise, by improving the construction of the blind, the blind can be made lighter yet strong, while being more efficient to ship, transport, assemble, and/or disassemble.
[0036] FIGS. 1 and 2 show a hunting blind 100 according to an exemplary embodiment. As shown in FIGS. 1 and 2 , hunting blind 100 has a generally cylindrical shape with roughly circular end portions. That is, in various exemplary embodiments, hunting blind 100 has a generally circular shaped cross-section in a latitudinal direction and a generally rectangular shaped cross section in a longitudinal direction. Additionally, hunting blind 100 is covered with a material that has the appearance of baled hay or straw. In various exemplary embodiments, hunting blind 100 includes a fibrous covering 102 .
[0037] As shown in FIG. 1 , hunting blind 100 has an exterior appearance that resembles common hay bales (e.g., round bales). That is, the outer surfaces of hunting blind 100 give the appearance of natural fibers, such as straw or hay, and the general shape of hunting blind 100 is similar to the shape of a typical hay bale, such as, for example, a round bale. Hunting blind 100 may be any size (e.g., larger or smaller than typical hay bales).
[0038] In general, fibrous covering 102 may give the appearance of rolled or bundled straw or hay and may include bale netting, string, or other bundling material found in hay bales. In various exemplary embodiments, fibrous covering 102 includes end portions that may be used for covering the roughly circular end portions of hunting blind 100 . In various exemplary embodiments, fibrous covering 102 is made from a material and/or is treated (e.g., with a material or chemical) that is fire-resistant and/or fire-retarding. In various other exemplary embodiments, the end portions of the blind may be covered by another materials, such as, for example, canvas, that is treated (e.g., painted) to resemble the end of a bale.
[0039] In various exemplary embodiments, fibrous covering 102 is an erosion control blanket, which may include coconut fiber and/or straw with a capture net. Erosion control blankets are produced commercially in different grades, which vary in their durability. In preferred embodiments, a longer-wearing material is preferred as it will have to be replaced less frequently.
[0040] In addition to the fibrous layer, an additional layer of camouflage material may be added on the exterior of the blind. The camouflage layer may comprise natural materials such as, for example, hay, straw, or corn stalks, and/or artificial materials designed to mimic the appearance of natural materials.
[0041] It should be appreciated that, while hunting blind 100 is shown to have or simulate the appearance of a round hay bale, according to various exemplary embodiments, a hunting blind may resemble any shape of hay bale. For example, the hunting blind may be substantially square or rectangular and/or may resemble one or more square or rectangular hay bales in any desired configuration (e.g., like a stack of rectangular bales). Likewise, hunting blind 100 may simulate or give the appearance of bales (e.g., round bales) composed of materials other than hay. For example, hunting blind 100 may have the appearance of baled straw, corn stalks, or other cut and/or raked crops.
[0042] Hunting blind 100 may be usable to help obscure; hide, or mask one or more sensory indicators of a hunter located within hunting blind 100 from animals near hunting blind 100 . For example, hunting blind 100 may help mask or hide a smell, heat, sound, and/or an appearance of a hunter located within hunting blind 100 . As such, animals near hunting blind 100 may not be aware of the presence of the hunter located within hunting blind 100 . It should be appreciated that hunting blind 100 may be utilized to help obscure, hide, or mask any indicator used by any animal to detect the presence of a person.
[0043] It should be appreciated that, while hunting blind 100 is shown as being nearly fully enclosed in FIGS. 1 and 2 , in various exemplary embodiments, hunting blind 100 includes a substantially open portion. For example, in various exemplary embodiments, hunting blind 100 may have an open roof and may be particularly useful for hunting birds (e.g., ducks and/or geese).
[0044] FIG. 2 shows a portion of hunting blind 100 without fibrous covering 102 (e.g., a portion of a skeleton of hunting blind 100 ) according to an exemplary embodiment. As shown in FIG. 2 , in various exemplary embodiments, hunting blind 100 includes a series of spaced apart ribs 120 and a barrier 130 . In various exemplary embodiments, series of ribs 120 includes at least one terminal rib 125 positioned near each end of hunting blind 100 . In various exemplary embodiments, the ribs and/or base are formed from hollow tubing. The tubing may have any cross-sectional shape such as, for example, square, round, rectangular, triangular, oval, etc. The tubing may be made from any material of sufficient strength including, for example, metals, such as stainless steel or aluminum, or plastics. The hollow tubing provides reduced weight and more flexibility while providing sufficient strength to support the structure. Ribs 120 and barrier 130 help provide a skeletal structure upon which fibrous covering 102 may be supported. It should be appreciated that, in various exemplary embodiments, one or more additional members may also be connected to ribs 120 (e.g., between adjacent ribs to, for example, add rigidity). It should be appreciated that barrier 130 may include apertures in positions that correspond to each window 104 or any other openings. It should also be appreciated that barrier 130 may be any net, web, grid, mesh, screen, wall, or the like that helps provide suitable rigidity between ribs 120 and/or to hunting blind 100 . It should be appreciated that either ribs 120 and/or barrier 130 may comprise one or more pieces each (e.g., five rib sections may be joined to form a single rib 120 ).
[0045] As shown in FIG. 2 , in various exemplary embodiments, barrier 130 is coupled to ribs 120 . It should be appreciated that, while barrier 130 is shown in FIG. 2 coupled to an external surface of ribs 120 , in various exemplary embodiments, bather 130 may be coupled to an internal surface of ribs 120 .
[0046] In various exemplary embodiments, barrier 130 is a lightweight metal fence material. In various other embodiments, barrier 130 may be a more solid material with fewer apertures. For example, in various exemplary embodiments, bather 130 may be a plastic or plywood layer. It should be appreciated that the desired strength and/or rigidity of barrier 130 may depend, at least in part, on the number of and distance between ribs 120 . Likewise, the desired strength, and/or rigidity of barrier 130 may depend, at least in part, on the weight, thickness, size, and/or rigidity of fibrous covering 102 . In various exemplary embodiments, fibrous covering 102 may be sufficiently rigid such that barrier 130 may be omitted. In various exemplary embodiments, additional layers may be provided (e.g., between barrier 130 and fibrous covering 102 ). For example, a fire resistant and/or fire retardant layer may be provided between barrier 130 and fibrous covering 102 .
[0047] In various exemplary embodiments, fibrous covering 102 includes margins or end portions that have one or more pockets, sleeves, or similar structures for coupling the end portions to a terminal rib 125 of hunting blind 100 . For example, an end portion may include a pocket around its outer dimension into which a terminal rib 125 may be fed through to help couple the end portion to terminal rib 125 .
[0048] In various exemplary embodiments, as shown in FIG. 3 , frame 110 includes a base 118 that may be a single piece or be assembled from multiple pieces. In various exemplary embodiments, the base 118 comprises four pieces coupled together.
[0049] In various exemplary embodiments, frame 110 is generally rectangular shaped and helps define a lower, outer perimeter of hunting blind 100 . That is, in various exemplary embodiments, frame 110 helps define the perimeter of hunting blind 100 at or near ground level. In various embodiments, frame 110 helps provide a foundation for hunting blind 100 . In various exemplary embodiments, frame 110 includes one or more projections 112 (e.g., posts, pegs, or the like) extending from a top surface of frame 110 . Each rib 120 may interact with one or more projection 112 to couple that rib 120 to frame 110 . As shown in FIG. 3 , in various exemplary embodiments, in place of or in addition to projections 112 , frame 110 may include projecting sleeves 116 . In such exemplary embodiments, each rib 120 may be inserted into one or more sleeves 116 to couple that rib 120 to frame 110 . Likewise, in various exemplary embodiments, in place or in addition to projections 112 and/or sleeves 116 , frame 110 may include depressions, pockets, cutouts, and/or the like to receive a portion of one or more ribs 120 , thereby coupling ribs 120 to frame 110 .
[0050] In various exemplary embodiments, as illustrated in FIGS. 4 and 7 , the frame may comprise panels 117 and 119 containing rib sections 121 and barrier sections 131 . FIG. 4 shows one exemplary embodiment of a side panel 117 and FIG. 7 shows one exemplary embodiment of a top panel 119 .
[0051] As illustrated in FIG. 5 , according to various exemplary embodiments, the frame 110 is formed by attaching side panels 117 to each side of the base 118 . As illustrated in FIG. 6 , additional side panels 117 are attached to the side panels 117 previously attached to the base 118 . In various exemplary embodiments, as shown in FIGS. 7 and 8 , the frame 110 is completed by attaching top panel 119 to the side panels. In various exemplary embodiments, the panels 117 and 119 are attached to the frame and one another with a projection 112 and sleeve 116 , but it should be appreciated that any means for attaching the panels 117 and 119 . In various exemplary embodiments, side panels 117 may have different curvatures (e.g., the lowest section may have a larger radius than higher sections in order to increase the angle between the base and the lowest panels). In various exemplary embodiments, the lowest rib sections have a radius of 72 inches and the remaining rib sections have a radius of 36 inches.
[0052] FIG. 11 shows a screw and a bracket or clip usable to attach barrier 130 to one or more ribs 120 according to an exemplary embodiment. In various exemplary embodiments, the screw is thread cutting, self-guiding, or self-tapping to help facilitate the screw entering the ribs. FIG. 12 shows use of a screw and a bracket or clip for coupling the barrier to a rib according to an exemplary embodiment. It should be appreciated that any suitable known or later-developed connection method or device, or combinations thereof, may be used to attach or couple barrier 130 to one or more ribs 120 . For example, the barrier may be tied to the ribs, welded to the ribs, glued to the ribs, etc.
[0053] In various other exemplary embodiments, as shown in FIG. 9 , blind 100 is assembled by attaching ribs 120 to the base 118 . Ribs 120 may comprise one or more segments. As shown in FIG. 10 , the barrier 130 is coupled to the ribs 120 . Barrier 130 may comprise one or more sections. In various exemplary embodiments, the barrier 130 is coupled to the ribs 120 with clip 132 , as shown in FIGS. 11 and 12 . The disclosed clip is particularly useful when the ribs 120 and barrier 130 are made of dissimilar metals that are not readily welded or soldered. Although the barrier is shown and described as coupled to the ribs with clip 132 , it should be appreciated that any means for coupling (e.g., welding) may be used within the scope of this disclosure.
[0054] FIGS. 8 and 10 shows schematic representations of a portion of hunting blind 100 according to a second exemplary embodiment. As shown in the exemplary embodiment shown in FIGS. 8 and 10 , hunting blind 100 includes a frame 110 and three ribs 120 connected to frame 110 . Frame 110 has a generally rectangular planar shape and each rib 120 has an arched or roughly circular shape. As such, frame 110 and ribs 120 collectively provide a roughly cylindrical or tubular shape. In various exemplary embodiments, frame 110 includes one or more legs 114 , which may help stabilize hunting blind 100 (e.g., by helping prevent hunting blind 100 from tipping or rolling over).
[0055] It should be appreciated that rib 120 may include any number of sections or portions, which are interconnected to provide the general shape shown in FIGS. 1-10 . In various exemplary embodiments, the portions of each rib 120 can be packaged and shipped using conventional shipping methods, as opposed to, for example, relying on specialty (e.g., freight) shipping. It should be appreciated that each rib 120 may be constructed from any desirable material and have any desired dimensions. In various exemplary embodiments, each rib 120 is constructed of hollow tubing (e.g., square tubing, rectangular tubing, circular tubing, etc) of metal (e.g., aluminum). Using aluminum tubing, for example, may help lower the total weight of the fully constructed hunting blind 100 . Additionally, hollow tubing may be easier to penetrate with fasteners (e.g., self-tapping or thread cutting screws) used to secure barrier 130 to each rib 120 .
[0056] As shown in FIGS. 8-10 , in various exemplary embodiments, one or more ribs 120 (e.g., a terminal or end rib) may include one or more horizontal struts (not shown) and/or one or more vertical struts 128 . As shown in FIGS. 8-10 , vertical struts 128 help provide support for a door or other entry. It should be appreciated that hunting blind 100 may include any number of doors. In various exemplary embodiments, a single door is provided between horizontal strut 126 , vertical strut 128 , portions of frame 110 , and portions of rib 120 . It should also be appreciated that, in various exemplary embodiments, either or both of horizontal strut 126 and vertical strut 128 may be omitted. That is, vertical strut 128 , and thus the door, may extend from a bottom portion of hunting blind 100 , where it may be coupled to frame 110 , to semi-circular portion 122 and horizontal strut 126 may be omitted. Likewise, the door may extend between each elbow portion 124 and vertical strut 128 may be omitted.
[0057] It should be appreciated that, vertical strut, if present, may be located at any desirable position. For example, vertical strut 128 may be located to one side in order to provide a larger door. In various exemplary embodiments, two vertical struts 128 may be provided and the door may be provided between the two vertical struts 128 . In various exemplary embodiments, the door is wide enough for a standard wheel chair to pass through the door. Likewise, in various exemplary embodiments, the door is wide enough for an all-terrain-vehicle (e.g., an ATV, a “four-wheeler”, etc.) to pass through the door. In various exemplary embodiments, hunting blind 100 (e.g., frame 110 ) includes a ramp or a similar structure to facilitate entrance into hunting blind 100 by a wheelchair, an all-terrain-vehicle, or other wheeled apparatus.
[0058] In various exemplary embodiments, hunting blind 100 is provided as a kit for assembly. The kit, in various exemplary embodiments, includes a frame base 118 in one or more pieces, panels 117 and 119 (in any desired number and size) having rib sections and barrier sections, fibrous cover, and end covers (the end panels may comprise a fibrous cover). In various exemplary embodiments, the kit includes ribs a frame base 118 in one or more pieces, ribs in one or more segments, a bather in one or more sections, a fibrous cover, and end covers.
[0059] In various exemplary embodiments, the parts of the kit are assembled to provide hunting blind 100 . In an exemplary method of assembling the kit, the one or more base members are coupled together to provide roughly rectangular base 110 . Each elbow or support portion 124 of each rib 120 is then coupled to base 110 (e.g., by sliding a first generally straight portion or a curved portion of each elbow or support portion 124 onto or around posts 112 or into sleeves 116 of base 110 ). Each semi-circular portion 122 is then coupled to the corresponding elbow or support portions 124 (e.g., by sliding semi-circular member 122 onto or around post structures of the two corresponding elbow or support portions 124 ) to provide ribs 120 . Barrier 130 is then coupled to ribs 120 to complete a skeletal structure of hunting blind 100 . Fibrous covering 102 is then coupled to an outer surface of the skeletal structure.
[0060] In various exemplary embodiments, baling string, netting and/or the like may be utilized to help couple fibrous covering 102 to the skeletal structure. In various exemplary embodiments, bailing string, netting and/or the like, and/or structures that give the appearance of bailing string, netting, and/or the like, may be provided as part of fibrous covering 102 .
[0061] It should be appreciated that the above-outlined method of assembling a kit of hunting blind 100 may additionally include steps usable to provide windows, doors, and/or other openings in hunting blind 100 . In various exemplary embodiments, such additional steps may include providing an opening in barrier 130 (e.g., by cutting, tearing, ripping, or the like) in locations of desired openings. For example, a generally u-shaped tear or cut in barrier 130 may be provided in a desired location of a window such that the portion of barrier 130 within the u-shape tear or cut may be usable as a portion of the above-outlined coverings of windows (e.g., cover 106 of window 104 ). Likewise, similar actions may be taken with regard to fibrous covering 102 .
[0062] As shown in FIGS. 1 and 2 , in various exemplary embodiments, hunting blind 100 includes at least one window 104 . Window 104 may be utilized by a user located within hunting blind 100 to see outside of hunting blind 100 . Window 104 may also be useful to fire projectiles, such as, for example, pellets, bullets, arrows, darts, and the like, at objects (e.g., animals) located in an area around hunting blind 100 and/or to photograph objects (e.g., animals) located in the area around hunting blind 100 .
[0063] Additionally, in various exemplary embodiments, each window 104 may include a cover 106 . Cover 106 may be utilized to close a window when that window is not in use. For example, cover 106 may be used to help prevent or inhibit an animal or other observer from seeing into the interior of hunting blind 100 . Likewise, cover 106 may be used, at least in part, to conceal, mask, or hide other sensory indicators, such as, for example, the appearance, heat, smell, sounds, and/or the like coming from any occupants or other contents of hunting blind 100 . In various exemplary embodiments, the cover 106 includes two elastic straps between which a sheet of material is suspended. The straps are capable of connecting to the interior of the hunting blind so that the sheet of cover material obstructs a window. In various exemplary embodiments, the straps are longer than the cover, which makes it easier to uncover a window. In various exemplary embodiments, the curvature of the hunting blind (e.g., for a round bale) will create a gap between the window and the cover. In some such embodiments, a rod is attached to the frame to push the cover toward the window.
[0064] While this invention has been described in conjunction with the exemplary embodiments outlined above, various alternatives, modifications, variations, improvements, and/or substantial equivalents, whether known or that are or may be presently foreseen, may become apparent to those having at least ordinary skill in the art. Accordingly, the exemplary embodiments of the invention, as set forth above, are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit or scope of the invention. Therefore, the invention is intended to embrace all known or earlier developed alternatives, modifications, variations, improvements, and/or substantial equivalents. | An exemplary embodiment relates to a hunting blind comprising a frame comprising one or more rib members and a barrier layer, a fibrous covering, and a camouflage layer. Another exemplary embodiment relates to a method of assembling a hunting blind comprising providing a generally rectangular frame base, providing one or more frame panels comprising at least one rib and a barrier layer, attaching two frame panels to opposite sides of the frame base, forming a canopy from two or more joined frame panels, and covering the canopy with a fibrous covering. Another exemplary embodiment relates to a method of assembling a hunting blind comprising providing a generally rectangular frame base, attaching one or more ribs to the frame, attaching one or more barriers layers to the ribs with a clip, attaching a fibrous covering to the ribs or barrier layers, and attaching a covering to the ends of the blind. | 4 |
BACKGROUND OF THE INVENTION
This invention relates to magnetic induction type pickups for stringed musical instruments, and deals more particularly with an improved mounting system for attaching such a pickup to the body of an instrument.
Magnetic induction type pickups for stringed musical instruments are ones which are conventionally mounted beneath and close to the strings of an instrument and wherein, as a string vibrates, the reluctance of an associated flux path through the pickup is varied to produce a varying magnetic flux which in turn induces a varying electrical output voltage in an associated coil. Thee output signal is then amplified, and perhaps also distorted and modified in various different ways, to produce an output signal driving one or more electro-acoustical speakers. Sometimes, the performer is located so close to the speakers, and the sound level from the speakers is so great, that the sound vibrations in the air set up vibrations in the instrument body which are fed back through the body to the electrical pickup to vibrate the pickup and to thereby establish a positive feedback conditions producing microphonics or squeal in the speaker output. Also, as the instrument is played, it is subject to various knocks or blows from the performers' hands or other objects, and vibrations from these impacts are also often transmitted to the pickup to produce an undesirable audible response from the speakers.
The general object of this invention is, therefore, to provide a mounting system for an electrical pickup in a stringed musical instrument whereby transmission of vibrations from the instrument body to the pickup is minimized to reduce undesirable microphonics and other noise in the associated speaker output.
A further object of the invention is to provide a pickup mounting system for a stringed musical instrument which is of a relatively low cost, of a simplified and easily assembled construction and which allows for adjustably raising and lowering the pickup or tilting it about various different axes to vary its position relative to the strings.
Other objects and advantages of the invention will be apparent from the drawings and from the following description thereof.
SUMMARY OF THE INVENTION
The invention resides in an electrical pickup mounting system for a stringed musical instrument of the type wherein at least a part, and usually the major portion, of the pickup is located in a cavity below a top plate of the instrument, with the pickup having a part extending through an opening in the top plate toward the strings. Below the top plate the pickup has a laterally outwardly extending mounting flange, preferably in the form of two ears at its opposite ends. The flange carries a number of mounting elements of rubber or similar resilient material, and each mounting element has an opening facing the top plate. A plurality of screws, one for each mounting element, extend through the top plate and each has a threaded shank extending into the opening of its associated mounting element and threadably connected thereto by a coengaging part received in the mounting element opening and separate from the mounting element. A helical compression spring is received on each screw shank and is compressed between the top plate and the associated retaining element. Together the resilient mounting elements and the helical compression springs introduce such spring and damping factors between the instrument body and the pickup as to minimize the transmission of vibration between the two parts over a wide range of frequencies. Preferably, the resilient mounting members are externally waisted grommets assembled with the mounting flange by being laterally slid into blind slots of the pickup flange; and, the parts which threadably engage the shanks of the screws are self-threading bosses of Delrin or similar thread stripping resistant plastic extending into the grommet eyes from a retaining member located below the grommets and to which all of the bosses are fixed to both hold the bosses from turning as the screws are threaded into or out of them and to hold the bosses laterally in place in their mounting flange slots.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a port of a guitar having an electrical pickup with a mounting system embodying this invention.
FIG. 2 is an enlarged fragmentary sectional view taken on the line 2--2 of FIG. 1.
FIG. 3 is an end view taken on the line 3--3 of FIG. 2.
FIG. 4 is an end view similar to FIG. 3 but shows the pickup of FIG. 3 in a different condition of adjustment.
FIG. 5 is an exploded perspective view of a portion of the mounting system shown in FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, this figure shows a guitar 10 having a body 12, a neck 14 and a set of strings 16 extending along the length of the neck and attached at their lower ends to a bridge and tail piece unit 18 fixed to the body 12. Included in the instrument are two electrical pickups 20 and 22 located beneath the strings 16 and at spaced points along the length thereof. Because of the different locations of the two pickups 20 and 22 and the fact that the character of the vibration of each string is different at different points along its length, slightly different output signals will be produced from each of the two pickups 20 and 22, and by suitable switches the performer may select either one or both of the pickups as the electrical signal source. The illustrated arrangement of the two pickups 20 and 22 is in general well known and is shown by way of example only. That is, the mounting system of this invention pertains to the mounting of an individual pickup from the associated instrument body. Where the instrument includes two pickups, as in the case of FIG. 1, both pickups may and preferably do utilize the mounting system of this invention. In cases where the instrument has only a single pickup, the mounting system of this invention may be used with such pickup with equal effect.
Further, the guitar 10 of FIG. 1 is of the "solid body" type wherein the body 12 is made of a single piece of solid wood or other material having relatively small cavities for receiving the pickups and other components. This again, however, is a matter of choice for purposes of explanation, and the invention is not necessarily limited to such type of guitar and may as well be used in mounting pickups to various other kinds of stringed instruments including hollow bodied instruments having bodies made of relatively thin-walled material enclosing relatively large cavities.
Regardless of the type of instrument involved, the pickup mounting system of this invention is one wherein a major part of the pickup is mounted within a body cavity defined in part by a top plate having an opening through which the pickup projects outwardly toward the strings. In the illustrated case, as shown by FIG. 2, the cavity, indicated at 24, is of a relatively small size, is cut out of the material of the body 12 and is covered by a top plate 26 constituting a portion of a pick guard 28 fastened to the top surface of the body 12.
FIG. 2 illustrates the pick 20 and its associated mounting system. A similar mounting system, not shown herein in detail, may be used with the pickup 22. Each of the pickups 20 and 22 is of the magnetic induction type and may be any one of various different forms and constructions well known in the art. Preferably, however, it is of the type shown and described in copending patent application, filed Mar. 10, 1975, Ser. No. 556,896, entitled MAGNETIC INDUCTION STRINGED INSTRUMENT PICKUP, to which application reference may be had for further details of its construction.
Referring to FIGS. 2 to 5, the pickup 20 includes a main body 30 which extends through a conforming opening 32 in the top plate 26. Inwardly or rearwardly of the top plate 26 the pickup includes a laterally outwardly extending mounting flange in the form of two ears 34 and 36 located at opposite ends of the pickup. These ears are outwardly extending continuations of a base plate 38 to which a rectangular cup-shaped case or housing 40 of the main body is attached. Both the case 40 and the base plate 38 are made of an electrically conductive non-magnetic material, such as brass. Carried by the ears 34 and 36 are three resilient mounting elements in the form of rubber grommets 42, 42. The grommets are received in blind slots 44, 44 extending inwardly from the outer edges of the ears 34 and 36. Each grommet 42 is of the type having a central eye 46 and an external waist or reduced diameter portion 48. The waist portion 48 has an external diameter substantially equal to the width of each blind slot 44, 44, and an axial length substantially equal to the thickness of the ears, so that each grommet may be assembled with its ear 34 or 36 by being slid laterally into its associated blind slot 44, and once a grommet is in such assembled position it is restrained against movement relative to its ear in all directions except for outward sliding movement.
After the three grommets 42, 42 are assembled with the two ears 34 and 36, they are locked in such assembled positions by inserting into their eyes 46, 46, and from their rears, the three bosses 50, 50 of a retaining member 52, the retaining member 52 having a Y-shaped body 54 to which all three bosses 50, 50 are fixed. From inspection of FIG. 5, it will be understood that the three blind slots 44, 44 face in such relatively different directions that after the bosses are inserted in the grommet eyes, movement of any one of the grommets along the length of its slot is prohibited. In particular, the slot 44 of the ear 34 faces outwardly along an axis generally transverse to the strings 16, 16 and the two slots 44, 44 of the ear 36 face in the opposite directions along an axis generally parallel to the strings.
Passing through the top plate 26 are three screws 56, 56 having slotted heads which engage the outer surface of the top plate. Extending inwardly from its head each screw includes a threaded shank 58 which extends into the eye of its associated grommet and threadably engages the boss 50 also received in the grommet eye.
Finally, to complete the mounting system, each screw 56 has a helical compression spring 60 received on its shank 58 and compressed between the top plate 26 and the associated grommet 42. Accordingly, the three springs 60, 60 provide a degree of resiliency in the support of the pickup 20 from the top plate 26 and urge the pickup to its illustrated normal position. Also, the three grommets 42, 42 add further resilience and damping in the connection between the top plate and the pickup, and this together with the resilient influence of the springs 60, 60 provides a connection which is highly effective in inhibiting the transmission of unwanted vibrations from the top plate to the pickup.
The described mounting system is also relatively inexpensive to produce and easy to assemble. For example, the blind slots 44, 44 are easily cut into the ears 34 and 36, the grommets 42, 42 are readily available at little expense, and the retaining member 54 may be made as a relatively low cost plastic injection molded part. The plastic used for the part 54 is preferably Delrin or some other plastic which allows the screws 56, 56 to self thread into the bosses 50 and which is resistant to thread stripping. Therefore, in making the support system, no machine threading operations are required.
Still further, the illustrated mounting system is one which allows the pickup 20 to be readily moved to different adjusted positions relative to the strings 16, 16 as may be desired to produce a different effect in the output signal. For example, by turning all of three screws 56, 56 the same amount in the same direction, the pickup may be bodily raised or lowered relative to the strings. By turning the two screws 52, 52 of the ear 36 the same amounts in the same direction, while not turning the screw 56 of the ear 34, the end of the pickup adjacent the ear 36 may be raised or lowered relative to the other end. Likewise, by turning the one screw 56 of the ear 34, while not touching the two screws of the ear 36, the end of the pickup adjacent the ear 34 may be raised or lowered relative to the other end. Lastly, as shown in FIGS. 3 and 4, by turning the two screws of the ear 36 in opposite directions while not touching the screw 56 of the ear 34, the pickup 20 may be tilted about an axis extending transversely of the strings. In this connection, it should be observed that the one blind slot 44 of the ear 34 and its associated screw 56 is located midway between the two slots 44, 44, and their associated screws 56, 56 of the ear 36, as measured longitudinally of the strings, so that when the two screws of the ear 36 are adjusted as shown in FIGS. 3 and 4, the pickup 20 pivots about a transverse axis generally defined by the screw 56 of the other ear 34. | A guitar or similar stringed musical instrument includes an electrical pickup located beneath the strings for transforming the string vibrations into electrical signals subsequently amplified to provide an electronically enhanced reproduction of the string sound. The pickup is of the magnetic induction type having no direct mechanical connection with the strings. The system for mounting the pickup from the body of the instrument inhibits the transmission of vibrations from the instrument body to the pickup to minimize extraneous noise in the output signal, and it is also one which is of relative simplicity and low cost and which provides for easy adjustment of the pickup relative to the strings. | 6 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates generally to the field of computer systems, and specifically to a method and structure of managing memory resources in a computing environment.
[0002] A computing environment can be comprised of a single computer unit, such as a PC, or a plurality of nodes in processing communication with one another. The nodes themselves may be comprised of one or more individual units, such as PCs or even monitors, or large computing networks that are electronically linked to one another locally or remotely. Independent of the size of the environment, processing tasks are performed through the use of messages. Messages can be used to perform functions for a single application running on a single unit, or for multiple applications running on multiple nodes. In a larger and more complex computing environment, messages are also used to establish communications between nodes or provide access to shared common resources.
[0003] A message is simply a string of data comprised of bits and bytes, representing different items. For example, a message can include names and addresses, images and documents that need to be transferred (sent or received) at a given processing time. Such data can include character strings, bit strings, binary integers, packed-decimal integers, floating-point numbers and the like. The data string may also include destination information or the return address of the requesting node or application, when applicable, depending on the message type. There are generally four types of messages: a “request” message, a “reply” message, a “one-way” message such as a command, and a “report” message that is used when something unexpected occurs.
[0004] At any one time, many messages may be in transit concurrently. Due to the extent of the messages and to prevent their loss, queues are established to hold unprocessed messages up until processing time. In more complex environments, a plurality of applications or nodes may even share one or more queues at any one time. Therefore, it is important that the type of message queuing implemented provides reliable storage and transfer of information independent of the underlying running application or even the device type. To address such issues and minimize compatibility concerns, sophisticated commercial message queuing packages, such as IBM's MQSeries, have been developed that offer a high-level application program interface (API) which shields programs from the complexities of different operating systems and underlying networks.
[0005] Regardless of the type of queuing provided, in most instances, a collection of different types of queues may be implemented to address the transfer needs of a particular environment. In such instances, a queue manager, stores the implemented message queues in a storage area set-aside in a dedicated memory location in the computing environment. This memory location, hereinafter referred to as the permanent memory or permanent memory location, is designed to hold transferred information (i.e. messages and queuing information) in transit until processing completion.
[0006] Unfortunately, the permanent memory has only a finite storage capacity. In critical peak periods, depending on the amount of messages requiring concurrent storage, the storage capacity may become exhausted. This is especially true in situations when executing applications utilize files that are growing at a rate faster than the data can be processed and removed.
[0007] When capacity is met or exceeded, further storage becomes impossible and a “queue full” condition is established. The inability to provide further storage when needed may cause loss of important information and impact further processing, at least until the condition is relieved.
[0008] In recent years, memory management techniques have been introduced to boost storage capacity by providing a temporary memory, such as a disk, at a different location in order to complement the capacity of permanent memory during critical peak periods. When the permanent memory reaches capacity or nears capacity, new or previously stored information is reallocated and stored in the temporary memory for later retrieval. The reallocated information will be later transferred back to the permanent memory once the storage capacity concerns of the permanent memory have been alleviated.
[0009] The challenge, however, with prior art methodologies that utilize reallocation techniques remain in the transferring of the reallocated information back to the permanent memory. In complex environments, it is of utmost importance to determine correctly how much data can be transferred back during each processing period without overwhelming or under-utilizing the permanent memory and the processing environment. Transferring too little information back at any one time from the temporary memory into the permanent memory, will require information to be retrieved frequently and transferred back, causing unintended processing delays. It is more efficient to transfer back larger quantities of information at any one time when possible, rather than to transfer the same amount over multiple transfers.
[0010] Similarly, too much data transfer at one time can cause an over-capacity condition leading to more reallocation of data from the permanent memory back to the temporary memory. The key, therefore, is to transfer back the largest amount of data without exceeding the storage capacity of the permanent memory.
[0011] One other consideration is to control the data transfer in such a way that doesn't impact one or more of the running applications. A sudden increase in data influx may easily overwhelm a running application, even in instances where the permanent storage capacity is not a consideration. The latter is especially important when queuing packages are utilized that offer a high-level application program interface (such as IBM's MQSeries).
[0012] Consequently, a new method and structure is needed that can determine an optimal rate of information retrieval and transfer back to the permanent memory after information is reallocated to a temporary memory due to storage capacity concerns.
SUMMARY OF THE INVENTION
[0013] A structure and method is provided for optimizing memory resources, by establishing a history file for recording data processing criterion. The history file is then recorded in a first memory. Information either stored in the first memory or scheduled to be stored in the first memory can then be selectively reallocated and stored in an alternate memory. All or portions of the reallocated information can then be restored back to the first memory subsequently, with reference to the history file.
[0014] In an alternate embodiment of the present invention, a method of optimizing memory resources in a computing environment is provided with at least one running application using message queuing. This method provides for the establishing of a history file containing a historical message processing rate for the running application. The history file is then stored in a memory location in the computing environment. Queuing Information residing or scheduled to be stored in this first memory can then be selectively to an alternate memory. Reallocated information can then be restored to the first memory by reference to the history file. The history file will determine how much queuing information can be restored back to the first memory by unsweeping after comparing the history file including the historical message processing rate to a current message processing rate and determining current storage capacity available in the first memory.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a flowchart illustrating an embodiment of the invention;
[0016] FIG. 2 is a flowchart illustrating the creation of a history file as per one embodiment of the present invention;
[0017] FIG. 3 is a flowchart depicting information retrieval using the history file created as per the embodiment of FIG. 2 ; and
[0018] FIG. 4 is a flowchart depicting an embodiment of the invention as it relates to message queuing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The present invention addresses and solves the problems associated with the prior art methodology currently in practice for the management of storage and retrieval of information, especially as it relates to information stored in messaging queues. The present invention provides for a technique that utilizes both a permanent memory and an alternate complementary memory, hereinafter referenced as alternate memory, to address information storage needs of the environment. Information may be reallocated either selectively, such as by a user, or based on capacity restrictions. After reallocation, the present invention provides for a retrieval technique during which the reallocated information can be restored back to the permanent memory under optimal processing conditions, so that the permanent memory and the environment are neither under-utilized nor overwhelmed during the process of information restoration.
[0020] FIG. 1 is a flowchart illustrating an embodiment of the present invention. As depicted in FIG. 1 , to achieve optimal processing conditions during the retrieval of reallocated information, past processing history must be first established and tracked over a period time to ensure its reliability. This process is conducted during initialization procedures, shown at 100 in FIG. 1 , and may be inclusive of several processing characteristics including but not limited to frequency of access and processing time. The processing characteristics may pertain to a single application running on a single computer unit, or to many aspects of a large computing environment. For simplicity of reference and ease of understanding, however a single application is used in the discussion of the present invention provided below and in the embodiments illustrated in FIGS. 2 and 3 , but it should be understood that the teachings of the present can be equally applied to multiple applications or an entire large computing environment having many nodes and components.
[0021] To accomplish this task, the past processing history when obtained is stored in a history file located in a memory location, preferably in the permanent memory, for later use. The processing history, as per one embodiment of the present invention, is periodically adjusted so as to reflect any major processing changes. A history file is maintained in the computing environment for the processing history of an application, for example. FIG. 2 illustrates an example of maintaining a processing history as per an embodiment of the present invention and will be discussed in detail later.
[0022] Once a history file is established, whether containing a peak access rate or additional information, the file will be periodically updated to reflect updated information. Normal operation will then continue, with data and information being stored in the permanent memory until reallocation either becomes necessary or desired as shown at 120 . Note that with the advent of having access to an alternate memory, the user or a program, may interactively or automatically (i.e. by scheduling etc.) desire to take advantage of the expanded memory capacity and reallocate information before capacity concerns even arise, just for ease of processing or other similar reasons.
[0023] Required or selective reallocation is conducted in the same manner for either case, as provided at 130 . Data and information, either destined for permanent memory or already stored in the permanent memory, is reallocated to the alternate memory instead. Reallocated information, is ultimately restored to permanent memory for a variety of reasons such as processing ease and permanency.
[0024] Restoration of the reallocated information back to the permanent memory, under the teachings of the present invention is performed using historical behavior determined during the initialization process and stored in the history file as shown at 140 . It may not be feasible, necessary or even desired to retrieve and/or restore all of the reallocated information from the alternate memory at once. For example, if the reason for reallocation was the exhaustion of permanent memory, once the capacity has been partially restored, restoration of only a portion of the reallocated information may be possible at a specific time. Transferring the entire reallocated information can, in such a case can overwhelm the permanent memory once again. If only partial restoration is possible or desired, records can be previously established in the history file that enable the restoration to be conducted based on a certain criteria. For example, restoration can be performed on the basis of restoring the most frequently accessed data first. Alternatively, restoration can be performed on the basis of most recently reallocated data to be restored first, etc. In this example, the history file is used primarily to establish how much information is to be retrieved and restored to permanent memory during any one processing time period as shown in 150 in FIG. 1 . To illustrate the retrieval and restoration process in greater detail, an embodiment of the present invention is provided in FIG. 3 and will be later discussed in detail.
[0025] Referring now to FIG. 2 , an example of generation of a history file is illustrated as per an embodiment of the present invention. In FIG. 2 , it is desired to establish an optimal processing rate to be stored in the history file for later use. To accomplish this task, the most recent performance of a given application is first tracked over time. It is important in this approach to maintain an accurate history of the rate of retrieval of data by an application accounting for periods when there may be a spike in the rate, while at the same time not preserving that spike indefinitely.
[0026] In FIG. 2 , each time an application accesses a certain file as shown at 200 , the access count is incremented in a counter, as provided in 210 . The counter is incremented until a predetermined sampling value is reached. The sampling value may relate to a time period, for example of 10 seconds. In this way frequency of access is established during a certain time period. In this example, thee sampling time value must be sufficiently large to minimize the influence of statistical anomalies. When the sampling period is not yet deemed sufficient to save the retrieval rate, the process of monitoring the count continues ( 225 ). Once the sampling period is deemed sufficient, the frequency of access or the value of the counter at that time is then saved, as shown at 222 . Based on the sampling time value and the frequency of access, a sample access rate (per second) can then be calculated (by dividing the frequency of access by the sampling time) and saved, as shown at 230 .
[0027] In addition to tracking the number of accesses and calculating the sample access rate (of the most recent period), the processing rate is also calculated during the high peak processing periods. This rate, hereinafter referenced as the “peak rate”, is calculated in a similar manner to the sample access rate. In the embodiment illustrated in FIG. 2 , the peak rate is tracked over a one hour period as shown at 250 . Here a measure is implemented to assure that the peak rate maintained in the application history does not represent a stale value. As shown in FIG. 2 , if the peak rate is calculated prior to a certain time, one hour in this example ( 252 ), the peak rate is then adjusted downward e.g. by dividing it in half as shown at 255 .
[0028] Before the peak rate is saved in the history file, the peak rate is compared against the current sample access rate. This comparison is made because in order to achieve optimal processing time, it is important to obtain and save the highest rate of retrieval during the current cycle. Therefore as shown at 260 , the peak rate is compared to the sampled rate. If the current sample access rate has a higher value, then the current sample access rate is stored as the peak rate in the history file, as shown at 270 . In either case, the rate with the higher value, be it the old or divided peak rate value or the current sample access rate, will be stored in the history file as the new peak rate and will be referenced as the peak rate for retrieval purposes during subsequent steps. The counters and timers are then reset ( 280 ) to allow monitoring to begin for the next period ( 290 ).
[0029] Referring back to FIG. 1 , normal operation will then continue after the generation of the history file discussed in FIG. 2 until information is reallocated. Once a request for restoration of reallocated data is processed, all or portions of the reallocated data will be restored by using the information stored in the history file generated in the embodiment of FIG. 2 . FIG. 3 provides an illustration of how the information previously stored in the history file generated in the embodiment of FIG. 2 will be used.
[0030] In FIG. 3 , the history file established in FIG. 2 is used to predict the processing needs of the information during retrieval and restoration. In FIG. 3 , when an information retrieval request is processed as shown at 300 in FIG. 3 , it is first determined if the information already exists in the permanent memory, as shown at 310 . This is to ensure that attempts at retrieval are not made unnecessarily to the alternate memory if the information was never reallocated or already retrieved at an earlier time ( 312 ).
[0031] If the information is reallocated and has never been restored, however, the information needs to be retrieved from the allocated memory (path 311 ) and transferred back into the permanent memory. The history file is then accessed to determine the amount of the reallocated data scheduled to be transferred from the alternate memory back to the permanent memory should be transferred per processing period. In order to determine the current permanent memory capacity and consequently determine the optimal information transfer amount, several variables have to be checked. The first of these variables is the peak value obtained from the application history, as determined earlier. This step is shown at 320 in FIG. 3 . Once the peak value is retrieved, this historical peak is checked (as shown at 340 ) against a current sampling rate, as provided at 330 . The current sampling rate is the most recent processing rate obtained at retrieval request time. The higher of the current sampling value 345 or the historical value 350 is then compared against a user defined override, as shown at 360 .
[0032] The purpose behind this comparison procedure is to determine if the retrieval need is higher or lower than the current allowable storage allocation needs in the permanent memory at retrieval request time. In this manner, if it is possible to obtain the entire retrieval record at one time, then retrieval will be accomplished at once to allow for optimal processing time. If however, the present allocation in the memory cannot accommodate the entire retrieval of the particular requested information, the retrieval has to be parsed out and provided during multiple processing intervals. The user defined override can also ensure that in situations where it is desired to control the memory allocation so as to reflect a different capacity or when it is desired to set minimum values, such override can be incorporated into the methodology used herein.
[0033] Once the higher of the value of the current rate 345 is compared to the historical use rate 350 against the user override rate 360 , the higher of those values is then used as the target number of records to retrieve from file (either 365 or 370 as shown in FIG. 3 ).
[0034] After the target rate has been established, the target rate ( 370 or 365 ) will then be used to transfer records back into the permanent memory, as provided at 380 . The values then will be reset and the system will await a new retrieval request ( 390 ).
[0035] When a complete record retrieval cannot be satisfied in one retrieval attempt, e.g. because it exceeds a historical peak value, the retrieval is parsed out over several retrieval processing intervals. In such instances, the procedures described above relative to FIG. 3 will be reiterated until all requested information is retrieved using optimal overall processing retrieval time. This concept is also illustrated in FIG. 1 . The decision box shown at 170 in FIG. 1 , provides for either the reiteration of the process until all requested information is retrieved or a return to the normal procedure until another request for information retrieval is received.
[0036] The present invention, provides a simple algorithm that relies on predictive and recent past performance of a given application so that high performing applications or other similar components of a computing system can be provided sufficient memory resources that will allow them to process data quickly even in an environment where there is an insufficient amount of memory available to satisfy the needs of all the applications currently running on the system.
[0037] An example of an instance where the teachings of the present invention can improve both memory resources availability and overall performance is the application of these teachings to complex message queuing algorithms such as IBM's MQ Series as illustrated in FIG. 4 . Memory resident queues such as that of IBM MQ series, are monitored at predefined time intervals. In such cases, when the monitoring indicates that a particular queue is not being serviced at a desired level, then action is taken to sweep one or more messages from the queue. The swept messages are removed from the queue and reallocated to an alternate memory location as provided in FIG. 4 at (path) 422 . The sweeping of the messages frees up system resources associated with the messages, thus allowing other tasks to be serviced. If, after the sweeping it is determined that the queue can handle additional messages, then one or messages are transferred back on to the queue from the alternate memory location, a process known as unsweeping.
[0038] Sweeping can also occur when a large number of messages arrive on a queue that is being serviced. The excess messages, the amount that exceeds the queuing capacity, is reallocated to an alternate memory location, similar to the information retrieval process discussed earlier. At unsweep time, the excess messages are retrieved from a resident file or other allocated location back to the queue again as shown at 442 .
[0039] One existing challenge with the unsweep function is that the transfer of messages back to the queues puts an unnecessary burden on the running operating system which can result in an immediate need to sweep the queues again. The problems associated with prior art currently in practice are also similar in this arena to the previously discussed problems of information retrieval in general. For one, it is difficult to know when and how much queuing messages are needed to be reallocated or retrieved during subsequent message transfer periods. In addition, the continuous threshing of messages during subsequent sweeping and unsweeping can waste system resources and impact performance speed and cause integrity problems.
[0040] An embodiment of the invention addresses such problem. By establishing a prior history file, the unnecessary sweeping and unsweeping of information can be eliminated. Continuous and unnecessary sweeping and unsweeping of information can negatively impact an application's ability to get messages from the queue and may even impact the underlying operating system running in the environment.
[0041] During the creation of a history file as shown at 400 , the message queuing (MQ) queue rate is tracked and used in determining the number of messages that can be left in the memory when sweeping the queues so that sufficient messages will be left to be processed at any given time period. This will help the overall system performance as it cuts down on idle time and performance issues by trying to reach an optimal level by a reiteration process of sweeping and unsweeping.
[0042] As per the teachings of the invention, a user override can also be established, for example as a field identified as “SWEEPDEPTH” that can allow the user to specify a minimum number of requests to be overriding while performing the unsweep function.
[0043] It is also possible under the teachings of the present invention to avoid complete unsweeping of messages. As not all messages are needed to be retrieved at one time, whether controlled by the past history or by user overrides, a partial unsweep can be conducted which will tremendously alleviate system performance problems. In other words the unsweep function will only retain part of the messages until the number of messages in memory reaches either the user defined “SWEEPDEPTH” or a rate previously established in the history file, similar to the peak rate (selectively named as “Getrate”) whichever has a higher value (similar to the embodiment depicted in FIG. 3 ). In this manner, sufficient messages are returned to permanent queue memory to allow the application to process messages from the memory queue for a specified period of time and the remainder of the excess messages are left in the alternate memory location until the application needs them. Unsweep will also be controlled by the resources that are available to the system based on assessing current needs of the environment (current processing rates) and referencing the previously stored information in the history file, as shown at 450 . The history file will be used, if necessary during several processing periods, until all messages are restored as provided in 470 .
[0044] Note that there are other instances where an unsweep function can affect system performance. In such instances when unsweep process becomes so excessive that it interferes with normal operation of an application and processing of data, under the teachings of the present invention, the sweeper monitoring will prevent certain queues to be swept. These queues(s) will be skipped based on determining which queues have just been unsweeping, by perhaps setting a certain time variable (up to a certain pre-established period of time), in order to avoid unnecessary sweeping after unsweep has started. This is especially true when an artificially low sampling rate occurs occurring during a period when the unsweep process first commences.
[0045] While the invention has been described in accordance with certain preferred embodiments thereof, those skilled in the art will understand the many modifications and enhancements which can be made thereto without departing from the true scope and spirit of the invention, which is limited only by the claims appended below. | A structure and method is provided for optimizing memory resources, by establishing a history file for recording data processing criterion. The history file is then recorded in a first memory. Information either stored in the first memory or scheduled to be stored in the first memory can then be selectively reallocated and stored in an alternate memory. All or portions of the reallocated information can then be restored back to the first memory subsequently, with reference to the history file. | 6 |
TECHNICAL FIELD
[0001] The present invention relates to a particular formulation for a chemical tablet. More particularly, the present invention relates to a chemical tablet that removes phosphorus and provides consistent chemical dissolution in water.
BACKGROUND
[0002] Phosphorus (P) is commonly found in municipal and agricultural wastewater, originating from the digestion of phosphorus-containing food sources. Soluble reactive phosphorus, typically in the form of orthophosphate (PO 4 +3 ), can be a nutrient for aquatic plants, such as algae, which can be either a health risk to aquatic life or an aesthetic nuisance to those living near or using the waterways. In the case of blue-green algae, toxic by-products can be produced, which create health issues if a lake or reservoir would be used as a source of drinking water.
[0003] Control of phosphorus can be achieved by forming a precipitant when the soluble phosphorus, in the form of orthophosphate, combines with a soluble metal, such as aluminum or iron. Several coagulants are also applicable to remove phosphorus from wastewater or sewage.
[0004] Aluminum sulfate is commonly used for phosphorus control due to its low metal to phosphorus ratio required for formation of a precipitant. It is widely used in some wastewater treatment plants and municipal sewage treatment plants for removing phosphorus. In these plants, aluminum sulfate needs to be added into wastewater, or secondary treated or tertiary treated effluent in certain methods. The chemical needs to be added to a treatment unit constantly. In on-site sewage treatment plants, it is difficult to use special equipment to add any coagulant for phosphorus removal treatment. Therefore, a special composition, form and method need to be developed to carry out the phosphorus removal task in on-site sewage treatment plants.
SUMMARY
[0005] In accordance with one or more embodiments of the present invention, is an aluminum sulfate tablet that can be dissolved into water or wastewater constantly.
[0006] In accordance with one or more embodiments of the present invention, is an efficient phosphorus removal system based on the aluminum sulfate tablet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a side view of an aluminum sulfate tablet showing a cylindrical central body portion and a large beveled top and a large beveled bottom, in accordance with one or more embodiments of the present invention.
[0008] FIG. 2 is a cross-sectional side view of a treatment system with a tablet dispenser unit in which aluminum sulfate tablets shown in FIG. 1 can be used to remove phosphorus from wastewater, in accordance with an embodiment of the present invention.
[0009] FIG. 3 is a cross-sectional side view of a treatment system with a tablet dispenser unit in which aluminum sulfate tablets shown in FIG. 1 can be used to remove phosphorus from wastewater, in accordance with another embodiment of the present invention.
[0010] FIG. 4 is a close-up, cross-sectional, isometric view of a bottom portion of the tablet dispenser unit of FIGS. 2 and 3 , in accordance with one or more embodiments of the present invention.
[0011] FIG. 5 is a top view of a filtering system in which a tablet dispenser unit is installed, in accordance with an embodiment of the present invention.
[0012] FIG. 6 is a cross-sectional, side view of the filtering system in which a tablet dispenser unit is installed in FIG. 5 along line A-A, in accordance with an embodiment of the present invention.
[0013] FIG. 7 is a flow chart showing the process for manufacturing a tablet, in accordance with an embodiment of the present invention.
DESCRIPTION
[0014] In accordance with one or more embodiments of the present invention, a composition for and a method to make an aluminum sulfate tablet includes (i.e., comprises) making the aluminum sulfate tablet with a diameter ranging from 1″ to 3.5″ and a weight ranging from 30 to 200 grams. The tablet is made using granular aluminum sulfate particles with a size ranging from 10 to 200 mesh and a binder or binding agent or an organic bonding material made from plant or plants or a viscosity liquid made from fruits. The bonding material can have a chemical formula of, for example, but not limited to: C 6 H 12 O 6 or C 12 H 22 O 11 . The bonding material also can be a mixture of these two or more different bonding materials. The bonding material can be, for example, but not limited to, a food grade starch hydrolysate. The food grade starch hydrolysate can be, for example, but not limited to, one of the following starch hydrolysates: Apple, corn, molasses, cane and other binders made from fruits or plants.
[0015] While the use of coagulants such as aluminum sulfate to assist in the removal of suspended solids in an aqueous media is well established these coagulants previously have only been available in a granular or pre-diluted liquid form. As a result, using these products required the use of pumps, granular dosing equipment, electricity, and plant modifications. Furthermore, existing dosing systems do not account for variations in the flow rate to be treated, which leads to overdosing of chemical, excess sludge generation and reduced product efficiency.
[0016] In this embodiment of the invention, the aluminum sulfate contained within the agent will assist in the precipitating out of phosphorus from domestic wastewater, thereby minimizing the growth of algae in the environment.
[0017] The formula and ranges for the components of different embodiments of the tablets are listed in Table 1. In general, the process takes place at ambient temperatures between 60° F. to 90° F.
[0000] TABLE 1 Material Ranges of Aluminum Sulfate Tablet Material Al 2 (SO 4 ) 3 Aluminum Aluminum Magnesium Sulfate Stearate Stearate Inert Binder H 2 O Percentage (%) 50-92 0.3-3.5 0.3-10 1.0-25 2-10 6.46 Percentage (%) 83.9-91.1 0.3-1.1 0.8-1.8 3-5 0.3-12 4.5-7.0
The inert component can include, for example, but is not limited to, Calcium Hydroxide, and the binder component/material can include, for example, but is not limited to, starch hydrolysate.
[0018] The tablets can be made using an automated high-speed or manual molding process from the mixed material. For example, but not limited to, an eight-ton arbor press that can be used with at least one die having an internal shape configured to produce a predefined shaped tablet from the mixed material, for example, but not limited to, the tablet shape shown in FIG. 1 .
[0019] FIG. 1 is a side view of an aluminum sulfate tablet 100 showing a cylindrical central body portion 110 , a beveled top 120 and a beveled bottom 130 , in accordance with one or more embodiments of the present invention. In FIG. 1 , the beveled top 120 and the beveled bottom 130 of the tablet 100 aid in the insertion of each tablet into a feeder device, provide additional surface area for contact by the wastewater as it flows through the feeder, and permit a greater flow rate through the feeder device through the channels created between adjacent tablets by the beveled tops and bottoms.
[0020] Still other embodiments of the tablet shown in FIG. 1 can include protrusions on the tops and bottoms of the tablet 100 for example, but not limited to, dimples/bumps, cones, ridges, and the like to provide additional spacing between the tablets to promote water flow and tablet dissolution and to prevent adjacent tablets from becoming stuck together.
[0021] Treatment System for Removing Phosphorus. A phosphorus removal system can consist of different combinations of components, but, in general, the removal process includes the following steps:
(1) Flowing water, wastewater or treated sewage through a tablet feeder or a similar apparatus that is filled with the aluminum sulfate tablets made in accordance with this invention to dissolve the tablets into the liquid at a certain dissolve rate. (2) Optionally, using a mechanical mixer or an air mixing apparatus to mix the liquid that contains the dissolved aluminum sulfate. The purpose of mixing is to accelerate the reaction between the aluminum sulfate and the phosphates. Any mixing method can be applied in this process. As seen, for example, in FIGS. 2 and 3 , a pump-diffusion apparatus is applied. (3) Flowing the treated water to a settling or filtration unit. After the addition of the aluminum sulfate (coagulant), floc grows gradually in this unit and is removed in the settling tank, or clarifier or a filter. The key point of the unit design is that the settling tank volume supplies enough room for chemical sludge storage.
This system contains mixing, flocculation, settling or filtration, or a combined chemical sludge removal unit, and a sludge storage zone.
[0025] FIG. 2 is a cross-sectional side view of a treatment system in which aluminum sulfate tablets shown in FIG. 1 can be used to remove phosphorus from wastewater, in accordance with an embodiment of the present invention. In FIG. 2 , a treatment system 200 is shown to include a tank 205 through which an inlet pipe 210 passes from an outside of the tank to an inside of the tank. A tablet feeder 220 is connected to an end of and is in fluid communication with the inlet pipe within the tank and the tablet feeder 220 is filled with multiple tablets 230 in, for example, a vertical stack. The tablet feeder 220 includes an upside-down, “T”-shaped base portion 221 and a cylindrical tablet holding portion 225 in which the tablets 230 are stacked. As wastewater flows into the tank 205 through the inlet pipe 210 and the tablet feeder 220 it passes over and dissolves the tablets 230 and spills into a mixing chamber 207 in which an air diffuser 270 is located to provide a mixing action to accelerate the reaction the aluminum sulfate and the phosphates in the water. The air for the air diffuser 270 is provided by an air pump 260 that is, generally, located outside of the tank 205 . The treated water then flows into a settling or filtration chamber 209 in which a filtration media 240 is located and through which the wastewater is upwardly filtered to remove the coagulant formed by the reaction of the aluminum sulfate and the phosphates before the filtered water exits through an outlet pipe 250 . The coagulant and other sludge solids eventually settle down onto a floor of the settling chamber 209 .
[0026] FIG. 3 is a cross-sectional side view of a treatment system in which aluminum sulfate tablets shown in FIG. 1 can be used to remove phosphorus from wastewater, in accordance with another embodiment of the present invention. In FIG. 3 , another treatment system 300 is shown to include a tank 305 through which an inlet pipe 310 passes from an outside of the tank 305 to an inside of the tank. A tablet feeder 320 is located outside of the tank 305 and is connected to an end of and is in fluid communication with the inlet pipe 310 within the tank 305 and a cylindrical tablet tube 325 of the tablet feeder 320 is filled with multiple tablets 330 in, for example, a vertical stack. The tablet feeder 320 includes an upside-down, “T”-shaped base portion 321 and the cylindrical tablet tube 325 in which the tablets 330 are stacked. A cap 329 is located on a top end of the cylindrical tablet tube 325 to close the top end of the cylindrical tablet tube 325 . An outer cylindrical tube 335 encircles and covers the cylindrical tablet tube 325 and the cap 329 and a top end of the outer cylindrical tube 335 is similarly covered by an outer tube cap 339 . As wastewater flows into the tank 305 through the inlet pipe 310 and the tablet feeder 320 it passes over and dissolves the tablets 330 at a bottom end of the cylindrical tablet tube 325 and spills into a mixing chamber 307 in which an air diffuser 370 is located to provide a mixing action to accelerate the reaction the aluminum sulfate and the phosphates in the water. The air for the air diffuser 370 is provided by an air pump 360 that is, generally, located outside of the tank 305 . The treated water then flows into a settling or filtration chamber 309 and exits through an outlet pipe 350 as the coagulant and other sludge solids eventually settle down onto a floor of the settling chamber 309 .
[0027] FIG. 4 is a close-up, cross-sectional, isometric view of a bottom portion of the tablet dispenser unit of FIGS. 2 and 3 , in accordance with an embodiment of the present invention. In FIG. 4 , the tablet dispenser 220 includes an upside-down, “T”-shaped base portion 410 and an upright cylindrical tablet holding portion 425 in which the tablets 230 are stacked. The upright cylindrical tablet holding portion 425 includes an open top end (not shown) that is covered with a cap (not shown) and one or more ridges 427 across a bottom of the upright cylindrical tablet holding portion 425 to raise the tablets 230 off the bottom of the upright cylindrical tablet holding portion 425 . Raising the tablets 230 off the bottom of the cylindrical tablet holding portion 425 increases the surface area of the bottom tablet 230 that is exposed to the wastewater, which results in better dissolution of the tablets 230 . The cylindrical tablet holding portion 425 is installed through a top opening 441 defined by a top cylindrical wall 440 and rests on a bottom wall 442 of the tablet dispenser 220 . A sealing member 444 , such as, for example, but not limited to, a flexible gasket, fits between an outer surface of the upright cylindrical tablet holding portion 425 and an inside of the top cylindrical wall 440 to form a watertight seal. An opening 426 is defined in and near a bottom of the upright cylindrical tablet holding portion 425 to permit the wastewater to flow into, around and past the tablets 230 . In general, a similar opening 426 is also defined on an opposite side of the upright cylindrical tablet holding portion 425 . The tablet dispenser 220 also includes an inlet cylindrical wall 422 that defines an inlet opening 424 through which the wastewater flows into the tablet dispenser 220 and opposite to the inlet cylindrical wall 422 is an outlet cylindrical wall 432 that defines an outlet opening 434 through which the wastewater flows into the tablet dispenser 220 . The tablet dispenser 220 still further includes a central body portion 443 that defines a central body opening 445 to which are connected and in fluid communication with the inlet opening 424 , the outlet opening 434 and the top opening.
[0028] FIG. 5 is a top view of a filtering system in which a tablet dispenser unit is installed, in accordance with another embodiment of the present invention. In FIG. 5 , a top of a filtering system 510 , for example, but not limited to, the Bio-Kinetic Filter system sold by Norweco of Norwalk Ohio, is shown to have protruding from it a cylindrical tablet feeding tube 525 that with its top covered by a removable tablet feeding tube cap 529 . The cylindrical tablet feeding tube 525 is located slightly off-center in the top of the filtering system 510 . A second cylindrical tube 560 is located along a diameter of the top of the filtering system 510 and is centered approximately an equal distance away from a center of the top of the filtering system 510 as the cylindrical tablet feeding tube 525 . A tube 560 is connected between and provides for fluid communication between the cylindrical tablet feeding tube 525 and the second cylindrical tube 560 .
[0029] FIG. 6 is a cross-sectional, side view of the filtering system in which a tablet dispenser unit is installed in FIG. 5 along line A-A, in accordance with another embodiment of the present invention. In FIG. 6 , the cylindrical tablet feeding tube 525 is seen holding multiple tablets 530 for treating the wastewater flowing into the filtering system 510 through inlet openings (not shown). The wastewater then passes down through and back up the filter member 612 , spills over a flow control weir (not shown) and then passes out of the filtering system 510 through an outlet opening 640 .
[0030] Test results show that the aluminum sulfate tablets can be used to remove phosphorus successfully in an on-site sewage treatment plant. The removal efficiency is directly based upon the tablets dissolve rate, mixing condition and chemical sludge removal efficiency. Tablets made from the formula shown in Table 2 can remove phosphorus to a low level, for example, the phosphate concentration in the treated effluent can be as low as 0.04 ppm.
[0000]
TABLE 2
Tablet Formula for Testing
Material
Al 2 (SO 4 ) 3
Organic gel
Aluminum
Aluminum
Magnesium
Lime
forming
Sulfate
Stearate
Stearate
(Inert)
Binder
H 2 O
Weight (g)
124.7
1.0
2.0
6.0
1.0
9.3
Percentage (%)
86.60
0.69
1.39
4.17
0.69
6.46
[0031] FIG. 7 is a flow chart showing the process for manufacturing a tablet, in accordance with an embodiment of the present invention. As seen in FIG. 7 , after the process starts ( 700 ) then:
1) The wet components are mixed ( 710 ), by combining the binder/binding material, e.g., starch hydrolysate, and the water together until they are completely mixed to form a solution. 2) The dry components are mixed ( 720 ) together by combining the aluminum sulfate, aluminum stearate, magnesium stearate and calcium hydroxide together for 1 to 10 minutes to form a dry material. For embodiment 1, the mixing time is 2 minutes to form the dry material. 3) The solution is poured into the dry material and then mixed ( 730 ) together for 1 to 10 minutes to form a mixed material. For embodiment 1, the mixing time is 3 minutes to form the mixed material. 4) The mixed material is placed in a sealed container and allowed to stand ( 740 ) for 10 to 180 minutes. For embodiment 1, the mixed material is let stand for 40 minutes. 5) A mold in a tablet press is filled with enough of the mixed material to make a tablet and the press is closed and the mixed material is subjected to 5 to 30 tons of pressure for about 1 second to make ( 750 ) each tablet. For embodiment 1, the mixed material is subjected to 20 tons of pressure for about 1 second. 6) The newly pressed tablets are now ready for use. 7) If more tablets are to be made ( 760 ), then the process returns to mixing ( 710 ) the wet components. If not, then the process ends ( 770 ).
[0039] Two points to evaluate tablet quality are strength of a tablet and dissolve rate of the tablets. Dissolve rate of the tablets is very important to the quality of treated effluent. If the dissolve rate is too high, extra Aluminum Sulfate will be present in the treated effluent. The extra added coagulant affects the formation of the floc and solids removal efficiency. If the dissolve rate is too low, the ratio of Aluminum to Phosphates will be too low to remove phosphorus efficiently. Therefore, the composition of the tablets is important. The formula of the tablets can be adjusted based on the characteristics of the wastewater or sewage to be treated.
[0040] While the invention(s) has/have been described in conjunction with a number of embodiments, it is evident that many alternatives, modifications and variations would be or are apparent to those of ordinary skill in the applicable arts. Accordingly, Applicant intends to embrace all such alternatives, modifications, equivalents, and variations that are within the spirit and scope of the invention(s) described herein. | The invention includes a tablet made from a coagulant that will improve the settling of suspended solids in an aqueous media such as wastewater, recycled water, potable water, storm water, swimming pool water, spa water, boiler water, cooling tower water and industrial process water. The agent is a tablet containing at least one salt from the aluminum sulfate family in a mixture of organic and inorganic binders. The mixed material is especially adapted to lend itself to high speed molding operations. Such agent, when in molded form, provides controlled dissolution in an aqueous media, exhibits strength and non-chipping characteristics which is a benefit in shipping and handling and is free from dusting, flaking or other deteriorative factors. In its tablet form, this agent can be used in combination with a holding apparatus having slotted opening zones. | 2 |
BACKGROUND
[0001] U.S. Pat. Nos. 6,335,818, 6,362,915 and 6,496,298 are assigned to the same assignee of the present application. The entire disclosures of these patents and others that are cited in the REFERENCES below are incorporated herein by reference in their entirety.
[0002] Disclosed are additives used in making well-behaved bichromal elements in display media, such as Gyricon displays, which are known. Bichromal elements, which are spherical in shape and of about 50 microns in diameter, perform the function of pixels in images formed in these displays, as described further below. Usually, the images suffer from poor quality because the bichromal balls having oppositely colored hemispheres with opposite charges do not assume proper positions; that is, they do not rotate in a precise manner, so as to make the images sharp and clear. What is needed, therefore, is a means for making the bichromal balls behave well and predictably. The charge control agents (CCAs) that are disclosed herein are used as an additive during compounding of black and white waxes that are components of bichromal Gyricon balls to provide better hemispherical control of charges, and hence improved performance under varied electric fields to yield enhanced images on especially Gyricon displays.
[0003] Display media, such as Electric Paper or twisted ball panel display devices, are known and are described, for example, in REFERENCES given below and are incorporated herein by reference in their entirety. The media generally are comprised of an encapsulant medium material, for example, an elastomer, such as a cured polysiloxane, sandwiched between two indium tin oxide coated substrates, such as glass or Mylar™. Generally, the elastomer layer has closely packed cavities, each containing a bichromal sphere suspended in a dielectric liquid. The dielectric liquid may also be present in substantial amounts in the elastomer matrix. In media that are active in an electric field, the bichromal spheres have a net dipole due to different levels of charge on the two sides of the sphere. An image is formed by the application of an electric field to each pixel of the display, which rotates the bichromal spheres to expose one color or the other to the viewing surface of the media. The spheres may also have a net charge, in which case they will translate in the electric field as well as rotate. When the electric field is reduced or eliminated, the spheres ideally do not rotate further; hence, both colors of the image remain intact. This image bistability is one feature of display media made with bichromal Gyricon balls.
[0004] The composition of certain bichromal spheres is known, for example, as set forth in the references given below. The spheres comprise black polyethylene with a light reflective material, for example, titanium oxide, sputtered on one hemisphere. In a different approach, a rotary ball is prepared by coating white glass balls of about 50 microns in diameter, with an inorganic coloring layer such as indium by evaporation. In a similar process, bichromal balls comprising glass balls are first heavily loaded with a white pigment such as titanium oxide, followed by coating from one direction in a vacuum evaporation chamber with a dense layer of nonconductive black material which coats only one hemisphere.
[0005] Methods and apparatus for fabricating bichromal elements are known and referenced below. One apparatus comprises a separator member having opposing first and second surfaces and an edge region in contact with both surfaces, and delivery means for flowing first and second colored hardenable liquid material over the first and second surfaces, respectively, so that the liquid materials arrive at the edge, usually at substantially the same flow rate, and form a reservoir outboard of the edge region. The reservoir comprises side-by-side regions of different colors, which in a preferred embodiment, do not intermix. Further means are provided for propelling the first and second liquid materials away from the separator member and out of the reservoir into a fluid medium. As this occurs, a plurality of forward ends of side-by-side bichromal streams become unstable and break up into droplets. The droplets form into spherical balls, each of the balls approximately comprising hemispheres of differently colored hardenable liquids. These bichromal balls are from about 5 to about 200 microns in diameter.
[0006] The aforementioned display media can suffer from drawbacks caused by incomplete or lack of rotation of the bichromal balls. When the balls do not rotate close to 180 degree, the switching from one color to the other is not complete. As a result, image quality suffers. In some cases, increasing the strength of the electric field used to rotate the spheres can help in achieving more complete rotation, but in other cases sufficient rotation cannot be attained, even at higher fields. In the latter cases, it is believed that the dipole strength of the sphere relative to the monopole strength is too small, rendering it difficult to get sufficient rotation before the sphere translates across its cavity in the elastomer matrix. Many of the balls lack sufficient monopole and dipole strengths to dislodge them from the cavity walls.
[0007] Materials that can improve the rotational behavior of bichromal balls could enable display media to be used in a wider variety of applications than is currently possible. For example, materials that provide a more reproducible and lower voltage for rotation and a sharper voltage threshold above a certain value can be used to make bichromal passive matrix displays in which balls that do not experience a sharp threshold voltage do not alter their state. Therefore, it is desirable to provide a display media wherein a threshold voltage of a particular value exists. It is further desirable to provide a display media wherein the threshold voltage is sharper to eliminate most, or ideally all, of the rotation below the threshold voltage and more complete rotation can be obtained at a lower applied voltage. It is still further desirable to provide a display media in which the balls have sufficient monopole and dipole strengths to allow the electric field not only to pull them from the cavity walls and translate, but also to rotate those 180° completely.
[0008] Disclosed herein are additives used in making well-behaved bichromal elements in display media. The additives comprise charge control agents (CCAs) that enable lower switching voltages, faster and more complete rotation of balls, less stiction on the cavity walls, and more distinct voltage thresholds for displays and display media containing bichromal spheres or balls, and in particular, Gyricon balls. The bichromal ball formulation disclosed herein provides improvingly stronger monopole and dipole strengths.
REFERENCES
[0009] U.S. Pat. No. 6,496,298 describes a display media with an encapsulant medium, and bichromal beads having a charge adjuvant, wherein the bichromal beads are dispersed or contained in the encapsulant medium is set forth.
[0010] U.S. Pat. No. 6,485,280 describes an apparatus for fabricating bichromal elements comprising a separator member having a central rotating point, the separator member having first and second spaced apart, opposed surfaces with an edge region in contact with both of said opposed surfaces. The spacing between the opposed surfaces varies with the distance outwardly from the central rotating point such that the spacing is the largest at the central rotating point and the spacing decreases outwards from the central rotating point and the spacing is a minimum at the edge region. Further each of the opposed surfaces has a substantially annular cup spaced apart from and substantially surrounding the central rotating point. The apparatus for fabricating bichromal elements also includes apparatus for dispensing first and second differently colored hardenable liquids in the cups of the first and second surfaces, respectively, and an apparatus for substantially uniformly spreading the liquid material in the annular cups located in the first and second surfaces and for substantially uniformly spreading the liquid material from the cups over the first and second surfaces toward said edge region to form a reservoir of liquid material outboard of said edge region, and for forming ligaments from said reservoir.
[0011] U.S. Pat. No. 5,389,945 describes an addressable display system including a paper-like sheet comprising a light transparent host layer loaded with a plurality of repositionable elements, the elements are movable from a first orientation in which they will present a first visual appearance, to a second orientation in which they will present a second visual appearance, and independent external addressing means relatively movable with respect to the display sheet for affecting the orientation of the repositionable elements
[0012] U.S. Pat. No. 4,438,160 describes a method for manufacturing rotary ball display devices wherein a plurality of such balls are provided with a coating of a color different from the remainder of the ball, the ball members are coated with a thin coating insoluble in the settling medium into which they are introduced, so that upon settling into a low viscosity liquid, they form a uniform layer. A high molecular weight hardenable coating material which is soluble in the low viscosity liquid is then poured onto the coated ball members to cover the layer. Then, the low viscosity liquid is removed and the hardenable coating material is caused to harden. The thin coating is then dissolved away from portions of the ball members to leave cavity portions thereabout into which a high resistivity liquid is introduced. The resulting ball members have a refractive index on the colored layer which is substantially the same as the refractive index of the high resistivity liquid contained in the cavities.
[0013] U.S. Pat. No. 4,261,653 describes a light valve formed of a plurality of spherical dipolar particles suspended in a matrix material. Each spherical dipolar particle has a unified body formed in three discrete symmetrical sections. A central section is configured to permit light transmission when in a first orientation with respect to a path of light travel, and generally not permit light transmission when in a second, transverse orientation with respect to the path of light travel. Pair of intermediate sections bound the central section and is formed of a transparent material having an electrical permittivity that varies through a range of values as a function of the frequency of an applied electric field. A pair of outer sections bounds the intermediate sections and is formed of a material having a relatively stable electrical permittivity within the range of values of the intermediate sections. An applied electric field at one frequency extreme will cause the spherical dipolar particle to align in the first orientation to permit light transmission, and an applied electric field in the other frequency extreme will cause the particle to anti-align in the second, transverse orientation to shutter or reflect light. The matrix material is preferably formed of a plasticized elastomer that has a plurality of expanded cavities, with each cavity containing an outer lubricating layer to allow free rotational motion of a dipolar particle in the cavity. The use of a light valve of the invention and method of manufacturing the spherical dipolar particle construction are also disclosed.
[0014] U.S. Pat. No. 4,143,103 describes a method of making a display characterized by a plurality of particles which have an electrical anisotropy due to hemispherical surface coatings of different Zeta potential and their distribution in a volume of a dielectric liquid and which also have an optical anisotropy due to the hemispherical surface coatings having different optical characteristics. The particles are mixed with a light transparent liquid which is subsequently cured to form an elastomeric or rigid slab. Following curing of the liquid, the slab is immersed in a plasticizer (dielectric liquid) which is absorbed by the slab and which causes the slab to expand slightly. Expansion of the slab around the particles provides a plasticizer-filled cavity around each particle which cavities allow the particles to rotate to provide a display in accordance with their optical anisotropy but does not allow substantial translation of the particles.
[0015] U.S. Pat. No. 4,126,854 describes a display system in which the display panel is comprised of a plurality of particles which have an electrical anisotropy due to hemispherical surface coatings of different Zeta potential and their distribution in a volume of a dielectric liquid, and which also have an optical anisotropy due to the hemispherical surface coatings having different optical characteristics which may be due to the color or other optical properties of the hemispherical coatings. Under the action of an external electric field, the particles will rotate in accordance with their electrical anisotropy to provide a display in accordance with their optical anisotropy. The display has switching threshold and memory capabilities.
SUMMARY
[0016] Aspects disclosed herein include
[0017] a display comprising bichromal elements having portions containing components that control—substantially independent of the influence of other materials in said portions—the motion of said bichromal elements encapsulated in cavities formed in a medium; wherein the medium forms the display.
[0018] a display media comprising an encapsulated medium; and bichromal balls comprising a charge control agent; wherein the bichromal balls are dispersed in the encapsulant medium;
[0019] wherein the charge control agent comprises Copy Charge PSY, Copy Charge N4P, Hostacopy N4P-N101 VP2624, Hostacopy N4P-N203 VP2655, Hostacopy Charge PX04, Copy Charge NY VP2351, Copy Level NCS or Copy Blue PR Solvent Blue 124;
[0020] wherein charge control agent comprises triphenylmethane, ammonium salts, al-azo complex, Ca-polymer salt, modified inorganic polymeric compounds, chromium compounds, aluminum salicylate, zinc salicylate, zirconium salicylate, boron salicylate, boron acetyl type, chrome-azo complex, iron-azo complex or silicon oxide.
BRIEF DESCRIPTION OF DRAWINGS
[0021] FIG. 1 a is a cross sectional drawing of a portion of a display media showing spherical bichromal elements with hemispheres of different pigments and charges.
[0022] FIG. 1 b is an enlarged drawing of a bichromal element of FIG. 1 a showing polymers dispersed in a hemisphere.
[0023] FIG. 2 a is a drawing of a graph showing an aspect of an embodiment of the reduction of the operating voltage when Charge Control Agents are used in formulations for bichromal elements in a display media.
[0024] FIG. 2 b is a drawing of a graph showing another aspect of an embodiment of the increase in the contrast ratio in the image of a display media when Charge Control Agents are used in the formulations for bichromal elements in the display.
[0025] FIG. 3 is a photograph of a plurality of bichromal spheres.
DETAILED DESCRIPTION
[0026] In embodiments there is illustrated:
[0027] a display media using charge control agents (CCA) in bichromal elements of the display. The elements are generally spherical in shape, such as a ball, though they may also assume oval and cylindrical shapes, as well as other non-spherical shapes such as beads. However, for illustrative purposes, these terms may be used interchangeably. Also, a bichromal element may have a plurality of portions comprising two hemispherical parts or several sectors forming the body of the bichromal element.
[0028] The charge control agents incorporated to one or both hemispheres of the bichromal balls provide different and precisely controlled properties. In the presence of the charge control agents, the hemispheres become positively or negatively charged without relying on the pigments. It will be understood that either hemisphere may be positively or negatively charged. The type and amount of the specific charge control agent is selected to provide desired amount of charge generated. Appropriate selection of the charge control agents for use in one or both hemispheres allows precise control of both monopole and dipole charge on the bichromal ball. Ability to precisely control electric properties of bichromal balls provides reliable and consistent manufacturing of the bichromal balls and well-behaved operation of electronic display. Ability to manipulate amount of charge on the balls as a whole and individually on each hemisphere independently, as disclosed below, provides flexibility to make electronic displays that can operate in a wide range of voltage requirements. Long-term reliability of the displays is also improved.
[0029] Referring to FIG. 1 a , there is shown a cross sectional view of a portion of a display media 10 comprising a plurality of bichromal elements 20 disposed in their respective cavities 25 which have a darker pigmented hemisphere 20 D on one side and a lighter hemisphere 20 L on the other side. FIG. 1 b is an enlarged view of the bichromal balls 20 depicting lighter pigments “L” dispersed or contained in hemisphere 20 L, and darker pigments “D” in hemisphere 20 D. Polymers 23 are dispersed in hemisphere 20 D containing the darker pigment “D”. The display media 15 can be any media capable of displaying an image, such as a sheet, and may comprise any suitable material for housing the bichromal balls such as, for example, an elastomer material.
[0030] As shown in FIG. 1 a , each of the hemispheres 20 L and 20 D contain electrical charges. Usually, the values of these charges are found to be dependent upon both the concentrations of pigments and the presence of the charge control agent (where present). However, it is desirable to minimize the influence of the pigment and maximize the influence of the charge control agents in order to be able to control the monopole and dipole charges for precise translation of the ball from one side of the cavity wall 25 to the other, and rotate completely. Charge control agents which promote improved control of monopole and dipole charges of bichromal elements are disclosed further below.
[0031] The monopole charge comprises the net charge on the bichromal element, expressed as proportional to CL+CD, where CL represents the total charge on one side, the white or lighter L side of the ball 20 and CD is the total charge on the black or darker D side of the ball, as shown in FIG. 1 a . If CL (+) and CD (−) are of equal and opposite polarity, then the monopole charge CL+CD would be zero, as expected. Typically, they have the same polarity. The monopole charge is responsible for causing the ball to move from one cavity wall position to the opposite position, upon application of an electric field. Without this charge, the ball would remain locked to the cavity wall and rotation would be very difficult. The dipole moment causes the ball to rotate as it moves across the oil-filled cavity. The force causing this rotation is proportional to the dipole moment, which itself is proportional to CL-CD.
[0032] It is known that some charge enhancers, or adjuvants, augment the monopole and dipole charge distributions on the bichromal element. Examples of charge adjuvants include polymers such as polyalkyls such as polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide copolymers, ethoxylated alcohols, amides, amines, acids, phenols and derivatives thereof. The bichromal spheres or balls comprise a polymer having polyether functionality. The alkyl poly (alkylene oxide) have at least 4, and preferably from about 20 to about 100 alkylene oxide units per polymer molecule. Polymers having the highest ethylene oxide levels are desirable.
[0033] Commercially available examples of charge adjuvants include those from Baker/Petrolite UNITHOX® such as 5175 (acetate ester, E 16.7 EO 42 , where the subscripts 16.7 and 42 indicate the percentage by weight of the molecules comprising ethylene, and ethylene oxide, respectively). There are several other commercially available adjuvants (see REFERENCES), but they are not described here any further in order not to unnecessarily obscure the present disclosure of the charge control agents. Suffice to say that charge adjuvants, as well as charge control agents, are selected so that they are not soluble in the dielectric liquid that fills the cavities in which the bichromal elements are contained. The adjuvants are added to the polymeric or wax base materials of bichromal elements, which are also available commercially. Examples of suitable waxes include carnauba wax and candelia wax. Pigments made by Ferro Corporation and Dupont are also used as pigments in the bichromal elements. However, because the total charge levels of the adjuvants are influenced to a considerable extent by the presence of pigments added to the hemispherical elements, further improvement is required by introducing agents that will have a larger influence in the control of the motion of the bichromal elements while leaving the contrast level of the colors of the hemispherical parts to the pigments with minimal influence on the over-all charge levels.
[0034] The following Table I shows exemplary Formulations 1-9 which are suitable for making bichromal elements having hemispherical portions that are positively or negatively charged without undesirable charge influence by the pigments:
Bichromal Titanium Spinel Carbon Copy Copy FORMULATIONS Hemispeheres Polyethylene Ox. Black Black 5175 Charge PSY Charge N4P Silicon Powder Standard White Side 70.00% 30.00% Black Side 77.00% 20.00% 3.00% Formulation 1 White Side 70.00% 29.25% 0.25% Black Side 77.00% 23.00% Formulation 2 White Side 70.00% 30.00% Black Side 77.00% 22.50% 0.50% Formulation 3 White Side 70.00% 29.25% 0.75% Black Side 77.00% 22.75% 0.25% Formulation 4 White Side 80.00% 19.00% 1.00% Black Side 77.00% 22.50% 0.50% Formulation 5 White Side 80.00% 19.25% 0.75% Black Side 69.75% 30.00% 0.25% Formulation 6 White Side 80.00% 20.00% Black Side 69.90% 30.00% 0.10% Formulation 7 White Side 80.00% 19.50% 0.50% Black Side 70.00% 30.00% Formulation 8 White Side 80.00% 20.00% Black Side 68.00% 30.00% 2.00% Formulation 9 White Side 80.00% 19.00% 1.00% Black Side 70.00% 30.00%
[0035] The first Formulation shown is a standard formulation used as described above for comparison with the disclosed exemplary nine Formulations that use Charge Control Agents manufactured by Clariant Corporation under the brand name of Copy®. Table I lists various compositions comprising relative percentages of charge control agents Copy Charge PSY®, Copy Charge N4P® used with white pigment titanium oxide TiO 2 and black Spinel Black or Carbon Black in base material polyethylene. As is known, Spinel Black comprises MgAl 2 O 4 , magnesium aluminum oxide, while carbon black is a derivative of hydrocarbon. Silicon oxide powder shown in the Table and any other material with strong triboelectric properties, such as glass, may also be used suitably to control charges well. It should be noted that the compounds disclosed herein are not limited to those shown in Table I above, and that the percentage combinations may vary as follows:
[0036] Exemplary Formulation 1:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Copy Charge N4P® from about 0.1% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%;
[0041] Exemplary Formulation 2:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%; Copy Charge PSY® from about 0.1% to about 10%;
[0047] Exemplary Formulation 3:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Copy Charge N4P® from about 0.1% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%; Copy Charge PSY® from about 0.1% to about 10%;
[0054] Exemplary Formulation 4:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Copy Charge N4P® from about 0.1% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%; Copy Charge PSY® from about 0.1% to about 10%;
[0061] Exemplary Formulation 5:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Copy Charge N4P® from about 0.1% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%; Copy Charge PSY® from about 0.1% to about 10%;
[0067] Exemplary Formulation 6:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%; Silicon oxide from about 0.05% to about 10%;
[0073] Exemplary Formulation 7:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Silicon oxide from about 0.05% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Spinel Black from about 5% to about 50%;
[0079] Exemplary Formulation 8:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Black Side—Polyethylene from about 50 to about 97%; Carbon Black from about 3% to about 50%; Copy Charge PSY® from about 0.1% to about 10%;
[0085] Exemplary Formulation 9:
White Side—Polyethylene from about 50% to about 100%; TiO2 from about 0.5% to about 50%; Copy Charge N4P® from about 0.1% to about 10%; Black Side—Polyethylene from about 50 to about 95%; Carbon Black from about 3% to about 50%;
[0091] The amount of charge control agency (CCA) may be in the range from about 0.1 to about 10% of total formulation by weight, mostly under 3% total formulation.
[0092] Further, any of Clariant Corporation's CCAs for toner applications under the brand name Copy® may also be used. These include: Hostacopy N4P-N101 VP2624; Hostacopy N4P-N203 VP2655; Hostacopy Charge PX04; Copy Charge NY VP2351; Copy Level NCS or Copy Blue PR Solvent Blue 124.
[0093] In addition, any similar charge control compounds manufactured by Aztech Ltd., Hitachi Chemical, Hodogaya Chemical, Esprix technologies may also be used, including: triphenylmethane, ammonium salts, al-azo complex, Ca-polymer salt, modified inorganic polymeric compounds, chromium compounds, aluminum salicylate, zinc salicylate, zirconium salicylate, boron salicylate, boron acetyl type, chrome-azo complex, iron-azo complex.
[0094] It will be appreciated that the introduction of inorganic charge control agents (CCAs), which are known in xerographic industry, to the formulation of bichromal elements, brings their proven properties to electronic display media, such as the Gyricon display. These include: consistency in manufacturing process, sharper white/black hemispherical boundary; higher contrast ratios, enhanced performance at lower voltages with the attendant longer life. For example, FIG. 2 a shows the reduction in the operating voltage of bichromal elements that have charge control agents 30 shown in Table I above versus those that do not 40. The reduction may be as high as 20 volts. FIG. 2 b shows also the improvement in contrast ratio by about 50% when using CCAs 35 at 80 volts in comparison with the use of standard formulation 45 shown in Table I above. Five batches of the standard formulation 45 without CCA and four formulations 35 containing CCAs were made and contrasted throughout the day they were made. FIG. 3 shows a photograph of the bichromal spheres 50 of the present disclosure with their respective white hemispheres 53 and black hemispheres 55 .
[0095] Though these numerous details of the disclosed display media are set forth here, such as formulation compositions, it will be understood that these specific details need not be employed to practice the present disclosure. At the same time, it will be evident that other portions, in the form of multi-sectors, or segments—instead of only hemispherical portions—may be used to form a multichromal element having multi-colors. The portions may comprise, but not limited to, from about 2 to about 16 sectors, more specifically from about 8 to about 16, and yet more specifically from about 2 to about 4 sectors of a body of revolution, such as a sphere or a spheroid. Multichromal elements may then be used to improve image definition through more precise rotation, with the aid of charge control agent (CCAS) disclosed above, to different orientations to expose (in sequence or in combination) more than two colors from the same multichromal element, and hence enhance the capabilities of the display media.
[0096] While the invention has been particularly shown and described with reference to a particular embodiment(s), it will be appreciated that variations of the above-disclosed embodiments(s) and other features and function, or alternatives thereof, may be desirably combined into many other different systems or applications Also that various presently unforeseen and unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. | Charge Control Agents In Display Media. Use of charge control agents in display media comprising bichromal elements increases the ability to control translation and rotation of spherical elements in their cavities more precisely, thus yielding sharper and clearer images and longer life at lower applied voltages. | 6 |
FIELD OF THE INVENTION
The present invention relates generally to containers and more particularly to insulated carrying containers for beverages and the like.
BACKGROUND OF THE INVENTION
Various types of insulated containers are known. U.S. Pat. Nos. 1,939,677 and 4,197,890 describe examples of known insulated containers.
Bubble packaging is also known in the art, normally for preventing impact damage to goods wrapped therein. The following U.S. patents describe various structures of bubble packaging and certain applications thereof: U.S. Pat. Nos. 5,088,686; 4,894,265; 5,271,980; 5,340,632; 5,084,324; 4,825,089; 4,921,746 and 4,868,025.
SUMMARY OF THE INVENTION
The present invention seeks to provide an improved, relatively low cost insulated container.
There is thus provided in accordance with a preferred embodiment of the present invention a thermally insulated container formed of multiwall flexible plastic heat sealed to define a multiplicity of sealed air bubbles.
In accordance with a preferred embodiment of the present invention, the container includes an integrally formed carrying handle.
Further in accordance with a preferred embodiment of the present invention, the container has printed on at least one of the walls thereof an advertising message.
Additionally in accordance with a preferred embodiment of the present invention, the container is formed with a radiation reflective coating.
In accordance with a preferred embodiment of the invention, the container has an overall tube shape and is configured to generally tightly surround a bottle.
In accordance with one preferred embodiment of the invention, the container has integrally formed therewith at least one bottle opening engagement flap for retaining the cover in surrounding relationship with the bottle.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawings in which:
FIG. 1 is a simplified illustration of a bottle and an insulated container therefor, constructed and operative in accordance with a preferred embodiment of the present invention;
FIG. 2 is a sectional illustration of part of the container shown in FIG. 1, along line II--II of FIG. 1;
FIG. 3 is a pictorial illustration of a first step in closing the container over the bottle of FIG. 1;
FIG. 4 is a top view illustration of the container after completion of the first step;
FIG. 5 is a pictorial illustration of a final step in closing the container over the bottle of FIG. 1;
FIG. 6 is a top view illustration of the container after completion of the final step;
FIG. 7 is a pictorial illustration of the container of FIGS. 1-6, fully closed over a bottle and held by a user;
FIG. 8 is a simplified illustration of a bottle and an insulated container therefor, constructed and operative in accordance with another preferred embodiment of the present invention;
FIG. 9 is a pictorial illustration of a first step in closing the container over the bottle of FIG. 8;
FIG. 10 is a top view illustration of the container of FIG. 8, in direction of the arrow X of FIG. 9, following completion of the first step;
FIG. 11 is a pictorial illustration of a final step in closing the container over the bottle of FIG. 8;
FIG. 12 is a top view illustration of the container, in direction of arrow XII of FIG. 11, after completion of the final step;
FIG. 13 is a pictorial illustration of the container of FIGS. 8-12, fully closed over a bottle and held by a user;
FIG. 14 is a simplified pictorial illustration of a container and a bottle, the container being constructed and operative in accordance with another preferred embodiment of the present invention;
FIGS. 15A and 15B are two side view illustrations of a container constructed and operative in accordance with a further alternative embodiment of the invention, where FIG. 15B is in the direction of arrow 15B of FIG. 15A; and
FIGS. 16A and 16B are two side view illustrations of the container of FIGS. 15A and 15B respectively upon insertion of a bottle thereinto and following insertion, where FIG. 15B is in the direction of arrow 16B of FIG. 16A.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Reference is now made to FIGS. 1-7, which illustrate a thermally insulative container 10 which is configured in a generally tubular configuration so as to accommodate a bottle 12, such as a conventional 1.5 liter soft drink bottle.
Referring specifically to FIG. 2, it is seen that most or all of container 10 is formed of a multi-ply sealed-bubble flexible plastic material, which is conventionally available from various vendors in the U.S.A. and elsewhere. The multi-ply sealed-bubble material typically comprises at least three plies of plastic which are sealed together in such a manner as to trap air bubbles at a multiplicity of predetermined locations therein.
In accordance with a preferred embodiment of the present invention, the container 10 bears printed advertising material on at least one ply thereof, which need not necessarily be the outer ply thereof.
Further in accordance with a preferred embodiment of the present invention, the container is formed on the outer surface thereof with a radiation reflective surface, such as a silvered or white surface, which may be coated over one of the plies of the sealed-bubble material or alternatively added as an additional ply and sealed thereto.
It is seen that the container defines a two-ply carrying handle portion 14 and a pair of attachment flaps 16, each of which has a central aperture 18 and which is separated from the handle portion 14 by a cut 19.
In accordance with a preferred embodiment of the present invention, the attachment flaps 16 are sequentially folded over the mouth 20 of the bottle 12, so as to secure the container tightly over the bottle, for maximum thermal insulation efficiency. FIG. 3 shows folding of a first flap, here indicated by reference numeral 22, over the mouth 20 of the bottle, such that the mouth extends through aperture 18, as seen in FIG. 4. FIG. 5 shows folding of a second flap, here indicated by reference numeral 24, over the first flap 22 and over the mouth 20 of the bottle, such that the mouth extends through aperture 18, as seen in FIG. 6.
FIG. 7 illustrates a pictorial illustration of the container of FIGS. 1-6, fully closed over a bottle and held by a user.
Reference is now made to FIG. 8-13, which illustrate a thermally insulative container 50, constructed and operative in accordance with an alternative embodiment of the present invention, which is configured in a generally tubular configuration so as to accommodate a bottle 52, such as a conventional 1.5 liter soft drink bottle.
The structure of the container may be identical with that described hereinabove with reference to FIG. 2. Similar to the container of FIGS. 1-7, the container may bear advertising material and may have an outer reflective surface.
It is seen that the container defines a pair of attachment flaps 56, each of which has a central aperture 58.
In accordance with a preferred embodiment of the present invention, the attachment flaps 56 are sequentially folded over the mouth 60 of the bottle 52, so as to secure the container tightly over the bottle, for maximum thermal insulation efficiency. FIG. 9 shows folding of a first flap, here indicated by reference numeral 62, over the mouth 60 of the bottle, such that the mouth extends through aperture 58, as seen in FIG. 10. FIG. 11 shows folding of a second flap, here indicated by reference numeral 64, over the first flap 62 and over the mouth 60 of the bottle, such that the mouth extends through aperture 58, as seen in FIG. 12.
FIG. 13 illustrates a pictorial illustration of the container of FIGS. 8-12, fully closed over a bottle and held by a user.
Reference is now made to FIG. 14, which is a simplified pictorial illustration of a container and a bottle, the container being constructed and operative in accordance with yet another preferred embodiment of the present invention. Here the handle is formed on the side of the bottle, but the closing the container over the bottle employing flaps, may be identical to that in the embodiment of FIGS. 8-13.
Reference is now made to FIGS. 15A-16B, which illustrate a container 80 constructed and operative in accordance with a further alternative embodiment of the invention. Here the container 80 is formed with an resilient elastic neck portion 82, which normally does not include sealed bubbles, but serves to retain the container on the bottle. The container is formed with a pair of carrying handles 84.
It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention is defined only by the claims which follow: | The disclosure of the present invention describes a thermally insulated container formed of multiwall flexible plastic heat sealed to define a multiplicity of sealed air bubbles and being formed with a radiation reflective coating. The container includes an integrally formed carrying handle. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
Reference is made to and priority claimed from U.S. Provisional Application Ser. No. 60/053,817 filed Jul. 25, 1997, entitled "Wall Deposition Monitoring System".
FIELD OF THE INVENTION
This invention relates to the field of deposition monitors, and more specifically to a monitoring system employing a quartz crystal sensor for measuring variations in wall deposit thickness in a etch or deposition chamber.
BACKGROUND OF THE INVENTION
A number of processes are known for depositing or removing thin film material onto or from a semiconductor substrate. Typically, these processes occur in a reaction (etch or deposition) chamber containing a highly reactive environment such as produced in a chemical vapor deposition (CVD) reaction between a carrier gas, such as hydrogen and a precursor, such as trimethylamine alane, or nickel pentamethylcyclopentadienyl allyl, among others, producing a solid reaction product, such as aluminum and nickel, respectively.
The resulting solid reaction product, however, produces a residue which is not only deposited onto the substrate, but on the interior of the walls of the reaction chamber, as well.
Over time, and in the course of an accumulated number of coating runs, sufficient buildup occurs produce a layer which, if unchecked, will eventually peel from the walls, and fall onto the substrate. Given the stringent specifications (on the order of 1×E-3 Angstroms) for the avoidance of particles, such peeling could produce a deleterious effect.
Therefore, after a certain number of coating or etching runs, processing must be interrupted in order to clean the chamber so as to remove the deposited wall residue. Presently, empirical data is used to determine the number of coating runs which can be performed prior to a necessity to clean the chamber walls. This data, however, is highly process dependent and can easily be influenced by extraneous factors (e.g., ambient atmosphere, humidity) or a change in processing conditions. There is no current detection apparatus available for determining when the interior walls of a deposition chamber have reached a threshold thickness value.
Moreover, it has been observed that the time required to clean the chamber does not vary linearly, but varies exponentially based on the thickness of the accumulated wall residue thickness. Time is an important factor because the variation in cleaning times (3-4 hours versus 15-18 hours) can greatly increase chamber down time. There is a perceived tradeoff to put off cleaning to an intermediate time, or put differently, a wall thickness threshold, to satisfy the competing concerns to optimize cleaning and down time most efficiently. In addition, it is frequently advantageous to leave a small amount of built up wall residue to avoid changing the surface of the chamber with time as would occur if all of the material were to be removed. To date, no means have been developed for monitoring the wall thickness on a real-time basis without resorting to empirical data, or by interrupting the process by opening the chamber.
It has been found that quartz-crystal sensors, such as these manufactured by Leybold Inficon, Inc., of East Syracuse, N.Y., are capable of the high precision resolution, reliability, and accuracy required to solve the above problem and to monitor wall thickness variation in a repeatable manner. However, a system incorporating these types of sensors has not been readily feasible due to concerns relating to the corrosive and highly reactive environment found within an etch or deposition chamber, as well as competing concerns which are electrical and thermal in nature.
SUMMARY OF THE INVENTION
It is a primary object of the present invention to improve the state of the art of deposition monitoring systems.
It is another object of the present invention to provide a wall residue monitoring system which can be easily installed with respect to a deposition or etch chamber and is suitably compact.
It is another object of the present invention to provide a wall monitoring system which is made from materials which will reliably perform despite the highly corrosive and reactive environments typically found in reaction chambers.
Therefore, and according to a preferred aspect of the present invention, there is provided a monitoring system for measuring variation in wall thickness in a deposition/etch chamber having a contained reactive environment, said system including at least one quartz or other piezoelectric crystal sensor installed through a wall of the chamber using a feed-through member. A cover assembly retains the sensor at a projecting end of the feed-through member in a position in proximity with the interior of a chamber wall. The cover assembly includes a cover member having an opening providing access to an active area of the sensor which is exposed to the reactive environment and means for providing a restraining force placing the sensor in contact with a resilient member electrically attached to a detection apparatus.
An oscillator device provides a voltage which is applied across the faces of the quartz crystal sensor, causing the sensor to distort and change shape in proportion to the applied voltage. At certain discrete frequencies of the applied voltage, a condition of very sharp electro-mechanical resonance is encountered. When mass is applied to the active area of the quartz sensor, the frequency of the resonances is reduced. The film thickness is proportional to the frequency change, and inversely proportional to the density of film applied. When used with highly reactive environments, the components of the monitoring system are constructed of non-reactive materials which are sufficiently electrical and thermally conductive.
Preferably, the quartz crystal sensor as retained by the cover member is positioned in alignment with the opening encompassing the sensor's active area, allowing exposure to the reactive environment of the chamber and allowing accumulation of particles. In addition, the cover assembly includes resilient means for placing the electrode of the sensor in electrical contact, the resilient means including a leaf spring which assures an electrical connection and which also biases the fully coated face of the sensor into the cover member to provide a grounding path.
An advantage of the present invention is that the wall deposit thickness of a deposition or etch chamber can be easily monitored, thereby reducing the frequency of opening the chamber to interrupt in-process activity.
A further advantage of the present invention is that an accumulated threshold wall deposit thickness value or limit for cleaning or other purposes can be selected, by which the described monitoring system can automatically inform the user when this threshold limit has been reached, despite variations in processing conditions or other extraneous factors.
These and other objects, features, and advantages will become apparent from the following Detailed Description of the Invention which should be read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of a vacuum deposition/etch chamber shown in section;
FIG. 2 is an exploded view of a chamber wall deposit monitoring system in accordance with a preferred embodiment of the present invention;
FIG. 3 is an end view of a cover used in the wall deposition monitoring system of FIG. 2;
FIG. 4 is a partial side sectional view of the cover of the chamber wall deposit monitoring system of FIGS. 2 and 3;
FIG. 5 is a view of the patterned side of a quartz crystal sensor used in the wall deposit monitoring system of FIGS. 2-4;
FIG. 6 is a side elevational view of the quartz crystal sensor of FIG. 5;
FIG. 7 is a plan view of the fully coated side of the quartz sensor of FIGS. 5 and 6; and
FIG. 8 is a side sectional view of the wall deposit monitoring system of FIGS. 1-4, as assembled in the wall of the deposition chamber of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
The following description relates to a monitoring system according to a specific embodiment used for measuring wall thickness variations in a specifically described deposition/etch chamber. Terms used throughout the course of discussion, such as "top", "upper", "lateral", "bottom", and the like, provide a frame of reference for the accompanying drawings, but should not be limiting as to the concepts embodying the present invention as claimed.
Referring specifically to the drawings, and more specifically to FIG. 1, there is shown the deposition/etch chamber 10, as is commonly known in the field, used for patterning the various structures and layers of a substrate (not shown), such as a semiconductor wafer. The chamber 10 includes a housing 14 having an enclosed interior 18 defined by side walls 22, and top and bottom walls 24, 26, respectively. The chamber 10 can be one of a number of separate chambers arranged in a clustered network (not shown), or can be an individual chamber, as shown.
The substrate (not shown) is loaded and unloaded to and from the interior 18 through an opening 21 in one of the side walls 22 of the chamber 10. A carrier gas and at least one precursor(s) are separately conveyed using known supply means to the interior 18 of the chamber 10, the interior being sealed in a known manner to allow a vacuum to be applied by means (not shown) whereby the reaction between the carrier gas and the precursor causes the formation of a solid reaction product which is deposited onto the surface of the substrate. As noted above, the solid reaction product is also deposited as a thin film onto the interior of each of the side walls 22 of the chamber 10. The specific workings of the chamber, and the process reaction conducted inside, except as described, does not necessarily form an essential part of the present invention and requires no further discussion.
Still referring to FIG. 1, a wall deposition monitoring system 40 (only partially shown) in accordance with a preferred embodiment of the invention, is mounted through respective openings provided in the side wall 22 and an adjacent exterior mounting plate 30. In brief, and as detailed below, the monitoring system 40 includes a quartz or other piezoelectric crystal sensor disposed at the end of a feed-through unit which extends into the chamber interior 18. A cover assembly is used to position and retain the quartz crystal sensor in a predetermined position relative to an electrical assembly and the interior of the chamber wall, the cover also having an opening to allow access of an active surface of the sensor to the process environment. The monitoring assembly will now be described in greater detail with reference to FIG. 2.
FIG. 2 provides an exploded view of the wall deposition monitoring system 40, including a disc-shaped quartz crystal sensor 44 which is positioned at a projecting end portion 52 of a feed-through member 56 and retained in a predetermined manner by a cover 46.
Referring briefly to FIGS. 5-7, the quartz-crystal sensor 44 is a thin wafer-like element having a pair of opposing sides 60, 64. Each side of the sensor 44 is coated with a layer of electrically conductive material which is resistant and non-reactive with the process environment in the interior 18 of the chamber 10. Side 60 is fully coated and side 64, commonly referred to as the patterned side, is coated mainly on the outer periphery, to define an electrical contacting surface or electrode 68. Typically, the coating thickness is approximately 2000-3000 angstroms. According to the present embodiment, the sensor 44 is coated with Nickel 200. A circularly shaped active portion 45 is defined in the center of the sensor 44, which can be resonated upon application of a proper voltage. Additional details relating to the theory and manufacture of quartz-crystal sensors are commonly known to those in the field as described in the text Introduction to Quartz Crystal Unit Design by Virgile E. Bottom, published 1981, the entire contents of which is hereby incorporated by reference. Therefore, no additional discussion is needed, except as required, in describing the present invention.
The chamber walls 22 and mounting plate 30 of the present embodiment are each fabricated from an electrically conductive material, which is also resistant and non-reactive with the processing environment within the chamber 10. According to the embodiment, each are made from anodized aluminum, though other suitable materials can be substituted. For example, chambers which are dielectric in nature can alternately be utilized.
Referring back to FIG. 2, the projecting portion 52 of the feed-through member 56 includes a substantially cylindrical cross section with the exception of an exterior circumferential groove 72 sized for retaining a circular coil spring 76. The distal or receiving end 80 of the projecting portion 52 includes a conical countersink 84 into which a sealing O-ring 88 is encapsulated or otherwise positioned. A ceramic spacer 92 is coaxially arranged onto the distal end 80 of the projecting portion 52, the spacer also including a similar countersink 96 extending partially into the interior thereof at its distal end for retaining the head 98 of a threaded fastener 100 and a leaf spring 104 having a series of spaced fingers 102, the details of which are supplied below.
The leaf spring 104, ceramic spacer 92 and sealing O-ring 88 each include central openings which are coaxially aligned with a through opening 108 of the feed through member 56.
An exterior mounting portion of the feed-through member 56, including an exteriorly threaded end 112 is disposed opposite the projecting portion 52. A center engagement portion 116 having a hex shape allows locking engagement relative to the mounting plate 30, FIG. 1, as described in greater detail below.
The opening 108 in the feed-through unit 56 is sized to accommodate a dielectric spacer 120 made from a suitable material such as Teflon™, a split lockwasher 124, and a hex nut 128, respectively, to lock the threaded fastener 100 in place and also to compress the O-ring 88, creating a vacuum seal. The threaded end 132 of the fastener 100 is engaged by an electrical support assembly 136 at the distal end of a BNC cable 140, partially shown in FIG. 8. The support assembly 136 includes a socket 144 sized for receiving the end 132 of the threaded fastener 100. A washer 146 and jam nut 150 are fitted over the threaded portion 112 of the feed through member 56 and sealed by an O-ring 154.
Critical to the workings of the present invention is providing adequate support and an electrical contact for the quartz crystal sensor 44. Referring to FIGS. 2, 3, and 4, the cover 46 is an open-ended cylindrical member configured to fit over the projecting portion 52 of the feed-through member 56 and having a spaced interior 158. The interior 158 is defined by an open bottom end 162, a cylindrical inner wall 166 and a top wall 170. The interior side of the top wall 170 is recessed at portions 174 to define a circumferential shelf 178, which is configured to engage the fully coated side 60 of the quartz-crystal sensor 44, FIG. 7. A central aperture 182 of circular configuration in the center of the top wall 170, allows access to the fully coated side 60, and more specifically the active area 45 of the quartz crystal sensor 44.
FIG. 8 more completely illustrates the monitoring assembly 40 as mounted to the chamber 10. Portions of the side wall 22 have been deleted for reasons of clarity.
The assembly 40 is attached to the side wall 22 by positioning the feed through unit 56 through the openings provided in the side wall and adjacent mounting plate 30. The assembly 40 is secured using the center portion 116 which engages and abuts the interior side 31 of the mounting plate 30. The jam nut 150 and associated washer 146 engage the exterior side 33 of the plate 30 to axially position the assembly 40 relative to the wall 22. Because the interior 18 of the chamber is evacuated and due to the corrosive environment therein, the O-ring 154 is preferably positioned in a circumferential groove 175 provided on the interior side 31 of the center portion 116 of the feed-through unit 56 to provide an adequate chamber vacuum seal. The O-ring 154 is made from Viton™, or can be made from any other convenient sealing material.
Because the through opening 108 in the feed-through member 56 also separates the chamber interior 18 from atmosphere, there is an additional sealing need. As noted, the O-ring 88 is positioned in the countersink 84 on the distal end 80 of the projection portion 52 of the feed-through member 56; that is, the end extending into the chamber interior 18. The O-ring 88 is encapsulated or otherwise attached within the countersink 84 and the ceramic spacer 92 is centrally placed over the distal end 80. The leaf spring 104 is then placed in the countersink 96 provided on the distal or facing side of the spacer 92, along with the fastener 100, which extends into the interior of the feed-through member 56 through the openings in the spacer into the provided opening 108 provided.
The dielectric spacer 120, the lockwasher 124, and the hex nut 128 are placed within the opposite side of the through opening 108 and over the threaded portion 132 of the attached fastener 100, whereby tightening of the hex nut 128 while using a screwdriver to hold the fastener head 98 in place supplies adequate force to compress the O-ring 88 into sealing engagement without inducing torsional forces. The head 98 of the fastener 100 is positioned in the countersink 96 and is substantially flush with the facing side 93 of the spacer 92. In this configuration, the fastener 100 is tightened into compression with the leaf spring 104 with the fingers 102 being circumferentially disposed on the facing surface 93.
The end 134 of the threaded portion 132 of the fastener 100 is fitted into the socket 144 of the electrical support assembly 136 which is sized to retain the end. The electrical support assembly 136 includes a cylindrical engagement portion adjacent the socket which is contoured to fit within an expanded portion of the through opening 108 of the feed-through member 56, the engagement portion preferably having a corresponding set of threads for engaging corresponding internal threads in the through opening. The socket 144 forms a sleeve covering the end 134 of the threaded portion 132 of the fastener 100 and establishes electrical contact therewith. As noted, the electrical contact assembly 136 is interconnected to one end of a BNC cable 140. The proximal end of the cable 140, is connected to an oscillating device 186, the details of which are known and described in U.S. Pat. No. 5,117,192, the entire contents of which are herein incorporated by reference.
Referring back to the inserted side of the monitoring assembly 40, the coil spring 76, made from an electrically conductive, environmentally resistant, and non-reactive material (Hastalloy, according to this embodiment) is inserted into the circumferential groove 72 of the projecting portion 52 and the quartz crystal sensor 44 is positioned within the interior 158 of the cover 46 and rests against the shelf 178. The cover 46 is then pressed over the projecting portion 52 of the feed-through member 56 and the protruding coil spring 76, with the open end of the cover 46 engaging the distal end of the center portion 116. When pressed into position, the cover 46 is releasably biased into position with the fingers 102 of the leaf spring 104 and the patterned side 64, and more particularly the peripheral electrode 68, is placed into intimate contact therewith. The entirety of the active area 45 of the quartz crystal sensor 44 is made accessible through the opening 182 in the cover 46. In addition, the engagement of the outer portion of the fully coated face 60 of the quartz crystal sensor 44 provides an electrical ground return point with the shelf 178, the cover 46 being preferably made of an electrically conductive material. According to the present embodiment, the feed-through unit 56, and the cover 46 are each fabricated from nickel.
In operation, and as noted the BNC cable 140 is attached at its proximal end to an oscillation generating device 186 which when powered applies a voltage through the electrical contact assembly into the socket 144, the voltage being transmitted through the conductive fastener 100 and into the leaf spring 104. The voltage is applied through the fingers 102 of the spring into the patterned side 64 and to the electrode 68. An appropriate voltage causes a sharp repeatable electromechanical resonation of the active area 45 of the quartz crystal sensor 44, e.g. 6 megahertz. A deposition sensor controller 188, shown schematically in phantom, and connected by known means to the oscillation device 186, can sense the frequency shift in the sensor based on the accumulation of mass. Knowledge of the mass density of the deposited solid product and the frequency shift produced due to the dampening of the sensor 44, FIG. 7, as film is deposited on the fully coated face 60, FIG. 7, can then be used to determine the thickness of the deposited film. Additional details relating to the operation and theory of the deposition controller 188 is known as described in an article written by C. Gogol and C. Cipro, entitled "The Hunt for High Performance Optical Coatings," published in Photonics Spectra, October 1995, the entire contents of which are herein incorporated by reference.
As noted, the environment within the chamber 10 is highly reactive and corrosive, containing such highly reactive agents as fluorine and bromide, for example as found in a polysilicon etch chamber. Therefore, it is necessary that the assembly within the chamber 10 be made from materials which will not react with the on- going process or will degrade due to exposure therewith. It has been found with polysilicon etch chambers, for example, that nickel or cold rolled steel with nickel plating is preferred, including the active area 45 of the quartz crystal sensor 44.
PARTS LIST FOR FIGS. 1-8
10 deposition/etch chamber
14 housing
18 interior volume
22 side walls
24 top wall
26 bottom wall
30 mounting plate
40 wall deposition monitoring system
44 quartz crystal sensor
45 active area
46 cover
52 projecting portion
56 feed-through member
60 fully coated face side
64 patterned side
68 electrode
72 circumferential groove
76 circular coil spring
80 distal end
84 countersink
88 O-ring
92 spacer
93 facing side
96 countersink
98 head
100 threaded fastener
102 fingers
104 leaf spring
108 opening
112 threaded portion
116 center portion
120 spacer
124 lockwasher
128 hex nut
132 threaded end
136 electrical support assembly
140 BNC cable
144 socket
146 washer
150 jam nut
154 O-ring
158 cover interior
162 open end
166 inner wall
170 top wall
174 recesses
175 groove
178 circumferential shelf
182 access opening
186 oscillator device
188 deposition sensor controller
Though the invention has been described in terms of a single preferred embodiment, it will be readily apparent that variations and modifications can be made within the spirit and scope of the invention as defined by the appended claims. | A wall deposit monitoring system for measuring variation in wall deposit thickness in an etch or deposition chamber having a contained reactive environment includes at least one quartz or other piezoelectric crystal sensor installed through a wall of the chamber using a feed-through member. A cover assembly retains the sensor at a projecting end of the feed-through member in a position in proximity with the interior of a chamber wall. The cover includes an opening providing access to the active portion of the sensor for exposure to the reactive environment. An attached oscillating device causes the active portion of the sensor to resonate. As processing is performed in the chamber, a solid reaction product accumulates on the exposed active portion, damping the vibration of the sensor. A detection device sensing the shift in frequency can then calculate the relative change in thickness for a given material. When used with highly reactive environments, the assembly is constructed of non-reactive materials which are sufficiently electrical and thermally conductive. | 2 |
RELATED APPLICATIONS
[0001] This application claims benefits of Provisional Application 61/220,674 filed on Jun. 26, 2009.
BACKGROUND OF THE INVENTION
[0002] The present invention generally relates to venting systems for building roofs and walls and, more particularly, to systems which provide for release of air from confined airspaces below to the exterior of the building.
[0003] Many buildings are constructed with an intervening airspace below a roof and above an occupied area. For example, residential buildings may be constructed with enclosed attics or other enclosed spaces between a roof and an interior ceiling. For any particular building at any particular time, exterior temperature and humidity conditions may differ from interior temperatures and humidity conditions. These differences may cause moisture accumulation and heat buildup in the enclosed spaces. In order to avoid this phenomenon, it is accepted practice in the building industry to provide venting of these enclosed spaces so that temperature and humidity in the enclosed spaces may equalize with exterior conditions.
[0004] Provision of such venting typically requires visible penetrations of roofs or attic walls. Such penetrations are subject to intrusion of rain, snow dust or sparks and are often costly and, in some instances, may be considered esthetically unattractive.
[0005] As can be seen, there is a need for venting systems which are not visible from an exterior of a building. Additionally, there is a need for a venting system which may preclude intrusion of rain, snow, dust, and sparks or flames.
SUMMARY OF THE INVENTION
[0006] In one aspect of the present invention, a system for venting enclosed spaces between a roof and attic space of a building may comprise: an opening in a roof deck; wherein exterior roofing material overlies the roof deck and completely overlies the opening; wherein the roofing material comprises roof material segments; and wherein the roof material segments have seams with spaces between segments through which air flow can pass.
[0007] In another aspect of the present invention, a vent assembly for venting an interior space of a building to an exterior of the building, the vent assembly may comprise: a frame for attachment to sheathing or a roof deck of the building; a framed opening with a shape and size that corresponds to a shape and size of an opening in the sheathing or roof deck; and the frame having a thickness no greater than a thickness of an elevating batten support onto which segments of exterior building covering are attached.
[0008] In still another aspect of the invention, a method for venting an interior space of a building to an exterior of the building may comprise the steps of: making an opening in sheathing or a roof deck of the building; attaching support for segmented building covering material adjacent the opening; and attaching the segmented building exterior covering material to the support: so that the building exterior covering material is elevated above the sheathing or roof deck; so that the exterior roofing material overlies the roof deck and completely overlies the opening; and so that the roof material segments are installed so that air can flow between the seams and spaces in the roof tile.
[0009] These and other features, aspects and advantages of the present invention will become better understood with reference to the following drawings, description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a simplified perspective view of a building with venting in accordance with an embodiment of the present invention;
[0011] FIG. 2 is a partial section view of the building of FIG. 1 taken along the line 2 - 2 of FIG. 1 in accordance with an embodiment of the present invention;
[0012] FIG. 3 is a partial section view of the building of FIG. 1 taken along the line 3 - 3 of FIG. 1 in accordance with an embodiment of the present invention;
[0013] FIGS. 4A , 4 B b and 4 C are views of a vent assembly in accordance with an embodiment of the present invention; and
[0014] FIGS. 5A , 5 B, 5 C, 5 D and 5 E are views of a vent assembly in accordance with a second embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The following detailed description is of the best currently contemplated modes of carrying out exemplary embodiments of the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.
[0016] Various inventive features are described below that can each be used independently of one another or in combination with other features.
[0017] Broadly, an exemplary embodiment of the invention may comprise a system of venting enclosed spaces of a building through an opening in sheathing or the roof deck of the building over which segmented exterior building covering material may be placed. The segmented exterior building covering material may be elevated from a surface of the sheathing or roof deck so that air may flow through the opening and through openings between segments of the exterior building covering material.
[0018] Referring now to FIG. 1 , a building 10 is illustrated in simplified form. In an exemplary embodiment of the invention a roof 12 may be provided with venting. The venting may be invisible to an observer outside of the building 10 . For purposes of illustration, areas of venting may be identified by the numeral 12 - 1 .
[0019] Referring now to FIG. 2 a partial cross sectional view of the roof 12 may illustrate an exemplary embodiment of a venting system in accordance with the invention. A roof deck 14 may have an opening 14 - 1 therethrough. The roof deck 14 may enclose an attic or other enclosed space 16 above a ceiling (not shown) of the building 10 . Battens or supports 18 may be attached to the roof deck 14 . Segments 20 of exterior roof material or exterior building covering material may be attached to the supports 18 . The segments 20 may be materials such as concrete or clay tile or segments of metal roofing. The segments 20 may be installed so that spaces between individuals ones of the segments 20 may permit air flow. In the exemplary embodiment of FIG. 2 , air may flow through he opening 14 - 1 and past the segments 20 so that humid and/or heated air may be vented from the enclosed space 16 .
[0020] In another embodiment of the present invention, a vent assembly 22 may be placed over the opening 14 - 1 as shown in FIG. 3 . The vent assembly 22 may have a thickness less than a thickness of the supports 18 . Thus the segments 20 may overlie the vent assembly 22 and the vent assembly may be invisible from an exterior of the building 10 .
[0021] Referring now to FIGS. 4A and 4B , an exemplary embodiment of one of the vent assemblies 22 may be seen in detail. The vent assembly may comprise a frame 22 - 1 and a screened opening 22 - 2 . FIG. 4A may illustrate a top side 23 (i.e., a side of the vent assembly 22 which when installed would be facing away from the sheathing or roof deck 14 of FIG. 3 . FIG. 4B may illustrate a bottom side 24 (i.e., a side of the vent assembly 22 which when installed would be facing toward the sheathing or roof deck 14 of FIG. 3 ). A main moisture diverter 22 - 3 may be attached to the top side 23 . Secondary moisture diverters 22 - 4 may also be attached to the top side 23 . The moisture diverters 22 - 3 and 22 - 4 may prevent incursion of moisture or rain water into the enclosed space 16 of FIG. 3 .
[0022] Referring now to FIG. 4C , the bottom side 24 of the vent assembly 22 may be seen in detail. In FIG. 4C , an exemplary embodiment of an installation arrangement of the vent assembly 22 is shown. The vent assembly 22 may be positioned adjacent to two of the battens or supports 18 . The vent assembly may have a rectangular portion 22 - 5 with a length L that is about the same as spacing between the supports 18 . The vent assembly may be provided with nailing holes 22 - 6 which are spaced apart a width W that corresponds to spacing between rafters (not shown) that support the roof deck 16 of FIG. 3 . An adhesive strip 22 - 7 may be applied to the bottom side 24 so that incursion of rain water or moisture incursion may be precluded between the bottom side 24 and the deck 14 .
[0023] Referring now to FIGS. 5A through 5E , there is illustrated an exemplary embodiment of a vent assembly 30 . The vent assembly 30 may have moisture diverters 30 - 1 which may preclude moisture or rainwater incursion. The vent assemblies 30 may have a chevron configuration with triangularly shaped openings 30 - 2 . In the case of the vent assembly 30 , the triangularly shaped opening 30 - 2 may be configured so that a single clay tile used as outer roofing material may overlie the entire opening 30 - 2 .
[0024] The vent assemblies 22 and/or 30 may be constructed from sheet metal or alternatively they may be constructed as molded plastic units. When used on roof decks, the vent assemblies 22 and/or 30 may have an overall thickness of about ¾ inch so that they do not protrude above the supports 18 .
[0025] While the vent assemblies have been described herein as roof vents, it may be noted the vent assemblies 22 and/or 30 may be employed to provide venting through vertical walls of buildings. The vent assemblies may also be used in conjunction with gable end vents, ridge vents, and soffit vents or dormer vents. For example, if a building has a large attic, some gable ends vents may be used and these gable ends vents may be supplemented with roof venting in accordance with the present invention and building code requirement.
[0026] It should be understood, of course, that the foregoing relates to exemplary embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims. | A system for venting enclosed spaces between a roof and an attic space of a building may comprise an opening in a roof deck; wherein exterior roofing material overlies the roof deck and completely overlies the opening; wherein the roofing material comprises roof material segments; and wherein the roof material segments are in spaces between segments through which air flow can pass. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Stage of International Application No. PCT/CR2008/000001, filed on Feb. 6, 2008, the contents of which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
This disclosure relates to correction processes of osseous development anomalies, more specifically, with regards to malformations that develop or bring about a deficiency in the ocular orbit development.
BACKGROUND
Today a significant number of patients with congenital or acquired defects in the ocular globe are treated successfully with ocular prostheses adaptation, achieving the stimulation necessary for the proper development of the orbit bone component. Opposing to this, there is a group of patients where this adaptation cannot be made due to the lack of space resulting from development deficiency, and, up to date, there is no other alternative effective treatment method.
SUMMARY
The present disclosure is focused on an apparatus that, after being implanted surgically, enables the stimulation of the orbit's progressive development in posteroanterior, superoinferior and lateral direction.
DESCRIPTION OF DRAWINGS
FIG. 1 shows a halo-like structure for fixing to the cranium.
FIG. 2 shows a portion of the halo-like structure of FIG. 1 .
FIG. 3 shows a bridge-shaped plate.
FIG. 4 shows a union plate.
FIG. 5 shows an orbital distractor.
DETAILED DESCRIPTION
This disclosure relates to a novel apparatus for persons presenting with a significant degree of deficiency in terms of orbit bone development. This novel apparatus is produced from titanium and comprises three devices, i.e. a halo-like structure for fixing to the cranium, a plate for connecting between the devices, and a device carried by the halo-like structure mentioned previously. The novel apparatus is secured to the orbit in order to bring about expansion. Said device is known as a distractor.
In some implementations, the apparatus is comprised of the following components in its manufacturing process. One component is a three-quarters circle titanium ring 1 . a that is fixed to the cranium and serves as a supporting means for the orbit distractor. The latter is formed by two semicircles, one of them being the mirror image of the other. The front section of the semicircle is flat and rectangular. In the frontmost section of said flat area there are five holes in superoinferior direction 1 . b —equidistant from each other—which enable the passing of the fixing bars 4 . c of the stabilizing plate. Further, the halo-like structure in the front face has five threaded equidistant holes 2 . a from front to back, matching with the five superoinferior holes. In the posterior half of the flat section there are two holes in the lateral side along its entire length, where two titanium circular bars (horizontally) 1 . c can be inserted, separated from each other, in order to enable the lateral movement of said two semicircles. Each semicircle can be maintained in its final specific position by means of a fastening screw mounted on a washer that secures those bars, preventing the ring from moving.
The posterior section of the halo-like structure—in its inferior side—has a bridge-shaped plate 3 . a , with upward convexity, which can be moved backwards by a screw 3 . b activated in its posterior section for fitting in the cranium. The bridge-shaped plate has a channel or rail in its superior section that enables its better displacement. A screw in the superior section 3 . b is used to fix the plate in the final specific section. Mounted on a washer, the screw can pass through the oval hole of the titanium ring in its superoposterior section, which, then, is introduced directly in a screw hole of the same size within the plate. In that way, the bridge-shaped plate is fixed and cannot move from the desired position. This bridge-shaped plate is detachable and will have 12 circular threaded holes 3 . c for inserting the screws that can be mounted on the cranium as a supporting means for the whole apparatus. The holes and screws are of the same size. The screw is an Allen screw.
The union plate 4 . a is a device that joins the halo-like structure or titanium ring with the distractor. This union plate is provided with two parallel holes 4 . c equidistant from the edges and that go through the plate completely. Perpendicular to these holes, there is a threaded hole 4 . b that penetrates in up to the tunnel formed by the hole in its journey. This hole has an Allen screw for fixing the union bars between the plate and the fastening halo-like structure. In its widest side it has a threaded ring 4 . d , which enables the insertion of the threaded section of the outer cylinder of the distractor. This distractor is comprised of a stem with a proximal outer threading 5 . a presenting four equidistant grooves in the opposing end of the threading section. Distally to these grooves, the stem has four holes where 4 cylinders 5 . b are placed to enable the displacement of the wheel axles; in that way, they can be opened and closed until they can converge with each other—movement that can be achieved by means of 4 connectors 5 . d sliding through the grooves with longitudinal movements. These connectors are connected to the wheel axles allowing them to move transversally through the little cylinders, which have a small groove, partially longitudinal, that allows the 4 booms to displace and, thus, achieving a continuous adjustment movement of the wheels. This movement can be regulated by means of a threaded axle, which slides interiorly across the main cylinder by means of a gear system that limits the movement of the wheels at 0.25 mm per round applied to the internal stem. The latter has a handle 5 . e with a graphic corresponding to the wheels' opening in millimeters.
The wheels are four bracket plates 5 . c with distal and horizontal perforation. The proximal and vertical section is perforated to be joined by using a screw to the wheel axles.
The system movement from back to front can be achieved by gearing the threaded section of the main axle with the inner thread of the plate hole we have described above. | In one aspect, an apparatus for correcting osseous development deficiencies at orbital level in persons includes a halo-like structure for fixing to a cranium, a union plate between the halo-like structure and the distractor, and the orbital distractor itself, which is supported by the halo-like structure and fixed to the orbit. | 0 |
[0001] The invention relates to an ironing system, more particularly to an induction ironing system.
BACKGROUND OF THE INVENTION
[0002] Induction ironing systems consist of irons whose soleplates are heated by electromagnetic radiation from an induction coil. This heating method requires the soleplate to be in close proximity to the induction coil. The ironing systems usually include a temperature regulating sub-system that switches on/off the heating means (induction coil) when the soleplate attains a pre-set temperature, based on the input from a temperature sensor (e.g. a thermistor or a thermostat). However, placement of the sensor is often difficult and has an impact on the mechanical construction of the induction ironing system. Furthermore, the response time of the sensor (due to air-gaps, moisture, etc.) results in an inaccurate and slow functioning of the temperature regulating sub-system thereby causing a wide soleplate temperature range that decreases ironing performance. In a case where the induction coil is located inside an ironing board, further problems arise. Due to the dynamics of the iron during ironing, it is difficult to locate the sensor at any position, as it is a probabilistic event that the iron would come right above the sensor and provide sufficient time to detect the temperature of the soleplate. Besides, when a garment to be ironed is placed between the ironing board and the iron, the garment would interfere with the function of the sensor.
[0003] UK Patent Application GB2392171 describes an induction ironing system comprising an iron and an ironing board with multiple induction coils. In order to trigger the electromagnetic field, the ferrous base of the iron has to be in contact with the electromagnetic field produced by the electromagnetic coils. To stop the heating process of the iron, either the current passing through the ironing board has to be switched off or the iron has to be lifted upwards until it goes out of range of the electromagnetic field. However, this system does not ensure controlled temperature and hence may result in the scorching of fabric.
SUMMARY OF THE INVENTION
[0004] In accordance with a first aspect of the invention, an ironing system comprises an iron including a soleplate, wherein said soleplate comprises an induction heatable material; and a unit including at least one induction coil and a device, wherein said induction coil is configured for charging said iron and said device is configured for detecting a temperature of said soleplate by sensing a change in current flowing through said induction coil or by sensing a change in voltage across said induction coil, said change in current or voltage being caused by a change in self inductance of said induction coil, said change in self inductance further being caused by a change in magnetic permeability of said soleplate as a function of its temperature, said device further being configured for switching said induction coil on or off depending on the temperature. The iron receives the necessary energy for ironing from the induction coil that is placed in the unit. An alternating magnetic field generated by the induction coil induces eddy currents in the soleplate and thus the soleplate gets heated up. The iron is then said to be charged. The induction heatable materials change their magnetic permeability with temperature. The self inductance of the induction coil and hence the current passing through the induction coil vary as a function of the magnetic permeability This is used as a trigger to switch the induction coil on or off based on the pre-determined relationship between the desired soleplate temperature and the current passing through the induction coil. In this manner, the temperature of the soleplate can be determined without the need of a temperature sensor.
[0005] According to another embodiment of the invention, said device comprises a current/voltage sensing circuit connected to said induction coil, wherein said current/voltage sensing circuit senses a change in current through said induction coil or senses a change in voltage across said induction coil. The device further comprises a current switching circuit, wherein said current switching circuit switches said induction coil on or off. The device furthermore comprises a temperature control circuit, wherein said temperature control circuit controls said current switching circuit depending on the current/voltage sensed by said current/voltage sensing circuit. The device is thus capable of switching said induction coil on or off based on the current/voltage in the coil that it can sense (this current/voltage having a relationship to the soleplate temperature as pre-established and programmed in the system.). Therefore, the temperature of the soleplate can be regulated without the help of a conventional temperature sensor
[0006] According to an embodiment of the invention, the induction heatable material is a ferro-magnetic material having its Curie temperature substantially close to the ironing temperature. Phytherm alloys are examples of such commercially available materials/alloys. Phytherm 230 or Phytherm 260 may be used as induction heatable materials. The Curie temperature of the induction heatable material of the soleplate is in the range of 100 to 300° C. This soleplate with above mentioned Curie temperature is suitable for ironing at temperatures in the range of 100 to 250° C. However, in order to ensure safe ironing of delicate garments such as silk, in another embodiment, a shoe could be detachably connectable to the soleplate to enable ironing-delicate garments at temperatures in the range of 50° C.-150° C.
BRIEF DESCRIPTION OF THE FIGURES
[0007] FIG. 1 is a schematic representation of a device of an ironing system according to an embodiment of the invention;
[0008] FIG. 2 is a representation of the output of a temperature control circuit;
[0009] FIG. 3 shows a response across an induction coil when a switch is opened for a high value of inductance;
[0010] FIG. 4 shows a current through a current/voltage sensing circuit for a high value of inductance;
[0011] FIG. 5 shows a voltage across a current/voltage sensing circuit for a high value of inductance;
[0012] FIG. 6 shows a response across an induction coil when a switch is opened for a low value of inductance;
[0013] FIG. 7 shows a current through a current/voltage sensing circuit for a low value of inductance;
[0014] FIG. 8 shows a voltage across a current/voltage sensing circuit for a low value of inductance;
[0015] FIG. 9 shows an ironing system according to an embodiment of the invention comprising an iron, an ironing board with one or more induction coils;
[0016] FIG. 10 shows an ironing system according to an embodiment of the invention comprising an iron, an ironing board and a charging base with one or more induction coils; and
[0017] FIG. 11 shows an iron with an ironing shoe according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention will be described with respect to particular embodiments and with reference to certain drawing figures, but the invention is not limited thereto but only by the claims. Any reference signs in the claims shall not be construed as limiting the scope of the invention. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn to scale for illustrative purposes. Where the term “comprising” is used in the present description and claims, it does not exclude other elements or steps. Where an indefinite or definite article is used when referring to a singular noun e.g. “a” or “an”, “the”, this includes a plural of that noun unless something else is specifically stated.
[0019] Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
[0020] Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.
[0021] FIG. 1 is an example schematically showing a first embodiment of the invention. As shown in FIG. 1 , a device 130 is connected to an induction coil 120 . Further as shown in FIG. 1 , the device 130 includes a current/voltage sensing circuit 150 , a current switching circuit 140 and a temperature control circuit 160 . The current/voltage sensing circuit 150 includes a switch 151 , a resistor 152 and a signal-conditioning device 153 . The current switching circuit 140 includes a bridge rectifier 141 and is connected to the supply voltage 142 . The induction coil 120 and a capacitor 121 together form a parallel resonant circuit 125 . A sole plate 180 is heated by electromagnetic radiation from the induction coil 120 .
[0022] While charging the iron either during ironing or during rest, the alternating magnetic field generated by the induction coil 120 induces eddy currents in the soleplate 180 . The magnetic properties of induction heatable material of the soleplate 180 are dependent on the temperature at which they are used. These properties progressively decrease and finally disappear beyond a characteristic temperature. This temperature is generally referred to as “Curie temperature” of the material.
[0023] The current/voltage sensing circuit 150 enables the temperature control circuit 160 to activate the current switching circuit 140 when the temperature of the soleplate 180 is below the Curie temperature. The self-inductance of the induction coil 120 changes when the temperature of the soleplate 180 exceeds the Curie temperature. This is because the magnetic permeability of the material of the soleplate 180 drops down to a low value approaching unity when the temperature is beyond the Curie temperature. This will be measured by the current/voltage sensing circuit 150 and the temperature control circuit 160 will be disabled. The current switching circuit 140 becomes inactive and the induction coil 120 gets switched off. The soleplate 180 cools down. The magnetism of the soleplate 180 is revived when the temperature of the soleplate 180 drops below the Curie temperature.
[0024] The current through the induction coil 120 can be calculated using the equation:
[0000]
i
=
1
L
·
∫
u
·
t
(
1
)
[0025] wherein i is the current through the induction coil 120 , L is the self-inductance of the induction coil 120 , u is the induced voltage and t is time. The self-inductance L is a function of magnetic permeability μ which in turn is a function of temperature T. For ferromagnetic materials, μ changes rapidly with temperature, when temperature T exceeds the Curie temperature. Hence the self-inductance L varies as magnetic permeability μ of the soleplate 180 varies as a function of its temperature T. According to equation 1, the current i through the induction coil 120 varies with changes in self-inductance L of the induction coil 120 .
[0026] The current i through the induction coil 120 is measured by the resistor 152 . The parallel resonant circuit 125 , formed by the induction coil 120 and the capacitor 121 , is connected to the supply voltage 142 via the switch 151 . When the switch 151 is closed, linearly increasing current flows through the parallel resonant circuit 125 , the switch 151 and the resistor 152 . This current i is transferred into a voltage u across the resistor 152 and is fed back via the signal conditioning device 153 to the temperature control circuit 160 . The signal conditioning device 153 provides signal conditioning (e.g. low pass filtering and amplification) to the voltage u across the resistor 152 . The temperature control circuit 160 provides the switch 151 with a square wave signal. The duty cycle of this control signal varies to enable power adjustment. It can be a fixed duty cycle (e.g. 50%) if no power control is necessary. Then it is simply a power on/off control. The switch 151 is controlled via a square wave as shown in FIG. 2 . It is a representation of the output of the temperature control circuit 160 , used to control the switch 151 . At a high signal level the switch 151 is closed. As soon as the switch 151 is closed, current i flows through the induction coil 120 , the capacitor parallel to the coil 121 , the switch 151 and through the resistor 152 . During this phase, energy is stored in the induction coil 120 . When the switch 151 is opened, the energy is released resulting in a (induction) voltage response across the coil 120 . The frequency of this response is determined by the self-inductance L of the coil 120 and the capacitance of the capacitor 121 . The voltage response across the induction coil 120 for a high value of self-inductance L of the induction coil 120 is shown in FIG. 3 when the switch 151 is opened. The response across the induction coil 120 for a low value of self-inductance L is shown in FIG. 6 . FIGS. 4 and 5 show the current i through and voltage u across the resistor 152 for a high value of self-inductance L of the induction coil 120 , whereas FIGS. 7 and 8 show the current i through and voltage u across the resistor 152 for a low value of self-inductance L of the induction coil 120 .
[0027] As the switch 151 is closed, current i flows through the resistor 152 , resulting in a voltage u across this resistor 152 . The amplitude of this voltage u is used to switch the temperature control circuit 160 on or off. The amplitude of the current i determines the trigger point for temperature control circuit 160 . It is clear that the self-inductance L of the induction coil 120 is mainly determined by μ of the soleplate to be heated. When the soleplate is heated up to the Curie temperature, μ of the soleplate drops significantly, resulting in a lower self-inductance L. As the self-inductance L of the induction coil 120 decreases, the current i through the switch 151 and the resistor 152 increases. It further results in a higher voltage u across the resistor 152 and a higher response voltage across the induction coil 120 when the switch 151 is released. Both can be used to trigger the temperature control circuit 160 .
[0028] Commercial alloys like Phytherm 230 or Phytherm 260 can be used whose Curie temperature can be customized. Phytherm 230 has a composition with 50 wt % Ni, 10 wt % Cr and rest Fe. The Curie temperature is 230° C. Phytherm 260 has a composition with 50 wt % Ni, 9 wt % Cr and rest Fe. The Curie temperature is 260° C.
[0029] FIG. 9 shows an embodiment of an ironing system 200 . The ironing system 200 shown in FIG. 9 includes an iron 210 and an ironing board 230 . The iron 210 is provided with a soleplate 212 comprising an induction heatable material. The ironing board 230 can be either a compact board or a full-size board. The one or more induction coils 220 positioned within the entire ironing board can charge the iron 210 continuously while ironing.
[0030] FIG. 10 shows an ironing system 500 comprising an iron 510 , an ironing board 530 and a charging base 520 with one or more induction coils 540 . The iron has a soleplate 512 made from a material whose Curie temperature is substantially close to the ironing temperature i.e. in the range of 100-300° C. The iron 510 has to be returned to the charging base 520 for charging. The alternating magnetic field generated by the induction coil 540 induces eddy currents in the soleplate 512 which then gets heated up. As the temperature of the soleplate exceeds the Curie temperature, the device 550 switches the induction coil 540 off and the iron 510 is ready for use.
[0031] FIG. 11 shows an iron 610 having an ironing shoe 620 . The soleplate 612 is equipped with a perforation into which the ironing shoe 620 is inserted. All above mentioned embodiments are suitable for single temperature ironing i.e., if a particular material is chosen for the soleplate of the iron, its Curie temperature is fixed and the temperature range at which the iron can be used is fixed. If the temperature chosen is high, then the delicate garments such as silk cannot be ironed. The ironing shoe 620 enables low temperature ironing for delicate garments. | An ironing system ( 500 ) comprises an iron ( 510 ) with a soleplate ( 512 ) comprising an induction heatable material. The ironing system ( 500 ) further comprises a unit ( 520, 530 ) that includes at least one induction coil ( 540 ) and a device ( 550 ). The induction coil ( 540 ) charges the iron ( 510 ) whereas the device ( 550 ) detects the temperature of the soleplate ( 512 ) by sensing a change in current flowing through the induction coil ( 540 ) or by sensing a change in voltage across the induction coil ( 540 ). The current or voltage changes as self inductance of the induction coil ( 540 ) changes with magnetic permeability of the soleplate ( 512 ) as a function of its temperature. The device ( 550 ) switches the induction coil ( 540 ) on or off depending on the detected temperature. | 3 |
BACKGROUND OF THE INVENTION
[0001] (1) Field of the Invention
[0002] The invention relates to industrial equipment. More particularly, the invention relates to the detonative cleaning of industrial equipment.
[0003] (2) Description of the Related Art
[0004] Surface fouling is a major problem in industrial equipment. Such equipment includes furnaces (coal, oil, waste, etc.), boilers, gasifiers, reactors, heat exchangers, and the like. Typically the equipment involves a vessel containing internal heat transfer surfaces that are subjected to fouling by accumulating particulate such as soot, ash, minerals and other products and byproducts of combustion, more integrated buildup such as slag and/or fouling, and the like. Such particulate build-up may progressively interfere with plant operation, reducing efficiency and throughput and potentially causing damage. Cleaning of the equipment is therefore highly desirable and is attended by a number of relevant considerations. Often direct access to the fouled surfaces is difficult. Additionally, to maintain revenue it is desirable to minimize industrial equipment downtime and related costs associated with cleaning. A variety of technologies have been proposed. By way of example, various technologies have been proposed in U.S. Pat. Nos. 5,494,004 and 6,438,191 and U.S. patent application publication 2002/0112638. Additional technology is disclosed in Huque, Z. Experimental Investigation of Slag Removal Using Pulse Detonation Wave Technique, DOE/HBCU/OMI Annual Symposium, Miami, Fla., Mar. 16-18, 1999. Particular blast wave techniques are described by Hanjalić and Smajević in their publications: Hanjalić, K. and Smajević, I., Further Experience Using Detonation Waves for Cleaning Boiler Heating Surfaces, International Journal of Energy Research Vol. 17, 583-595 (1993) and Hanjalić, K. and Smajević, I., Detonation-Wave Technique for On-load Deposit Removal from Surfaces Exposed to Fouling: Parts I and II, Journal of Engineering for Gas Turbines and Power, Transactions of the ASME, Vol. 1, 116 223-236, January 1994. Such systems are also discussed in Yugoslav patent publications P 1756/88 and P 1728/88. Such systems are often identified as “soot blowers” after an exemplary application for the technology.
[0005] Nevertheless, there remain opportunities for further improvement in the field.
SUMMARY OF THE INVENTION
[0006] Accordingly, one aspect of the invention involves an apparatus for cleaning a surface within a vessel. A vessel wall separates a vessel exterior from a vessel interior and has a wall aperture. The apparatus includes an elongate conduit having an upstream first and a downstream second end and positioned to direct a shockwave from the second end into the vessel interior. A pressure probe includes a body held in an operative position within the vessel so as to be exposed to the shockwave after the shockwave exits the conduit second end. The body has an exterior surface with a convergent nose portion. There is a first port in the body. A passageway extends between the first port and a pressure sensor. A support member holds the body in the operative position.
[0007] In various implementations, the probe may further include a cooling fluid circuit at least partially through the support member and body. The support member may include a cooling liquid-carrying conduit joining the body from above. The cooling liquid-carrying conduit may extend through the vessel wall. A source of fuel and oxidizer may be coupled to the conduit to deliver the fuel and oxidizer to the conduit. An initiator may be positioned to initiate a reaction of the fuel and oxidizer to produce the shockwave.
[0008] Another aspect of the invention involves a pressure probe apparatus with a body having an exterior surface with a forwardly-convergent nose portion. A passageway extends between a first port in the body and a pressure sensor. A support member holds the body in an operative position. A cooling fluid circuit extends at least partially through the support member and body.
[0009] In various implementations, the cooling circuit may extend around a periphery of a conduit defining the passageway. The body may have an aft surface with a second port and the cooling circuit may extend through the second port. The first port may be on a flat. The aft surface may have a third port and the cooling circuit may bifurcate so as to extend through the second and third ports. The apparatus may be combined with a cooling liquid flow in the cooling circuit. The support may carry a signal communication line from the pressure sensor. The nose may extend for at least 50% of a body length. Along at least 50% of a nose length, the nose may essentially converge forwardly with a half angle between 5° and 15°. The cooling circuit may span, within the body, at least 50% of the body length. An exemplary body length is between 2 cm and 20 cm and an exemplary maximum transverse dimension is no more than 4 cm. The apparatus may be used in combination with a detonative cleaning apparatus.
[0010] Another aspect of the invention involves a method for cleaning a surface within a vessel. Fuel and oxidizer are introduced to a conduit. A reaction of the fuel and oxidizer is initiated so as to cause a shockwave to impinge upon the surface. A pressure probe is used within the vessel to measure a pressure magnitude of the shockwave.
[0011] In various implementations, the method may be performed in a repeated sequential way. The reaction may include a deflagration-to-detonation transition. A cooling fluid may be passed through the pressure probe. The pressure probe may be repositioned by acting upon a support portion of a probe support member outside of the vessel.
[0012] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a view of an industrial furnace associated with several soot blowers positioned to clean a level of the furnace.
[0014] FIG. 2 is a side view of one of the blowers of FIG. 1 .
[0015] FIG. 3 is a partially cut-away side view of an upstream end of the blower of FIG. 2 .
[0016] FIG. 4 is a longitudinal sectional view of a main combustor segment of the soot blower of FIG. 2 .
[0017] FIG. 5 is an end view of the segment of FIG. 4 .
[0018] FIG. 6 is a partial side view of a pressure probe assembly associated with the outlet end of a combustion conduit.
[0019] FIG. 7 is a partial longitudinal sectional view of a probe unit of the assembly of FIG. 6 .
[0020] FIG. 8 is an aft end view of the probe unit of FIG. 7 .
[0021] FIG. 9 is a view of a pressure probe mounting bracket.
[0022] Like reference numbers and designations in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0023] FIG. 1 shows a furnace 20 having an exemplary three associated soot blowers 22 . In the illustrated embodiment, the furnace vessel is formed as a right parallelepiped and the soot blowers are all associated with a single common wall 24 of the vessel and are positioned at like height along the wall. Other configurations are possible (e.g., a single soot blower, one or more soot blowers on each of multiple levels, and the like).
[0024] Each soot blower 22 includes an elongate combustion conduit 26 extending from an upstream distal end 28 away from the furnace wall 24 to a downstream proximal end 30 closely associated with the wall 24 . Optionally, however, the end 30 may be well within the furnace. In operation of each soot blower, combustion of a fuel/oxidizer mixture within the conduit 26 is initiated proximate the upstream end (e.g., within an upstreammost 10% of a conduit length) to produce a detonation wave which is expelled from the downstream end as a shockwave along with associated combustion gases for cleaning surfaces within the interior volume of the furnace. Each soot blower may be associated with a fuel/oxidizer source 32 . Such source or one or more components thereof may be shared amongst the various soot blowers. An exemplary source includes a liquefied or compressed gaseous fuel cylinder 34 and an oxygen cylinder 36 in respective containment structures 38 and 40 . In the exemplary embodiment, the oxidizer is a first oxidizer such as essentially pure oxygen. A second oxidizer may be in the form of shop air delivered from a central air source 42 . In the exemplary embodiment, air is stored in an air accumulator 44 . Fuel, expanded from that in the cylinder 34 is generally stored in a fuel accumulator 46 . Each exemplary source 32 is coupled to the associated conduit 26 by appropriate plumbing below. Similarly, each soot blower includes a spark box 50 for initiating combustion of the fuel oxidizer mixture and which, along with the source 32 , is controlled by a control and monitoring system (not shown). FIG. 1 further shows the wall 24 as including a number of ports for inspection and/or measurement. Exemplary ports include an optical monitoring port 54 and a temperature monitoring port 56 associated with each soot blower 22 for respectively receiving an infrared and/or visible light video camera and thermocouple probe for viewing the surfaces to be cleaned and monitoring internal temperatures. Other probes/monitoring/sampling may be utilized, including pressure monitoring, composition sampling, and the like.
[0025] FIG. 2 shows further details of an exemplary soot blower 22 . The exemplary detonation conduit 26 is formed with a main body portion formed by a series of doubly flanged conduit sections or segments 60 arrayed from upstream to downstream and a downstream nozzle conduit section or segment 62 having a downstream portion 64 extending through an aperture 66 in the wall and ending in the downstream end or outlet 30 exposed to the furnace interior 68 . The term nozzle is used broadly and does not require the presence of any aerodynamic contraction, expansion, or combination thereof. Exemplary conduit segment material is metallic (e.g., stainless steel). The outlet 30 may be located further within the furnace if appropriate support and cooling are provided. FIG. 2 further shows furnace interior tube bundles 70 , the exterior surfaces of which are subject to fouling. In the exemplary embodiment, each of the conduit segments 60 is supported on an associated trolley 72 , the wheels of which engage a track system 74 along the facility floor 76 . The exemplary track system includes a pair of parallel rails engaging concave peripheral surfaces of the trolley wheels. The exemplary segments 60 are of similar length L 1 and are bolted end-to-end by associated arrays of bolts in the bolt holes of their respective flanges. Similarly, the downstream flange of the downstreammost of the segments 60 is bolted to the upstream flange of the nozzle 62 . In the exemplary embodiment, a reaction strap 80 (e.g., cotton or thermally/structurally robust synthetic) in series with one or more metal coil reaction springs 82 is coupled to this last mated flange pair and connects the combustion conduit to an environmental structure such as the furnace wall for resiliently absorbing reaction forces associated with discharging of the soot blower and ensuring correct placement of the combustion conduit for subsequent firings. Optionally, additional damping (not shown) may be provided. The reaction strap/spring combination may be formed as a single length or a loop. In the exemplary embodiment, this combined downstream section has an overall length L 2 .
[0026] Extending downstream from the upstream end 28 is a predetonator conduit section/segment 84 which also may be doubly flanged and has a length L 3 . The predetonator conduit segment 84 has a characteristic internal cross-sectional area (transverse to an axis/centerline 500 of the conduit) which is smaller than a characteristic internal cross-sectional area (e.g., mean, median, mode, or the like) of the downstream portion ( 60 , 62 ) of the combustion conduit. In an exemplary embodiment involving circular sectioned conduit segments, the predetonator cross-sectional area is a characterized by a diameter of between 8 cm and 12 cm whereas the downstream portion is characterized by a diameter of between 20 cm and 40 cm. Accordingly, exemplary cross-sectional area ratios of the downstream portion to the predetonator segment are between 1:1 and 10:1, more narrowly, 2:1 and 10:1. An overall length L between ends 28 and 30 may be 1-15 m, more narrowly, 5-15 m. In the exemplary embodiment, a transition conduit segment 86 extends between the predetonator segment 84 and the upstreammost segment 60 . The segment 86 has upstream and downstream flanges sized to mate with the respective flanges of the segments 84 and 60 has an interior surface which provides a smooth transition between the internal cross-sections thereof. The exemplary segment 86 has a length L 4 . An exemplary half angle of divergence of the interior surface of segment 86 is ≦12°, more narrowly 5-10°.
[0027] A fuel/oxidizer charge may be introduced to the detonation conduit interior in a variety of ways. There may be one or more distinct fuel/oxidizer mixtures. Such mixture(s) may be premixed external to the detonation conduit, or may be mixed at or subsequent to introduction to the conduit. FIG. 3 shows the segments 84 and 86 configured for distinct introduction of two distinct fuel/oxidizer combinations: a predetonator combination; and a main combination. In the exemplary embodiment, in an upstream portion of the segment 84 , a pair of predetonator fuel injection conduits 90 are coupled to ports 92 in the segment wall which define fuel injection ports. Similarly, a pair of predetonator oxidizer conduits 94 are coupled to oxidizer inlet ports 96 . In the exemplary embodiment, these ports are in the upstream half of the length of the segment 84 . In the exemplary embodiment, each of the fuel injection ports 92 is paired with an associated one of the oxidizer ports 96 at even axial position and at an angle (exemplary 90° shown, although other angles including 180° are possible) to provide opposed jet mixing of fuel and oxidizer. Discussed further below, a purge gas conduit 98 is similarly connected to a purge gas port 100 yet further upstream. An end plate 102 bolted to the upstream flange of the segment 84 seals the upstream end of the combustion conduit and passes through an igniter/initiator 106 (e.g., a spark plug) having an operative end 108 in the interior of the segment 84 .
[0028] In the exemplary embodiment, the main fuel and oxidizer are introduced to the segment 86 . In the illustrated embodiment, main fuel is carried by a number of main fuel conduits 112 and main oxidizer is carried by a number of main oxidizer conduits 110 , each of which has terminal portions concentrically surrounding an associated one of the fuel conduits 112 so as to mix the main fuel and oxidizer at an associated inlet 114 . In exemplary embodiments, the fuels are hydrocarbons. In particular exemplary embodiments, both fuels are the same, drawn from a single fuel source but mixed with distinct oxidizers: essentially pure oxygen for the predetonator mixture; and air for the main mixture. Exemplary fuels useful in such a situation are propane, MAPP gas, or mixtures thereof. Other fuels are possible, including ethylene and liquid fuels (e.g., diesel, kerosene, and jet aviation fuels). The oxidizers can include mixtures such as air/oxygen mixtures of appropriate ratios to achieve desired main and/or predetonator charge chemistries. Further, monopropellant fuels having molecularly combined fuel and oxidizer components may be options.
[0029] In operation, at the beginning of a use cycle, the combustion conduit is initially empty except for the presence of air (or other purge gas). The predetonator fuel and oxidizer are then introduced through the associated ports filling the segment 84 and extending partially into the segment 86 (e.g., to near the midpoint) and advantageously just beyond the main fuel/oxidizer ports. The predetonator fuel and oxidizer flows are then shut off. An exemplary volume filled the predetonator fuel and oxidizer is 1-40%, more narrowly 1-20% of the combustion conduit volume. The main fuel and oxidizer are then introduced, to substantially fill some fraction (e.g., 20-100%) of the remaining volume of the combustor conduit. The main fuel and oxidizer flows are then shut off. The prior introduction of predetonator fuel and oxidizer past the main fuel/oxidizer ports largely eliminates the risk of the formation of an air or other non-combustible slug between the predetonator and main charges. Such a slug could prevent migration of the combustion front between the two charges.
[0030] With the charges introduced, the spark box is triggered to provide a spark discharge of the initiator igniting the predetonator charge. The predetonator charge being selected for very fast combustion chemistry, the initial deflagration quickly transitions to a detonation within the segment 84 and producing a detonation wave. Once such a detonation wave occurs, it is effective to pass through the main charge which might, otherwise, have sufficiently slow chemistry to not detonate within the conduit of its own accord. The wave passes longitudinally downstream and emerges from the downstream end 30 as a shockwave within the furnace interior, impinging upon the surfaces to be cleaned and thermally and mechanically shocking to typically at least loosen the contamination. The wave will be followed by the expulsion of pressurized combustion products from the detonation conduit, the expelled products emerging as a jet from the downstream end 30 and further completing the cleaning process (e.g., removing the loosened material). After or overlapping such venting of combustion products, a purge gas (e.g., air from the same source providing the main oxidizer and/or nitrogen) is introduced through the purge port 100 to drive the final combustion products out and leave the detonation conduit filled with purge gas ready to repeat the cycle (either immediately or at a subsequent regular interval or at a subsequent irregular interval (which may be manually or automatically determined by the control and monitoring system)). Optionally, a baseline flow of the purge gas may be maintained between charge/discharge cycles so as to prevent gas and particulate from the furnace interior from infiltrating upstream and to assist in cooling of the detonation conduit.
[0031] In various implementations, internal surface enhancements may substantially increase internal surface area beyond that provided by the nominally cylindrical and frustoconical segment interior surfaces. The enhancement may be effective to assist in the deflagration-to-detonation transition or in the maintenance of the detonation wave. FIG. 4 shows internal surface enhancements applied to the interior of one of the main segments 60 . The exemplary enhancement is nominally a Chin spiral, although other enhancements such as Shchelkin spirals and Smirnov cavities may be utilized. The spiral is formed by a helical member 120 . The exemplary member 120 is formed as a circular-sectioned metallic element (e.g., stainless steel wire) of approximately 8-20 mm in sectional diameter. Other sections may alternatively be used. The exemplary member 120 is held spaced-apart from the segment interior surface by a plurality of longitudinal elements 122 . The exemplary longitudinal elements are rods of similar section and material to the member 120 and welded thereto and to the interior surface of the associated segment 60 . Such enhancements may also be utilized to provide predetonation in lieu of or in addition to the foregoing techniques involving different charges and different combustor cross-sections.
[0032] The apparatus may be used in a wide variety of applications. By way of example, just within a typical coal-fired furnace, the apparatus may be applied to: the pendants or secondary superheaters, the convective pass (primary superheaters and the economizer bundles); air preheaters; selective catalyst removers (SCR) scrubbers; the baghouse or electrostatic precipitator; economizer hoppers; ash or other heat/accumulations whether on heat transfer surfaces or elsewhere, and the like. Similar possibilities exist within other applications including oil-fired furnaces, black liquor recovery boilers, biomass boilers, waste reclamation burners (trash burners), and the like.
[0033] FIG. 6 shows a pressure probe assembly 150 having a head or probe unit 152 positioned facing the outlet 30 . In the exemplary embodiment, the probe is positioned in the area swept by the internal cross-section of the combustion conduit outlet in the direction of the centerline 500 and is in relatively close facing proximity (e.g., within 3 m of the outlet, more preferably 0.1 m-2 m). The probe unit 152 is held at the distal end 154 of a support arm 156 . As discussed below, the support arm 156 functions not only to support and locate the probe unit but to carry signal and cooling fluid communication for the probe unit. In the exemplary embodiment, the arm 156 is supported by a mounting bracket 158 held relative to some environmental structure (e.g., the furnace wall, or, as illustrated, the combustion conduit such as via the flange joints between the nozzle segment 62 and the segment upstream thereof). The bracket 158 may rigidly locate the arm or may provide for angular and translational excursions of the arm. In the exemplary embodiment, proximate an upstream end 160 of the arm, the arm is provided with port fittings for signal and fluid lines 162 and 164 , respectively discussed in further detail below. An exemplary arm length is 2-6 m and diameter is 2-5 cm. For pressure monitoring in locations more remote from the nozzle and/or wall aperture, other arm constructions and mounting arrangements may be more appropriate.
[0034] FIG. 7 shows further details of the exemplary probe unit. The unit has a body which may be formed of a material suitable for withstanding expected thermal and mechanical shock stresses. An exemplary body has a main piece 170 which may be machined from a metal (e.g., nickel- or cobalt-based superalloy, stainless steel, or the like). The main piece extends along a nose portion 172 aft from a tip 174 . The nose portion has a generally frustoconical surface 176 of half angle θ. Exemplary θ is ≦30°, more narrowly 5°-15°. The nose portion conical, or near conical, shape helps minimize formation of static shocks and the low angle taper helps keep the passing shockwave essentially attached to the body. The nose portion extends aft to an aft portion 178 which has a generally cylindrical external surface 180 provided with a single flat facet 182 . The body aft portion has an aft rim 184 secured relative to an aft endplate 186 . The body aft portion has a pair of opposed apertures. A first aperture 188 in the facet 182 accommodates a first (outboard) end portion 190 of a conduit 192 extending inboard (i.e., into an interior space 194 of the probe body) to a second (inboard) end portion 196 ). A second aperture 198 is in the cylindrical surface 180 opposite the aperture 188 and accommodates a support conduit 200 . The support conduit 200 may be formed as the distal end portion 154 of the arm 156 or may be secured thereto. Centrally within the conduit 200 , a pressure transducer 202 is held within a mounting fixture 204 . The fixture 204 extends from an upstream end portion 206 to a downstream end portion 208 . The downstream end portion 208 is coupled to the tube inboard end portion 196 to combine to define a flowpath 210 from an inlet 212 at the tube first end 190 to the operative end (e.g., membrane) of the pressure transducer 202 . An exemplary length of the flowpath 210 is 0.5-5 cm. The fixture 204 may be supported entirely by its interaction with the tube or may be supported via webs (not shown—e.g., left between longitudinally-drilled holes) extending radially outward to the conduit 200 . Overall body size may balance minimizing interference with the shockwave (indicating a small body) with appropriate robustness and economy of manufacture (indicating a potentially larger body). Exemplary body lengths are 2-20 cm and exemplary maximum transverse dimensions (e.g., diameter along the aft portion) are less than 4 cm.
[0035] The signal communication line 162 (e.g., coaxial cable). The line 162 may be connected to a control/monitoring system (not shown). As the length of the flowpath 210 may affect measured pressure values relative to the inlet 212 , the control/monitoring subsystem may be programmed to correct for this (e.g., ID pressure magnitude attenuation and phase corrections).
[0036] An annular or interrupted annular space 216 between the fixture 204 and conduit 200 accommodates the downstream flow of fluid from the fluid line 164 along fluid flowpaths 218 . In the exemplary embodiment, the probe body interior 194 has a series of progressively smaller cross-section areas, one ahead of the other within the nose, to permit the pathway to pass therewithin to cool the nose. In the exemplary embodiment, the endplate 186 has a pair of apertures 220 ( FIG. 8 ) associated with fittings 222 coupled to a coolant return line 224 ( FIG. 6 ) which may be secured relative to the arm 156 such as via hose clamps 226 .
[0037] FIG. 9 shows further details of the mounting bracket 158 . The exemplary bracket includes a body piece 240 formed as a sector of an annular metallic plate having first and second faces and extending between first and second circumferential ends and inner and outer diameter perimeter portions 242 and 244 . Near the inner diameter perimeter portion 242 bolt holes 246 correspond to the pattern of bolt holes of the associated nozzle and downstreammost doubly flanged segment flanges so as to permit the plate to be secured to the flanges by a group of the flange bolts. The outer diameter perimeter portion 244 includes a recess with a base portion 248 complementary to a portion of the cross-section of the arm 156 . A remaining portion of the recess is dimensioned to accommodate a clamp body 250 having an inner surface 252 complementary to an opposite portion of the arm cross-section (e.g., to form an approximate circle with the surface 248 ). Knob-headed bolts 254 may secure the clamp body 250 to the bracket body 240 to permit a secure clamping of the arm between the two to precisely hold the arm in a given position. This permits precise positioning of the probe unit a given distance from the outlet end. Due to an offset of the probe from the clamped length of the arm, the rotational orientation of the arm may be used to position the probe transversely relative to the outlet.
[0038] In operation, the shockwave passes downstream over the nose, and along the body aft portion 178 . When the shockwave reaches the port 212 , its effects can pass along the path 210 to the pressure transducer that in turn provides an output signal indicative of the pressure magnitude of the shockwave. The probe assembly is initially positioned so that the probe unit is at a predetermined location relative to the combustion tube outlet. This may be performed while the outlet is disengaged from the furnace. Thereafter, the outlet may be inserted into the furnace, and the reaction strap or other restraints installed. The firing process may then be initiated.
[0039] One or more embodiments of the present invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, the invention may be adapted for use with a variety of industrial equipment and with variety of soot blower technologies. Aspects of the existing equipment and technologies may influence aspects of any particular implementation. Accordingly, other embodiments are within the scope of the following claims. | Pressure probe methods and apparatus are disclosed. An exemplary probe includes a body having an exterior surface with a forwardly-convergent nose. A passageway extends between a first port in the body and a pressure sensor. A support member holds the body in an operative position. A cooling fluid circuit extends at least partially through the support member and body. The pressure probe may be used in conjunction with a detonative cleaning apparatus. | 5 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. Ser. No. 07/859,969 filed Mar. 30, 1992, now U.S. Pat. No. 5,307,951.
FIELD OF THE INVENTION
The invention relates to metal pots and pans, containers and/or lids, intended particularly for use as cooking utensils. The metal utensils are formed into a utensil system as a result of their specific shaping.
BACKGROUND OF THE INVENTION
Cooking utensils are generally multipurpose utensils and must therefore have a wide spectrum of characteristics. Particular significance is attached to characteristics such as the chemical and mechanical resistance of the surface, safe and easy handling (ergonamy) so as to keep accident risks low when cooking, together with the shape of the utensil adapted to the particular cooking function and the ease of cleaning. Significance is also attached to the thermal characteristics (material and material combinations) of such a utensil and finally robustness and, at the same time, low weight. It is to be assumed that all these characteristics cannot be combined in optimum manner in a single utensil and therefore every utensil is to a certain extent a compromise.
Cleanness or hygiene requirements dictate that such utensils should not have points such as joints on and around handle and grip attachments which are difficult to clean. Normally such grips are attached to the outer wall of the utensil either by rivets or by a soldered/welded joint. In many cases the handles are a relatively limited distance above the heat source, so that they can easily become heated. Utensils used in commercial kitchens are not thermally insulated at the handles, so that such insulating materials cannot suffer as a result of the heat or the rough handling in such kitchens. Such vessel handles are bulky and do not allow space-saving stacking of the cooking utensils. This makes difficult or even impossible bain marie or double boiler cooking with cooking utensils of different sizes fitted in one another.
SUMMARY OF THE INVENTION
A metal utensil having handles not suffering from such disadvantages and also having further advantages would be desirable and is brought about by the invention described hereinafter.
The invention shows how a metal utensil with hand grips or handles shaped out of the marginal part of the utensil can be manufactured in a simple, material-saving manner. Such a utensil can be used in a much more universal manner than conventional cooking utensils.
Information already exists on the provision of vessel handles mainly on non-metallic cooking utensils, but in the case of metallic utensils this has not proved successful for different reasons. Thus, German Utility Model G 90 01 134.1 discloses a utensil having a shaped-on rim, which cooperates with the lid and which is also constructed for grasping and picking up. These vessels are made from ceramic, glass or plastic and are mainly intended for use in microwave equipment. A similar construction is disclosed in WO 90/09133 of the same Applicant, namely a metal cooking utensil, but the shaped-on part only serves as a pouring rim or edge. For handling purposes such utensils have the usual vessel grips or handles. This utensil also cooperates with the lid so as to allow a better pouring off of a boiling product.
In neither case is there a shaped on vessel handle, although it would lead to considerable advantages. With such a handle in the case of metal utensils the aforementioned disadvantages would be avoided and additional advantages obtained. Importance is also attached to the stability of the utensil, particularly the container, whose strength in the hot and cold state and during loading through handling when cooking must always be adequate. However, this cannot be brought about by the utensil or parts therefor being made from very thick sheet metal in order to ensure such strength. For example with stainless steel, the disadvantages would be the poor thermal conductivity and high weight, whereas in the case of light metal the limited strength and the surface unprotected against discoloration and oxidation are disadvantages. In this connection the invention uses for the entire cooking utensil a laminated material whose structure corresponds to the bottom parts of conventional stainless cooking utensils. The laminated materials can be constituted by relatively thin, stainless steel sheets combined with a good heat conducting metal, e.g., aluminum in a thickness with which the strength deficiency of thin steel sheets is compensated. The resulting improved heat distribution not only extends to the bottom part, but to the entire surface of the cooking utensil. In this way a fully encapsulated system utensil is obtained.
This leads to the two advantages of a good heat distribution through the core material, e.g. aluminum and increased strength resulting from the plating of thin, stainless sheets. As a result of its strength, this makes it possible to shape random handles and grips from the utensil edge or rim allowing the special shaping of the handle attachments for a system utensil with e.g. improved stackability, reciprocal usability, e.g., bain marie cooking and more universal utility e.g. as a steaming, sieving or pouring vessel. Through shaping and using heat distributing laminated materials, local overheating within the vessel is virtually impossible. As the laminated material is characterized by high strength, the handles can be extended further outwards, so that they are positioned outside and well above the heat source and do not get in the way when fitting the vessels in one another.
BRIEF DESCRIPTION OF THE DRAWINGS
the invention is described in greater detail hereinafter relative to non-limitative embodiments and the attached drawings, wherein:
FIGS. 1A-1D show the steps of a basic manufacturing process of a metal utensil according to the invention;
FIG. 2A is a side elevation in partial section of a fully encapsulated utensil, namely a container and a matching lid;
FIG. 2B is a sectional view of a further embodiment of handles for the utensil of FIG. 2A seen in the direction of the center of the container;
FIG. 3 is a top plan view of the utensil of FIGS. 2A and 2B;
FIG. 4 is a top plan view of four containers placed in one another, the rested containers having different diameters and circularly displaced handles;
FIG. 5 is a partial side elevation of the handles of the stacked containers according to FIG. 4 showing the characteristic nature of such a utensil system;
FIG. 6 is a partial side elevation, in partial section, showing the cooperation between the container and lid, the latter being raised;
FIG. 7 is a view similar to FIG. 6 showing the cooperation between the container and the lid, the latter being kept flat, which gain shows the system character of the utensil; and
FIG. 8 is a schematic representation based on FIGS. 5, 6, and 7 of the possibility of vertical variations, made possible by the shaping of the handle attachments on the vessel rim.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1A and 1B show a sequence of steps involved in the formation of a material, in this case a laminated material (FIG. 1A), which comprises a good heat conducting core material 2 and thin stainless steel 1 bonded to either side of the core. The laminated material is cut to size as a square plate (FIG. 1B) and is deep drawn in this form. The deep drawn part (FIG. 1C) with the still uncoated rim 5 and the vessel interior 3 appears from above in the manner shown in FIG. 1D. The drawn-in profile line 6 illustrates the subsequent cutting of the edge or rim of the vessel, together with the handle attachments. The waste 8 resulting from the cutting operation is smaller by the material of the surfaces for the handle attachments 12 than with conventional circular vessels. Fundamentally such a container can also be used as a lid (raised lid) or in other words, with respect to the shaping, a lid is manufactured in the same way as the vessel. From the shaping standpoint, there need be no difference between the lid and the container of a utensil according to the invention. Laminated materials are used for the manufacture of the vessel parts of the utensil, whereas, although this is not prescribed, the lids are generally made from a single-layer material.
The preliminary product for the manufacture of a utensil according to the invention is characterized by its special shaping, the handle attachments 12 being subsequently shaped as part of a vessel blank. The blank in this example comprises a laminated material consisting of three layers, namely outer layers 1 (surface layers) and a central layer 2 positioned between them (heat conducting layer). The surface layers are preferably made from a material which optimally meets the surface requirements and the heat conducting layer is made from a material which optimally meets the heat storage and distribution requirements. These individual layers are combined by a known process to form a starting material. The surface layers are combined by a known process to form a starting material. The surface layers can be made from high-quality steel which, as a thin sheet in the cooking utensil, externally and internally protects the surface, whereas the heat conducting layer can be made from a good heat conducting material, e.g., aluminum which, as a correspondingly thicker sheet in the cooking utensil, stores and distributes heat. Compared with aluminum, high-grade steel is a poor heat conductor if it were used in a thickness which would give the utensil the necessary stability to enable the shaping of handles on the marginal portion of the utensil and the uniform heat distribution in the utensil would be inadequate and the weight too high. On the other hand, if this was brought about by heat-storing aluminum only, then the surface characteristics would be inadequate and the utensil would also have a much lower strength than when combined with high-grade steel.
Unlike in the case of cooking utensils with encapsulated bottoms, this cooking utensil is fully encapsulated except for the handles. This can be seen in FIG. 1C which, following a deep drawing process, shows such a fully encapsulated utensil with an interior volume 3. Particular reference is made to the fact that, because the handle attachments are fitted in the corners of the starting material, material can be saved in that there is less waste and no additional material is required for the handle fixing fittings, which saves cost in view of the expensive starting material. As a result of the shaping of the handle attachments 12 (FIGS. 2A and 3) on the blank, during the subsequent processing to the finished product, it is possible to economize certain operations serving solely a handle fitting function. Thus, this measure leads to a cooking utensil requiring less material and labor costs and which also has better characteristics with respect to the utensil geometry and heat balance.
FIG. 2A shows in section such a utensil in the form of a vessel 10 (as the end product) with an engaged, associated lid 15, in which the two handles 4 are fixed to the vessel rim extension 12. Various ways can be used for the shaping of e.g., straight extensions (12 on the left-hand side of the drawing) or bent extensions (12/12'/12 " on the right-hand side of the drawing), to form the handle attachments. There are no limitations with respect to this shaping, in the same way as handles riveted or welded to a similar vessel. Any random configuration can be given. The handle attachments 12 according to the invention must be produced in the same operation as the vessel, but still have the described advantages in spite of the savings. The handle attachments 12 (or 12/12'/12") for the vessel handles 4 are shaped in the same way on the lid, but here without using an encapsulated material.
FIG. 2B shows a special shaping of the vessel handle 4, namely either with a trough-shaped depression or a spherical protuberance, both designated 25. When the handles engage one another, they prevent reciprocal displacement between the lid and the container and space the vessel 10 and lid 15 from one another for forming a pouring and steaming opening. This special shaping (depression/protuberance) can also be fitted on the handle attachments 12, 12' or 12" for fulfilling the same function.
FIG. 3 shows the utensil according to FIG. 2 from above. It can be seen that the shaping for the vessel and the lid can be the same. As the lid dos not have to satisfy the same requirements regarding strength and heat distribution, its shape is mainly a matter of consistency within the system geometry. The logical shaping for system utensil purposes is made apparent by the fact that, when viewed from above, the vessel with or without the lid appears the same.
FIG. 4 shows four vessels fitted into one another, the vessels being of the same type but of different sizes. The individual containers have the external diameters D1 to D4, the handles are designated 12.1 to 12.4 and between the handle attachment 12 and the handle 4 (FIG. 3) no distinction is made at this point. On the top of each handle it is possible to see the depressions 25, in which can be inserted the matching protuberance on the lid handle. This detail has already been discussed in conjunction with FIG. 2B.
These utensils are inserted in one another up to the vessel rim, as is shown in the detail of FIG. 5. FIG. 5 shows a successive projection of the handles of the stacked containers according to FIG. 4, how the latter can be place din one another. The characteristic nature of this utensil system is also readily apparent. Such space-saving stacking would not be possible with handles not fixed to the vessel rim. Numerous further possibilities regarding handling and ergonamy result from these characteristics and can be further extended through the use of such vessels. The space-saving stacking extends to such a extent that the volume of such a utensil set corresponds to the volume of the largest vessel.
FIGS. 6 and 7 show possible constructions of the vessel handles of the vessel and lid in such a way that they can together assume special functions. If the vessel and lid handles are superimposed so that the protuberances 25 are engaged in the depressions 25, the lid rim is raised from the vessel rim. In this position the lid can be tilted about the rotation points formed by the spheres in the depressions 25, so that between the lid and vessel rim on one side a pouring or sieving opening is formed and on the other side a ventilating gap.
FIG. 6 shows an embodiment with a raised lid 15, which is placed on the container 10. From the shaping standpoint the lid 15 can be fundamentally the same as the container 10. As a function of the thermal and/or stability requirement, it is either produced only from a sheet material with shaped-on handle attachments, or from a laminated material in the same way as the container and in this case can be used as a cooking utensil. This fundamental similarity is represented by the same reference numeral 3 for the interior volume of a lid or a container of the utensil. The height of the raised lid can have any chosen dimension and in itself forms a container, because the handle arrangements of the openings of the container and the lid can be the same. As regards shaping there is no significant difference between the container and the lid, the materials to be used for production differing only as a result of the different uses.
FIG. 7 shows an embodiment with a flat lid 15 of in other words with a smaller interior volume 3. In this form the lid can scarcely be used as a container and it is usually only made from a single sheet (not laminated material) with shaped-on handle attachments. However, here again there is symmetry at the container opening as a result of the shaping as a system utensil.
Both lid embodiment of FIGS. 6 and 7 have the same handle requirements. The spherical protuberance 25 on the underside of the lid handle 4 and the trough-shaped depression 25 on the top of the vessel handle permits engagement of the lid in a raised position with respect to the container, so that as a result of a lid tilting movement on one side a pouring and sieving opening is formed, while on the other side a ventilation gap is formed. This is only possible because the handles are directly fitted to the marginal part of the utensil and are consequently arranged with the correct relationship to the lid handles. It is also apparent that the vessel handles on the upper vessel rim or the marginal part of the vessel are precisely in the correct location for obtaining numerous advantages. If the handles are not superimposed, then the cooking vessel is sealed by the lid resting directly on the vessel rim.
If the lid shaping, in the manner showing in FIG. 2A, is chosen in such a way that the lid surface 15 is constructed as a plane, it becomes possible to place on such a lid a second cooking vessel for keeping the second vessel hot and for energy saving purposes. This is once again only possible because the lid handles and also the vessel handles are located on the marginal portion and there is no centrally positioned lid grip.
As is showing by the reference numeral 16 in FIG. 3 and in the section of FIGS. 6 and 7, lids constructed in a plane can be provided with uniformly arranged, downwardly directed troughs 16, which on the one hand stabilize the lid plane and on the other allow the uniform dripping off over the cooking product of water of condensation formed during cooking.
FIG. 8 shows vertical variations (i.e. handle attachment shapings for varying the height of the handles with respect to the vessel rim with one or more steps) of shaped handle attachments, making it possible to vary the reciprocal functions of the utensil parts between individual vessels (bain marie cooking) and between the vessel and the lid (cooking/pouring), etc. The vessel wall 10 with the handle attachment 12 and the handle extension 12' and 12" are shown in FIG. 8 in different steps S1 to Sn on the vertical V according to which the handle part can be shaped.
Thus, two vessels 10 can differ as regards diameter and as regards the shaping of the handle attachments 12, 12' and 12" and the handle heights S 1 to S n . If the smaller vessel with the lower surface of the handle 4 rests on the upper surface of the larger vessel handle 4, a gap is formed between the bottom surfaces of the vessels, which e.g. one of the positions for bain marie or double boiler cooking. If two vessels of different diameters with reciprocally displaced handles are placed in one another so that the handles are no longer superimposed, then the smaller container with its handle attachment 12 would rest on the rim of the larger vessel, so that the vessel bottoms would be spaced by the height difference between the two vessels. This would represent the stacking position with the maximum stacking density (cf. also FIG. 5) and also a further position e.g. for bain marie cooking. The vessel-lid matching or coincidence e.g., makes it possible to turn around the utensil in the manner showing in FIG. 6, so that the lid functions as a flat vessel and the previous vessel function s as a deeply curved lid. From the use standpoint it would constitute, for example, a poultry cooking means. In this way, on the one hand with the shaping of the handle attachments on the vessel rim and on the other with the variation of the handle shaping, from the utensil according to the invention is developed a significantly extendable system utensil, which is subject to numerous variations and uses. Together with the laminated material further additional advantages are obtained, which further extend the system content.
It can be seen that the special shaping, the special arrangement of the handles or grips, the choice of materials (thermal and strength characteristics), as well as the cooperation between the different vessel and lid parts lead to a universal cooking utensil system. It has wider uses than conventional utensils, as is apparent from a comparison of standard functions such as the interaction of the container and the lid, e.g. for pouring, sieving or steaming, or the fitting into one another of two containers for bain marie cooking, which is readily possible as a result of the special container design and the improved stability of such vessels, which are very space-saving with regards storage, transportation (packing) and in the kitchen. The aforementioned measure leads to all these characteristics. | A metal utensil with handles shaped onto the marginal portions thereof can be manufactured in a simple, material-saving manner. Such a utensil can be used in a more universal manner than conventional utensils. A utensil usable as either a container part (10) and/or a lid part (15), has handles (4) for holding the utensil with a handle attachment (12) shaped onto the rim of the opening to which a handle is connected. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
DESCRIPTION OF ATTACHED APPENDIX
[0003] Not Applicable
BACKGROUND OF THE INVENTION
[0004] This invention relates generally to the field of measuring tools and more specifically to an apparatus for measuring surface (step) height or depth against another surface. Measuring tools are vital in the industrial work place. Engineers, machinists, and technicians rely on a variety of measuring tools to complete jobs. These workers need multiple tools to complete a complex or even simple measurement. Such daily tasks require many measurements, thus creating a lengthy and cumbersome process. This process is unwieldy but has become an accepted norm for each profession to carry out their jobs successfully. Measuring tools have advanced over time and professionals rely on specific tools to give them accurate readings when completing jobs. There are two well known measuring tools for measuring step height or depth against another surface that are necessary in the work place. To measure the height of an object a user must use a height gauge. To measure the depth of a channel, the user must use a depth micrometer. Another widely acceptable method is the use of two scales: one laid across the surface as a straight edge and one held perpendicular to the straight edge. Each of these tools or methods are fundamental to the professionals who measure step heights or depth on a daily basis.
[0005] The prior technology is deficient because these tools cannot measure both the height and depth of a surface. The height gauge measures only the height of an object and is recommended to be used on a surface plate. The depth micrometer only measures depth. In all prior technology, the user must use both hands to successfully use these measuring tools. The tools are too large to be carried in a user's pocket and too unsteady to be used with one hand due to their awkward shape and large size.
BRIEF SUMMARY OF THE INVENTION
[0006] An apparatus that accurately measures the difference in the height or depth of two adjacent surfaces. The apparatus has a compact size and can be held in one hand. The apparatus is portable, lightweight and can be carried in a user's pocket. The measuring apparatus enables a user to quickly and efficiently measure the difference in the height and the depth of two adjacent surfaces. In accordance with one embodiment of the invention, there is disclosed an apparatus for measuring a surface height or depth against another surface comprising: a measuring arm mounted to a backing plate and positioned horizontally to a scale which has a beveled end allowing precise readings of surface heights and depths regardless of whether or not the apparatus is held perpendicular to the surface being measured. Replaceable measuring arms with various reaching capabilities are provided for attaching to the backing plate, and a handle mounted to one end of the scale allows the apparatus to be operated easily with one hand.
[0007] The present invention relates to an apparatus for measuring height differences between a first and second surface comprising a scale having opposed ends, a display unit assembly configured to have a sensor and slide along the scale between the ends, a measuring arm mounted horizontal to the scale; and a handle connected to one end of the scale enabling one handed operation.
[0008] The apparatus has a measuring arm, which has a beveled end. In one embodiment, the scale has a beveled end opposite the handle. The handle has an upper portion with a slot with a circular lower portion to allow for easier handling. The scale is mounted in the slot in the upper portion of the handle. The present invention also relates to a method of measuring the difference in height between a first and second surface which comprises the steps of: providing an apparatus including a scale having opposed ends, a display unit assembly configured to slide along the scale between the ends and having a sensor, a measuring arm horizontal to the scale, and a handle at one end of the scale enabling one handed operation, positioning the end of the scale opposite the handle on the first surface, moving the display unit assembly along the scale until the measuring arm contacts the first surface, zeroing out the display unit assembly, positioning the end of the scale opposite the handle on the first surface adjacent the second surface so that the measuring arm is positioned adjacent the second surface, and moving the measuring arm toward the second surface until the tip of the measuring arm contacts the second surface. The measuring arm is easily removable to allow replacement with a different measuring arm having different capabilities. Other objects and advantages of the present invention will become apparent from the following descriptions, taken in connection with the accompanying drawings, wherein, by way of illustration and example, an embodiment of the present invention is disclosed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] 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.
[0010] FIG. 1 is a perspective view of one embodiment of the step gauge 10 shown after taking a measurement of a step D in a block X.
[0011] FIG. 2 is a perspective view of the step gauge 10 showing it held by a middle finger M against the palm of the user's hand H.
[0012] FIG. 3 is an exploded view of the step gauge 10 .
[0013] FIG. 4 is an exploded view of the display unit assembly 12 .
[0014] FIG. 5 is a front plan view of the step gauge 10 .
[0015] FIG. 6 is a side plan view of the step gauge 10 .
[0016] FIG. 7 is a back plan view of the step gauge 10 .
[0017] FIG. 8 is a plan view of the step gauge 10 showing a second embodiment of a measuring arm 50 A.
[0018] FIG. 9 is a plan view of the step gauge 10 showing a third embodiment of a measuring arm 60 A.
[0019] FIG. 10 is a perspective view of another embodiment of the step gauge 10 showing use of the measuring arm 50 A.
[0020] FIG. 11 is a perspective view of another embodiment of the step gauge 10 shown after taking a measurement of a panel P in relationship to a checking fixture gauge G.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] Detailed descriptions of the preferred embodiment are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure or manner.
[0022] The step gauge 10 is a bidirectional linear measuring apparatus that allows for measuring the difference in heights between two adjacent surfaces. The step gauge 10 can be positioned on either surface 101 or 102 to measure the height or depth of the adjacent surface 101 or 102 with respect to the other surface. In one embodiment, the first and second surfaces 101 or 102 are formed in a united piece ( FIG. 1 ). In another embodiment, the first and second surfaces 106 and 105 are two separate pieces ( FIG. 11 ).
[0023] The step gauge 10 includes a display unit assembly 12 : which is similar in appearance to, and functions the same as those found on conventional digital read out calipers, a measuring arm 26 A, a scale 25 A and a handle 23 A.
[0024] Turning now to the drawings, FIG. 1 illustrates one embodiment of the step gauge 10 of this invention after a step height measuring or reading of the adjacent surfaces 101 and 102 of the block X. By way of illustration, the step gauge 10 is shown being held and operated by the user with only one hand. In one embodiment, the scale 25 A is approximately 4.5″ (114 mm) in length. The length of the scale 25 A allows the step gauge 10 to be operated with one hand.
[0025] FIG. 2 shows how the step gauge 10 and more specifically, the handle 23 A of the step gauge 10 is held with one hand. To hold and use the step gauge 10 properly, the middle finger M is wrapped around the handle 23 A as the index finger F and the thumb T slide the display unit assembly 12 along the scale 25 A.
[0026] In accordance with the present invention, FIG. 3 shows an exploded view of the step gauge 10 . The step gauge 10 includes a display unit assembly 12 , which includes a back plate 31 A having a center groove 31 B with a gib slider 30 inserted on one side of a groove 31 B. The display unit assembly 12 also includes a display unit face 20 A having a linear sensor strip 20 B on the backside, which is connected to a digital, read out 20 C. A battery 21 powers the linear sensor strip 20 B and the digital read out 20 C. The battery 21 is mounted in a slot on the front side of the display unit face 20 A and is covered by a battery cover plate 22 . Using back plate screws 29 A- 29 D the display unit face 20 A is mounted on the back plate 31 A so that the backside of the display unit face 20 A and the groove 31 B of the backplate 31 A form an opening through the display unit assembly 12 . The linear sensor strip 20 B is located in the opening. The scale 25 A has an essentially rectangular shape with opposed ends 25 C and 25 E with a scale sensor strip 25 D located on a top surface of the scale 25 A between the ends 25 C and 25 E. The scale 25 A has a longitudinal axis A-A formed by the ends 25 C and 25 E of the scale 25 A ( FIG. 3 ). With the gib slider 30 in position, the display unit assembly 12 is mounted on the scale 25 A so that the scale 26 A extends through the opening in the display unit assembly 12 such that the scale sensor strip 25 D located on the top surface of the scale 25 A is adjacent to the linear sensor strip 20 B in the display unit face 20 A. The handle 23 A is positioned at one of the ends 25 E of the scale 25 A. The handle 23 A has a circular lower portion and a semi-circular upper portion. The upper portion has a slot 23 B. The scale 25 A is mounted into the handle slot 23 B in the upper portion so that when the back plate 31 A is moved along the scale 25 A, the back plate 31 A is spaced apart from the lower portion of the handle 23 A. The handle 23 A is secured to the scale 25 A by setscrews 24 A- 24 B. The scale 25 A extends outward from the front of the handle 23 A parallel and spaced apart from the lower portion of the handle 23 A. The back of the handle 23 A, opposite the scale 25 A, has a smooth and curved outer surface to allow for easier handling. The handle 23 A is durable, ergonomically correct and lightweight. In one embodiment, the handle weighs less than one ounce for easy handling. In FIG. 6 , the clearance between the handle 23 A and the scale 25 A allows the step gauge 10 to be hung or clipped onto a pocket or a pocket protector. The step gauge 10 can be carried in the user's hand. The compact size and shape of the handle 23 A allows for a secure grip while using the step gauge 10 for measuring awkward or difficult to reach places. For the purpose of handling the step gauge 10 with one hand, the back of the handle 23 A, shown in FIG. 7 , has a circular shape allowing for a comfortable and sturdy grip in the user's hand.
[0027] The measuring arm 26 A is mounted on the back plate 31 A horizontal to the scale 25 A. In one embodiment the measuring arm 26 A is mounted on the backplate 31 A using a measuring arm screw 28 and measuring arm dowel 27 ( FIG. 3 ). In one embodiment, ( FIG. 6 ) the measuring arm 26 A has a beveled end 26 B and the scale 25 A has a beveled end 25 B. The tips 26 C and 25 C of the beveled ends 26 B and 25 B enable the user to obtain precise height and depth readings regardless of whether or not the step gauge 10 is perpendicular to the surface on which the scale 26 A is positioned during measuring.
[0028] It is a feature of the step gauge 10 that the measuring arm 26 A is exchangeable. FIGS. 8 and 9 show two variations of exchangeable measuring arms 50 A and 60 A that can be used. The exchangeable measuring arms 50 A and 60 A have a first end and a second end with a first portion adjacent the first end and a second portion adjacent the second end. The first portion is essentially perpendicular to the second portion. The exchangeable measuring arms 60 A and 60 A are mounted at the first end to the display unit assembly 12 . The first portion of the exchangeable measuring arms 60 A and 60 A extend outward from the display unit assembly 12 essentially perpendicular to the display unit assembly 12 . The second portion of the exchangeable measuring arms 50 A and 60 A extend outward from the first portion in a direction away from the handle 23 A. However, there are several measuring arms that can be exchanged and attached. The exchangeable measuring arms, 50 A and 60 A, have a range in lengths between the ends 60 B and 50 D and 60 B and 60 D and a range of clearances between the scale 26 A and the inside of the arm 50 C and 60 C. These exchangeable measuring arms 60 A and 60 A have multiple reaching capabilities for different spacing or obstructions between the surfaces. FIG. 10 shows one embodiment of the step gauge 10 with the exchangeable measuring arm 50 A after having just taken a measurement over obstruction 203 to obtain the height differences of surfaces 202 and 201 of block Y. FIG. 11 illustrates the step gauge 10 after measuring the height difference of the surface 105 of an automotive panel P and the surface 106 of a checking fixture gauge G. FIG. 11 shows that the step gauge 10 can measure adjacent surface height differences where the surfaces are spaced apart and not connected such that the height of one surface is not dependent on the height of the adjacent surface.
[0029] In use
[0030] To measure height as seen in FIG. 1 , place the tip of the scale 25 C on the first surface 102 and move the display unit assembly 12 toward the first surface 102 until the tip of the measuring arm 26 C touches the first surface 102 . Then, zero out the display unit assembly 12 . Next, position the tip of the scale 25 C beside the step D being measured so that the measuring arm 26 A extends beyond the first surface 102 and is above the second surface 101 . Move the display unit assembly 12 toward the second surface 101 until the tip of the measuring arm 26 C contacts the second surface 101 . As the display unit assembly 12 moves along the scale 25 A, the linear sensor strip 20 B calculates the distance the display unit assembly 12 travels along the scale sensor strip 25 D. The digital readout 20 C will then read the correct height of the second surface 101 with reference to the first surface 102 . To measure height differences around an obstruction as seen in FIG. 10 , replace the measuring arm 26 A with a greater reaching arm 60 A and repeat the previously explained steps. Measuring the height difference between two spaced apart and disconnected surfaces ( FIG. 11 ) would be similar to that described above for measuring the height differences of two surfaces that are part of a unitary piece ( FIG. 1 and FIG. 10 ). While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. | An apparatus for measuring step height or depth against another surface with a measuring arm mounted horizontally beside the scale which has a beveled end allowing precise readings regardless if the apparatus is being held perpendicular, the apparatus has exchangeable measuring arms with various reaching capabilities, and a handle mounted to the top of the scale allowing the apparatus to be operated with one hand. A preferred embodiment includes the apparatus at four to five inches in length whereas an operator is able to measure height and depth in difficult to reach places. In one embodiment, the measuring arm is stainless steel and has longer measuring arms, the handle is made of any resilient material which allows the apparatus to be carried securely in one hand, pocket and or stored easily due to its small size, the apparatus disassembles for cleaning. | 6 |
This application is a continuation of U.S. Ser. No. 07/243,481, filed Sep. 12, 1988, now U.S. Pat. No. 4,956,673, which in turn is a continuation of U.S. Ser. No. 07/029,354, filed Mar. 23, 1987, now U.S. Pat. No. 4,814,823, which in turn is a continuation of U.S. Ser. No. 06/727,859, filed Apr. 26, 1985, and now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to an image forming apparatus capable of developing a copy image on a copy paper sheet, in a single cycle of its copying operation, using a developing agent of any desired color, and more specifically relates to an imaging-forming apparatus, such as a color copying machine, in which developing agents of different colors are used individually in a plurality of cycles of its copying operation, repeated for a single sheet of copy paper, thereby permitting multicolor copying.
Development of color versions has recently been promoted in the field of copying machines. For example, two-color copying machines have been developed for practical use, which can produce color images enjoying another color as well as black. In the conventional color copying machines of this type, however, developing agents of different colors are used individually in a plurality of cartridges which each include a developing unit and a photosensitive member in integral relation. A plurality of color copying operations are performed by alternatively replacing the cartridges with one another. Thus, the prior art color copying machines require a troublesome series of operations.
SUMMARY OF THE INVENTION
The present invention has been developed in consideration of these circumstances, and is intended to provide an image-forming apparatus which, in a selected image-forming mode, can form an image with a plurality of colors (including a standard color), without replace cartridges including development units.
According to one aspect of the present invention, there is provided an image-forming apparatus which comprises a housing; an image carrier located in the housing and adapted to carry thereon a latent image corresponding to an original image-developing means for developing the latent image formed on the surface of the image carrier, the developing means including first developing means for developing the latent image by means of a first developing agent, and second developing means for developing the latent image by means of a second developing agent-and means for alternatively driving the first and second developing means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view schematically showing a color copying machine, as one embodiment of an image-forming apparatus according to the present invention;
FIG. 2 is a vertical sectional view schematically showing a developing device;
FIG. 3 is a vertical sectional view schematically showing the developing device of FIG. 2 in a different mode;
FIGS. 4, 5 and 6 show the arrangements of driving force transmission systems in which FIG. 4 is a front view showing engagement between a group of gears; FIG. 5 is a sectional view showing the group of gears; and FIG. 6 is a sectional view showing the way a driving force is transmitted to a driving gear;
FIG. 7 is a plan view, partially in section, showing a magnet roll drive mechanism;
FIG. 8 is a side view of the magnet roll drive mechanism;
FIGS. 9A and 9B are side views showing the magnet roll drive mechanism in different positions;
FIG. 10 is a perspective view schematically showing the developing device;
FIGS. 11A and 11B are top views individually showing a pair of developing units;
FIG. 12 is a front view showing means for affixing the developing device;
FIGS. 13A, 13B and 13C are front views showing a handle and a hook in different relative positions;
FIG. 14 is a plan view of a control panel;
FIG. 15 is a block diagram schematically showing a general control circuit;
FIG. 16 is a diagram for illustrating developing unit presence signal generating mechanisms and discriminating information generating mechanisms;
FIGS. 17A to 17F are flow charts for illustrating an operation mode at the start of power supply;
FIGS. 18A to 18D are flow charts for illustrating a copy mode; and
FIGS. 19A and 19B are flow charts for illustrating an automatic interruption mode.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
One embodiment of an image-forming apparatus according to the present invention, applied to an electronic copying machine, will now be described in detail with reference to the accompanying drawings.
FIG. 1 shows a two-color copying machine, as an example of the image-forming apparatus of the present invention. In FIG. 1, numeral 1 designates a copying machine housing. The housing 1 carries thereon an original table 2 which can reciprocate in the longitudinal direction of the housing 1 as indicated by arrow a. A paper cassette 3, storing stack of copy paper P1 and a receiving tray 4 are removably attached to the right- and left-hand side portions of the housing 1, respectively. A cassette cover 5 is provided on the top of the paper cassette 3. The top surface of the cassette cover 5 serves as a sheet-bypass guide 6 for copy paper sheets P2, to be manually supplied as required. A photoconductive drum 7 is located in the substantially central portion of the housing 1, so as to be rotatable in clockwise direction a as indicated by arrow b. The photoconductive drum 7 is surrounded by a main charger 8, an optical system 9, a two-color developing device 10 (described in detail later), a transfer charger 11, a separation charger 12, a cleaning unit 13, and a discharge lamp 14, which are arranged successively in the rotational direction of the drum 7. At the lower portion of the housing 1 extends a paper conveying path 17, along which a paper sheet P1 (automatically delivered from the paper cassette 3 by a paper-supply roller 15) or a paper sheet P2 manually) supplied through the sheet-bypass guide 6) is fed and discharged into the receiving tray 4, through an image transfer section 16 defined between the photoconductive drum 7 and the transfer charger 11. A pair of aligning rollers 18 are arranged in the paper conveying path 17, on the upper-course side of the image transfer section 16 with respect to the direction of paper feed, and a pair of heat rollers 19, constituting a fixing unit, and a pair of exit rollers 20 are arranged on the lower-course side.
The optical system 9 includes an exposure lamp 22 backed by a reflector 21, mirrors 23, 24, 25, and 26, and a lens 27.
The photoconductive drum 7 is driven, in the direction indicated by arrow b, by a drive mechanism (not shown), in synchronism with the reciprocation of the original table 2. In operation, the surface of the photoconductive drum 7 is first charged uniformly by the main charger 8. Then, an original is uniformly irradiated by the exposure lamp 22 and the reflected light from the original is projected on the photoconductive drum 7 by the optical system 9, forming an electrostatic latent image thereupon. The electrostatic latent image formed in this manner is developed into a visible image by the developing device 10, and placed opposite the transfer charger 11.
The automatically or manually supplied sheet P1 or P2 is fed into the image transfer section 16 by the aligning rollers 18, timed to the formation of the visible image. In the image transfer section 16, the toner image previously formed on the photoconductive drum 7 is transferred to the surface of the sheet P1 or P2, by the transfer charger 11. Then, the sheet P1 (P2) with the transferred toner image thereon is separated from the photoconductive drum 7 by the separation charger 12, and delivered to the heat rollers 19, through the paper conveying path 17. After the transferred image is melted and fixed on the sheet P1 (P2) by the heat rollers 19, the sheet P1 (P2) is discharged into the receiving tray 4 by the exit rollers 20.
After the toner image is transferred to the surface of the sheet P1 (P2), the residual developing agent remaining on the photoconductive drum 7 is removed by the cleaning unit 13, and a any residual image on the photoconductive drum 7 is erased by the discharge lamp 14, so as to be ready for the next cycle of the copying operation.
Inside the housing 1, upper and lower frames (not shown) are pivotally mounted at one end portion, on a supporting shaft (not shown). With this arrangement, the other end portions of the two frames can be swung apart at a desired angle i.e., up to about 30 degrees from each other.
The upper frame is fitted by suitable means, with the photoconductive drum 7 and the other devices surrounding the same, including the main charger 8, the optical system 9, the exposure lamp 22, the developing device 10, the cleaning unit 13, and the discharge lamp 14. The upper frame is further mounted with the original table 2 and the paper-supply roller 15, thus constituting an upper unit 1a. On the other hand, the lower frame is fitted by suitable means with the paper cassette 3, the transfer charger 11, the separation charger 12, the heat rollers 19, the exit rollers 20, the receiving tray 4, and a main motor 28, thus constituting a lower unit 1b. Therefore, the paper conveying path 17 can be substantially fully exposed by removing a front cover (not shown) and then swinging the upper unit 1a upward from the lower unit 1b, by releasing a housing lock device (not shown).
The cleaning unit 13 is provided with a blade solenoid 29 for causing a cleaning blade 30 to make contact with and withdraw from the photoconductive drum 7.
The construction of the developing device 10 will now be described in detail.
As shown in detail in FIG. 2, the developing device 10 includes first and second developing rollers 31a and 31b, which are alternatively driven for regular developing using black as a standard color, or color developing using a color other than black, such as red, yellow, blue, or green.
The developing device 10 is vertically divided into two parts, a first developing unit 32a including the first developing roller 31a, and a second developing unit 32b including the second developing roller 31b. Both the first and second developing units 32a and 32b can be removably set in the housing 1. In this embodiment, the first or upper developing unit 32a is constructed so that a user can easily draw it out upward from the housing 1, while the second or lower developing unit 32b is designed for a serviceman's lateral attachment for detachment for maintenance or inspection. A black developing agent G2, in greater demand, is used in the second developing unit 32b, and a color developing agent G1 in the first developing unit 32a.
The first developing unit 32a comprises a developing mechanism section 33a and a developing agent supply section 34a. The developing mechanism section 33a includes the first developing roller 31a; a doctor 37a located on the upper-course side of a developing position 36a or a sliding contact region between the photoconductive drum 7 and a magnetic brush 35a of the color developing agent G1 formed on the surface of the developing roller 31a, whereby the thickness of the magnetic brush 35a is regulated; a scraper 39a located on the lower-course side of the developing position 36a and adapted to scrape off the magnetic brush 35a on the surface of the developing roller 31a and feed it into a developing agent storage portion 38a; a developing agent stirrer 40a in the developing agent storage portion 38a, and a casing 41a containing all these members. A developing agent density detector 42a is attached to that portion of the casing 41a which corresponds to the upper portion of the developing roller 31a. The density detector 42a detects the density of the color developing agent G1, by magnetically sensing a change in the permeability of the developing agent G1.
The developing roller 31a is formed of a magnet roll 43a, whose center lies on a straight line L2 which passes through the center of rotation of the photoconductive drum 7, and is inclined at an angle α (about 51 degrees) to a horizontal line L1, and sleeve 44a, fitted on the outer peripheral surface of the magnet roll 43a and rotating in the clockwise direction of FIG. 2. The magnet roll 43a includes first to fifth polar blocks 45a, 46a, 47a, 48a and 49a. The first, third and fifth polar blocks 45a, 47a and 49a are north poles, while the second and fourth polar blocks 46a and 48a are south poles. The angle θ 1 between the first and second polar blocks 45a and 46a is about 50 degrees, angle θ 2 between 46a and 47a is about 71 degrees, angle θ 3 between 47a and 48a is about 60 degrees, and angle θ 4 between 48a and 49b is about 60 degrees.
The developing agent supply section 34a includes a hopper 51a with a developing agent supply port 50a, facing the developing agent storage portion 38a of the developing mechanism section 33a; a developing agent supply roller 52a in the hopper 51a located so as to close the developing agent supply port 50a; and a pair of stirring rollers 53a for stirring the developing agent G1 in the hopper 51a so that the developing agent G1 is fed to the developing agent supply roller 52a.
The second developing unit 32b has substantially the same basic construction as the first developing unit 32a described above. The former differs from the latter in the shape of a hopper 51b of a developing agent supply section 34b, the arrangement of poles of a magnet roll 43b of the developing roller 31b, the attachment position of a developing agent density detector 42b, and the addition of a narrow scraper 54 (e.g., 50 mm thick) with a tilt of about 20 degrees to cope with the shift of the detector 42b. In the description to follow, like reference numbers, but with a suffix "b" each in place of "a", are used to designate like members as included in the first developing unit 32a, and a detailed description of these numbers is therefore omitted.
The magnet roll 43b of the developing roller 31b includes first to fourth polar blocks 45b, 46b, 47b and 48b. The first and third polar blocks 45b and 47b are north poles, while the second and fourth polar blocks 46b and 48b are south poles. The angle θ 5 between the first and second polar blocks 45b and 46b is about 70 degrees, angle θ 6 between 46b and 47b is about 70 degrees, and angle θ 7 between 47b and 48b is about 80 degrees. The center of the magnet roll 43b lies on a straight line L3 which passes through the center of rotation of the photoconductive drum 7, and is inclined at an angle β (about 1 degree) to the horizontal line L1.
The respective magnet rolls 43a and 43b of the first and second developing units 32a and 32b are allowed to rock through about 25 degrees each. As the magnet rolls 43a and 43b rock within this range, magnetic brushes 35a and 35b of the developing agents can be formed on the surfaces of the developing rollers 31a and 31b, respectively, or removed therefrom. When the magnet rolls 43a and 43b (of the first and second developing units 32a and 32b) are shifted to their prescribed positions by a magnet roll drive mechanism (mentioned later), the magnetic brush 35a and 35b is formed on the surface of only one of the developing rollers 31a and 31b (of the first and second developing units 32a and 32b).
In operating the first developing unit 32a, the magnet roll 43a (of the first developing unit 32a) is set in a position such that the third polar block 47a faces the developing position 36a, and that the doctor 37a is located substantially halfway between the first and second polar blocks 45a and 46b, while the magnet roll 43b(of the second developing unit 32b) is set so that the first polar block 45b faces a doctor 37b, as shown in FIG. 2. Thus, the magnetic brush 35a is formed only on the surface of the developing roller 31a of the first developing unit 32a.
In operating the second developing unit 32b, on the other hand, the magnet roll 43a(of the first developing unit 32a) is rocked clockwise through about 25 degrees from the position of FIG. 2, so that the first polar block 45a faces the doctor 37a, and the magnet roll 43b (of the second developing unit 32b) is rocked counterclockwise through about 25 degrees from the position of FIG. 2, so that the doctor 37b is located substantially halfway between the first and second polar blocks 45b and 46b, as shown in FIG. 3. Thus, the magnetic brush 35b is formed only on the surface of the developing roller 31bof the second developing unit 32b.
When the first polar block 45a (45b) of the magnet roll 43a (43b) is opposed to the doctor 37a (37b) (formed from a non-magnetic material) the magnetic brush 35a (35b) ceases to be formed on the surface of the developing roller 31a (31b) for the following reason. The magnetic brush on that portion of the surface of the sleeve 44a (44b), corresponding to the first polar block 45a (45b), is so sparse that it cannot positively attract the developing agent G1 (G2). Therefore, the formation of the magnetic brush 35a (35b) can easily be controlled by the doctor 37a (37b). Thus, by opposing the first polar block 45a (45b) to the doctor 37a (37b), the developing agent G1 (G2) is prevented from passing, by the doctor 37a (37b), even though the sleeve 44a (44b) rotates.
Driving forces for the moving parts of the first developing unit 32a, including the sleeve 44a of the developing roller 31a, the developing agent stirrer 40a, and the developing agent supply roller 52a, are transmitted by means of a first driving force transmission system 61, which will be described in detail later. Driving forces for the moving parts of the second developing unit 32b, including the sleeve 44b of the developing roller 31b and the developing agent stirrer 40b, are transmitted by means of a second driving force transmission system 62 mentioned later. The first and second driving force transmission systems 61 and 62, as shown in FIGS. 4 to 6, are adapted to alternatively actuate the drive system for one of the first and second developing units 32a and 32b when a reversible motor 63, as a common drive source, is rotated forwardly or reversely.
Referring now to FIGS. 4 to 6, the driving force transmission systems 61 and 62 will be described in detail. The first driving force transmission system 61 includes an intermediate gear 65 in mesh with a driving gear 64, which is driven by the reversible motor 63; a first driven gear 66 in mesh with the intermediate gear 65; an intermediate gear 67 in mesh with the driven gear 66; and a second driven gear 68 in mesh with the intermediate gear 67. The second driving force transmission system 62 includes a third driven gear 69 in mesh with the driving gear 64; an intermediate gear 70 in mesh with the driven gear 69; and a fourth driven gear 71 in mesh with the intermediate gear 70.
When the driving gear 64 is rotated forwardly or in the counterclockwise direction (indicated by full-line arrow A in FIG. 4) by the reversible motor 63, the individual gears 65, 66, 67 and 68 of the first driving force transmission system 61, and the gears 69, 70, and 71 of the second driving force transmission system 62, rotate in the directions indicated by the individual full-line arrows. On the other hand, when the driving gear 64 is rotated reversely or in a clockwise direction (indicated by broken-line arrow B) by the reversible motor 63, the gears 65 to 68 (of the first driving force transmission system 61) and the gears 69 to 71 (of the second driving force transmission system 62) rotate in the directions indicated by the individual broken-line arrows.
The first and second driven gears 66 and 68 are mounted on a driving shaft 72a, integral with the sleeve 44a, and a driving shaft 73a of the developing agent stirrer 40a, respectively, by means of their corresponding one-way clutches 74. The one-way clutches 74 transmit the driving force to the driving shafts 72a and 73a to rotate the same in the direction indicated by the chain-line arrows, only when the gears 66 and 68, in the direction indicated by the full-line arrows, that is, when the driving gear 64 rotates forwardly.
The third and fourth driven gears 69 and 71 are mounted on a driving shaft 72b, integral with the sleeve 44b of the second developing roller 31b, and a driving shaft 73b of the developing agent stirrer 40b, respectively, by means of their corresponding one-way clutches 75. The one-way clutches 75 transmit the driving force to the driving shafts 72b and 73b to rotate the same in the direction indicated by the chain-line arrows, only when the gears 69 and 71 rotate in the direction indicated by the broken-line arrows, that is, when the driving gear 64 rotates reversely.
As shown in FIG. 6, the driving gear 64 is fixedly mounted on a rotating shaft 79 which is rotatably supported by bearings 76, and linked to a driving shaft 78 of the reversible motor 63, by means of a gear mechanism 77. More specifically, a gear 80 is mounted on the rotating shaft 79. The gear 80 is in mesh with a gear 85 which is rotatably mounted, by means of a pair of bearings 84, on a supporting shaft 83 stretched between a motor mounting frame 81 and a stay 82 integral therewith. The gear 85 is integrally formed with a larger gear 86. The gear 86 is in mesh with a gear 87, which is mounted on the driving shaft 78 of the reversible motor 63. Thus, both the forward and reverse rotations of the driving shaft 78 (of the reversible motor 63) are transmitted to the rotating shaft 79, and hence to the driving gear 64, through the gears 87, 86, 85 and 80, so that the first and second developing units 32a and 32b can be alternatively actuated by only changing the rotating direction of the reversible motor 63.
The change of the rotational direction of the reversible motor 63 is accomplished by depressing a color selection key 156 on a control panel, which will be described in detail later. At the same time, the magnet roll 43a or 43b which is not engaged in operation is shifted by the magnet roll drive mechanism (described in detail later), so that its first polar block 45a or 45b faces its corresponding doctor 37a or 37b.
The intermediate gear 65, in mesh with the driving gear 64 and the first driven gear 66, is rotatably mounted on a supporting shaft 89, by means of a bearing 88. The supporting shaft 89 is attached to an arm 91, swingable around a housing 90 for holding the bearings 76, which support the rotating shaft 79. Thus, the intermediate gear 65 can shift its position, so that it may securely engage the driving gear 64 and the first driven gear 66.
One stirring roller 53a of the first developing unit 32a is intermittently driven by a first actuating mechanism 92a shown in FIG. 4. The other stirring roller 53a and the developing agent supply roller 52a are simultaneously driven in association with the rotation of the one stirring roller 53a. A ratchet wheel 94a is mounted on one end of a shaft 93a, of the one stirring roller 53a, of the first developing unit 32a. The ratchet wheel 94a is intermittently rotated by regular angles, regulated by a pawl 97a attached to a swinging arm 96a, which rocks as a solenoid 95a is energized or deenergized. Sprocket wheels (not shown) are fitted individually on the respective shafts 93a and 98 of the pair of stirring rollers 53a, and on a shaft 99a of the developing agent supply roller 52a. A driving chain (not shown) is stretched between these sprockets, thereby constituting a driving force transmission system (not shown). The stirring rollers 53a and the developing agent supply roller 52a are driven together by this driving force transmission system.
A stirring roller 53b and a developing agent supply roller 52b, of the second developing unit 32b, are simultaneously intermittently driven by a second actuating mechanism 92b with the same construction as the first actuating mechanism 92a, as well as by another driving force transmission system constructed in substantially the same manner as the aforesaid one. In FIG. 4, like reference numerals, but with a suffix "b" each in place of "a", are used to designate like members of the second actuating mechanism 92b, as included in the first actuating mechanism 92a.
Referring now to FIGS. 7, 8, 9A and 9B, the construction of a magnet roll drive mechanism 100a will be described, which rotates the magnet roll 43a, to form on or remove the magnetic brush 35a from the surface of the developing roller 31a.
One end of a shaft 101a of the magnet roll 43a is supported by a bearing 103a, which is attached to a frame 102. A lever 104a is attached to the extreme end of the shaft 101a. The distal end of the lever 104a is fitted in an engaging groove 107a of an arm 106a, which is rockably mounted on a supporting shaft 105a. A support portion 108a formed at the lower portion of the arm 106a, on its pivotal end side, is coupled to a plunger 110a of a solenoid 109a. One end of a tension spring 112a is coupled to a support portion 111a, which is formed at the upper portion of the arm 106a on the pivotal end side.
In the arrangement described above, when the solenoid 109a is off, the arm 106a is caused, by the urging force of the tension spring 112a, to hold the lever 104a in a position indicated by two-dot chain lines in FIG. 8, in which the doctor 37a faces the first polar block 45a, as shown in FIG. 9A. Thus, when the solenoid 109a is off, the magnetic brush 35a cannot be formed on the surface of the developing roller 31a. When the solenoid 109a is on, on the other hand, the arm 106a causes the lever 104a to rock against the urging force of the tension spring 112a, to a position indicated by full lines in FIG. 8, in which that portion of the magnet roll 43a halfway between the first and second polar blocks 45a and 46a, faces the doctor 37a, as shown in FIG. 9B. Thus, when the solenoid 109a is on, the magnetic brush 35a is formed on the surface of the developing roller 31a.
A magnet roll drive mechanism 100b for rotating the magnet roll 43b, to form on or remove the magnetic brush 35b from the surface of the developing roller 31b, is constructed in substantially the same manner as the magnet roll drive mechanism 100a described above. In FIGS. 7 to 9B, like reference numbers, but with a suffix "b" each in place of "a", are used to designate like members of the magnet roll drive mechanism 100b as included in the magnet roll drive mechanism 100a.
A solenoid 109b is designed so as to be off and on when the solenoid 109a is on and off, respectively. Thus, the magnetic brush 35a or 35b is alternatively formed on the surface of the first or second developing roller 31a or 31b.
As shown in FIGS. 2 and 3, the doctor 37b includes a doctor body 113b formed of nonmagnetic material, a magnetic member 114 formed of a beltlike iron plate extending along the longitudinal direction of the doctor body 113b, and a pair of magnetic members 115b (only one shown) at either end portion of the doctor body 113b. The magnetic members 114 and 115b and the first polar block 45b form lines of magnetic force between them, to positively prevent the developing agent G2 from being carried away from the hopper 51b, when the first polar block 45b is opposed to the doctor 37b, so that the developing agent G2, on the surface of the developing roller 31b, is removed.
The doctor 37a includes a doctor body 113a formed of nonmagnetic material, and a pair of magnetic members 115a (only one shown) at either end portion of the doctor body 113a. The doctor 37a serves to prevent the developing agent G1 from being carried away, in the same manner as does the doctor 37b. Unlike the doctor 37b, the doctor 37a is not provided with any magnetic member extending along the longitudinal direction of the doctor body 113a. The developing agent G1 is prevented from being carried away from the hopper 51a, by, taking advantage of lines of magnetic force formed between the first polar block 45a of the developing roller 31a, opposite the doctor 37a and the fourth polar block 48b of the developing roller 31b.
As shown in FIGS. 2 and 3, a magnetic plate 116 is interposed between the two developing rollers 31a and 31b. The magnetic plate 116 serves to reduce the influences of the magnetic flux density and polar distribution of the one magnet roll 43a (43b) on the other magnet roll 43b (43a), thereby ensuring satisfactory feed of the developing agents.
As shown in FIGS. 2 and 3, moreover, a developing agent shortage detecting unit 117b is located in the hopper 51b of the second developing unit 32b. The developing agent shortage detecting unit 117b detects reduction of the residual quantity of the developing agent G2, in the hopper 51b, to a predetermined level. The developing agent shortage detecting unit 117b includes a detecting lever 118, adapted to rock in accordance with the residual quantity of the developing agent G2 in the hopper 51b, an actuator 119 integral with the detecting lever 118, a permanent magnet 120 attached to the actuator 119, and a reed switch 121 as a sensor outside the hopper 51b. When the quality of developing agent G2, in the hopper 51b, is reduced, the permanent magnet 120 approaches the reed switch 121 to actuate the same. A developing agent shortage detecting unit 117a (not illustrated in FIGS. 2 and 3), similar to the detecting unit 117b, is located in the hopper 51a of the first developing unit 32a.
As shown in FIGS. 2, 3 and 10, a hopper cover 131, constituting part of the top face of the housing 1, is swingably located on the top side of the developing device 10. When the hopper cover 131 is removed, a lid 133a covering a top opening 132a for developing agent supply of the first developing unit 32a and a lid 133b covering a top opening 132b for developing agent supply of the second developing unit 32b are exposed at the same time. Thus, with the lids 133a and 133b taken off, the developing agents G1 and G2 can readily be supplied from the top side. The lids 133a and 133b are provided with color indicator 134a and 134b, respectively. The color indicators 134a and 134b facilitate discrimination by color between the developing agents G1 and G2 stored in the hoppers 51a and 51b, preventing the developing agents of different colors from being mixed.
In FIGS. 2 and 3, number 135 designates a cover position detecting unit for detecting the state of the hopper cover 131. The cover position detecting unit 135 includes a permanent magnet 136 attached to the front end portion of the hopper cover 131, and a reed switch 137 as a sensor attached to the housing 1, and adapted to be turned on when the hopper cover 131 is shut down, to bring the magnet 136 into contact with the reed switch 137.
As shown in FIGS. 10, 11A and 11B, integrating timers 139a and 139b as life indicators, for indicating the remainder of the life of the developing agents, and developing agent absent indicators 140a and 140b, for indicating reduction in the quantity of developing agents in the hoppers 51a and 51b (of the first and second developing units 32a and 32b) to a predetermined level, are provided on top surface 138a and 138b of the hoppers 51a and 51b, on either side of the lids 133a and 133b. The integrating timers 139a and 139b indicate the remainder of the life of their corresponding developing agents by, for example, measuring the amount of rotation (time) of the sleeves 44a and 44b which constitute the developing rollers 31a and 31b, respectively. In this embodiment, for example, FC Timer (trademark of electrolytic integrating timer produced by Fuji Ceramics Co., Ltd.) is used for the integrating timers 139a and 139b.
The first developing unit 32a, storing the color developing agent G1, is in the form of a cartridge which can be removably set in the housing 1 from the top side thereof. The first developing unit 32a can easily be removed from the housing 1 by raising and drawing up a handle 141 (FIG. 10). A pair of positioning members 142 (only one of which is shown) are attached individually to the front and rear walls of the developing agent supply section 34a of the first developing unit 32a. Both end support portions 144 of the handle 141 are individually swingably mounted on the positioning members 142 by means of supporting shafts 143, individually. As shown in FIGS. 12, 13A, 13B and 13C, each support portion 144 of the handle 141 is fitted integrally with a hook 145 which can rock around its corresponding supporting shaft 143. The hook 145 engages its corresponding retaining pin 146 on the housing 1, thereby restraining the handle 141 from moving upward. An engaging recess 147 as a first positioning portion, and an end face 148 as a second positioning portion, both formed on the bottom side of each positioning member 142, are adapted to engage and abut against positioning pins 149 and 150 on the housing 1, respectively. Thus, the first developing unit 32a is held in a prescribed position.
When the handle 141 is raised, the hook 145 is disengaged from the retaining pin 146, as shown in FIG. 13A. when the handle 141 is brought down to a substantially horizontal position, on the other hand, the hook 145 engages the retaining pin 146, as shown in FIG. 13B. When the handle 141 in the horizontal position is further pressed downward, the hook 145 and the retaining pin 146 engage each other, more securely as shown in FIG. 13C, so that the first developing unit 32a is held down. Thus, when the handle 141 is raised, the first developing unit 32a can be loaded or unloaded from the top side of the housing 1, and when the handle 141 is brought down after the first developing unit 32a is loaded, the first developing unit 32a can be affixed. In conclusion, the setting of the first developing unit 32a is very easy.
The developing operation of the developing device 10 will now be described. If the first developing unit 32a is selected for operation by means of the color selection key 156 shown in FIG. 14, the magnet rolls, 43a and 43b will be situated as shown in FIG. 2. Meanwhile, the reversible motor 63 rotates forwardly, and only the sleeve 44a of the first developing roller 31a rotates clockwise from the position of FIG. 2. As a result, the magnetic brush 35a is formed on the surface of the sleeve 44a. Then, the electrostatic latent image, previously formed on the photoconductive drum 7, is developed by the color developing agent G1. When the developing of the electrostatic latent image is accomplished in this manner, the magnet roll 43a rotates clockwise through about 25 degrees so that the polar block 45a faces the doctor 37a. Thus, the magnetic brush 35a ceases to be formed afresh on the surface of the sleeve 44a. In this state, the sleeve 44a further rotates through a predetermined angle, causing the magnetic brush 35a to be removed from the surface of the first developing roller 31a. At this time, the magnetic brush 35b is not formed on the surface of the second developing roller 31b, either. Thus, color mixing or any other trouble cannot be caused if the first or second developing unit 32a or 32b is selected for the next cycle of operation.
If the second developing unit 32b is selected for black developing operation, by means of the color selection key 156, the magnet rolls 43a and 43b are situated as shown in FIG. 3. Meanwhile, the reversible motor 63 rotates reversely, and only the sleeve 44b, of the second developing roller 31b, rotates clockwise from the position of FIG. 2. As a result, the magnetic brush 35b is formed on the surface of the sleeve 44b. Then, the electrostatic latent image on the photoconductive drum 7 is developed by the black developing agent G2. Thereafter, the magnetic brush 35b is removed from the surface of the sleeve 44b in the same manner as aforesaid, and the developing operation is thus completed.
The developing agent stirrer 40a (40b) and the stirring roller(s) 53a (53b) (of the developing unit 32a (32b)) when engaged in the developing operation, are normally rotating. Meanwhile, the developing agent supply roller 53a (53b) is rotated so that the developing agent G1 (G2) is supplied as required, in accordance with a control signal responsive to an output signal from the developing agent density detector 42a (42b). Thus, satisfactory developing operation can be maintained.
FIG. 14 shows the control panel. The control panel bears thereon a copying key 151 for starting the copying operation; an interruption key 152 for designating an interruption mode for interruption copying; an interruption indicator 153 for indicating the interruption mode, a ten-key array 154 for setting the number of copies to be made, a copy number display 155 for indicating the number of copies made; the color selection key 156 for selecting the copy color (e.g., black, red, blue, green, etc.), color indicators 157, 158, 159 and 160 for indicating the selected color; a liquid crystal display section 161 for indicating the operating mode or state; and a density setting section 162 for setting the copy density.
The liquid crystal display section 161 includes a ready-to-copy sign 163 for indication that the copying machine is ready for copying operation; a do-not-copy sign 164 for indication that the machine is not ready for copying operation, and a developing agent absent sign 165 for an indication that a hopper or hoppers of the developing device 10 have been emptied of the developing agent(s).
Alternative color selection can be accomplished with each successive depression of the color selection key 156. Here let it be supposed that the first and second developing units 32a and 32b store therein the developing agent G1 of, e.g., a red color, and the black developing agent G2, respectively. In this case, when the power supply is turned on, the black copy mode is automatically established, the second developing unit 32b is actuated, and the black color indicator 157 is lighted. If the color selection key 156 is depressed in this state, a red copy mode is established, the first developing unit 32a is actuated, and the red color indicator 158 is lighted. If the color selection key 156 is depressed again in this state, the black copy mode is resumed. Thus, the black and red copy modes can alternately be selected by repeatedly depressing the color selection key 156.
FIG. 15 shows a general control circuit of the copying machine. In FIG. 15, number 171 designates a microcomputer as a main control unit for the control of the copying machine as a whole. The input data of the microcomputer 171 is conveyed through an input interface circuit 172 with input switches 173, including the various keys on the control panel; various other switches and sensors 174 required for copying operation; the developing agent density detector 42a and the developing agent shortage detecting unit 117a of the first developing unit 32a, the developing agent density detector 42b and the developing agent shortage detecting unit 117b of the second developing unit 32b; and the cover position detecting unit 135. Also, the microcomputer 171 is connected directly with a memory unit 175. The memory unit 175 is backed up by a stand by power source 176, such as batteries.
The output data of the microcomputer 171 is conveyed through an output interface circuit 177, with a display unit 178 which includes the various indicators and display sections on the control panel; the pole position-- - --shifting solenoids 109a and 109b of the first and second developing units 32a and 32b; the reversible motor 63 the integrating timers 139a and 139b of the first and second developing units 32a and 32b; a developing bias power source 179; a charging power source 180 for the main charger 8; a transfer power source 181 for the transfer charger 11; a separation power source 182 for the separation charger 12; the discharge lamp 14; the developing agent absence indicators 140a and 140b; the main motor 28; various other solenoids 183; an original table drive mechanism 184 for driving the original table 2; and an exposure lamp control circuit 185. The exposure lamp control circuit 185 controls the exposure lamp 22, in response to an output signal from an automatic exposure sensor 186 for detecting light from the exposure lamp 22, and a signal from the microcomputer 171.
The first and second developing units 32a and 32b are provided, respectively, with developing unit presence signal generating mechanisms 187a and 187b for indicating the presence of the developing units, and discriminating information-- - --generating mechanisms 188a and 188b for producing discriminating codes (indicative of the colors of the developing agents) peculiar to the individual developing units. Signals and discriminating codes from these generating mechanisms 187a, 187b, 188a and 188b are applied to the input of the microcomputer 171, through the input interface circuit 172. The developing unit presence signal-- - --generating mechanisms 187a and 187b and the discriminating information-- - --generating mechanisms 188a and 188b deliver their respective signals and discriminating codes by utilizing developing unit connectors 191a and 191b, as Shown in FIG. 16, for electrically connecting the developing units 32a and 32b, respectively, to the input interface circuit 172.
Each connector 191a (191b) includes a jack 192a (192b) and a plug 193a (193b). The jack 192a (192b) is provided on the developing unit side, while the plug 193a (193b) is connected to the input interface circuit 172 of FIG. 15, by means of a cable. A developing unit presence signal is produced by connecting a common terminal 194 1 with a terminal 194 5 , in the jack 192a (192b). On the other hand, a 3-bit discriminating code is produced by connecting the common terminal 194 1 with any of terminals 194 2 , 194 3 , and 194 4 , depending on the developing unit concerned.
In the plug 193a (193b), a terminal 195 1 is grounded inside the input interface circuit 172. Thus, when the jack 192a (192b) and the plug 193a (193b) are connected, their respective terminals are connected correspondingly. By this connection, a three-bit discriminating code, indicative of the terminal connection of the jack 192, is obtained from terminals 195 2 , 195 3 and 195 4 , of the plug 193, and a "developing unit present" signal is obtained from a terminal 195 5 . When the jack 192 and the plug 193 are not connected, therefore, the "developing unit present" signal cannot be delivered from the terminal 195 5 of the plug 193, so that the developing unit(s) can be judged absent.
For example, the memory unit 175 is formed of a CMOS RAM (random access memory) which serves as a counter for counting copies made (or cycles of copying operation). In this embodiment, the memory unit 175 is provided with a plurality of copy counters (not shown) for counting copies for their corresponding developing units 32a and 32b, and a single total counter for ascertaining the total number of copies. These counters are selected by address designation responsive to the discriminating codes for the developing units, and can store their respective count data. The count data of each copy counter is formed of, for example, four bits by five, and is stored in the form of a BCD code. The count data of the total counter is formed of, for example, four bits by six, and is stored in the form of a BCD code.
The operation of the microcomputer 171 of the copying machine constructed in this manner will now be described in detail.
Referring first to the flow charts of FIGS. 17A to 17F, the operation of the microcomputer 171, following connection to power supply, will be described. When it is detected in step A0 that the power is on, step A1 is entered. In step A1, the second developing unit 32b, storing the standard-color or black developing agent is actuated, and the automatic exposure mode is selected. Then comes step A2, in which a heater lamp of the heat roller 19 is turned on. The operation then proceeds to step A3, in which the pole position shifting solenoid 109b of the second developing unit 32b is deenergized, and the reversible motor 63 is rotated reversely. Subsequently, in step A4, the reversible motor 63 is stopped. Then step A5 is entered in which the pole position shifting solenoid 109a of the first developing unit 32a is deenergized, and the reversible motor 63 is rotated forwardly. The operation then proceeds to step A6, in which the reversible motor 63 is stopped, whereupon step A7 is entered. Up to step A6, although the second developing unit 32b, for black developing, is in a drivable state after the start of power supply, the magnetic brushes 35a and 35b are prevented from being formed on the surfaces of the first and second developing rollers 31a and 31b. Thus, if an operator selects either developing mode, the copying machine will get ready for the start of developing operations at once.
In step A7, the main motor 28 is rotated for a prescribed time, and step A8 is then entered. In step A8, the heat roller 19 is checked to see if its warm-up is completed. If completion of the warm-up is detected, the "ready-to-copy" sign 163 on the control panel is lighted, and the copying machine enters a stand-by mode. Then, in step A9, the copying machine is enabled to accept key operation on the control panel.
Thus, the microcomputer 171 automatically executes a series of stand-by control processes after the start of power supply, providing for subsequent copying preparatory control, based on an operator's operation. When the operator performs key operation in step A9, step A10 is entered, in which the interruption key 152 is checked for activation. If the interruption 152 is off, step A11 is entered. If the key 152 is on, step A12 is entered. In step A12, the copying machine is checked to see if it currently is in the interruption mode. If the machine is not in the interruption mode, the operation proceeds to step A13. In step A13, the copying conditions immediately before the activation of the interruption key 152, including the copy density, copy color, and the set number of copies to be made, are saved, the second developing unit 32b storing the black developing agent, and the automatic exposure mode are selected, the copy number is set to "1", and the interruption mode is established. Then step A14 is entered. When the interruption mode is established in this manner, the preceding copying conditions are saved, and the machine is switched over to the standard-color or black copy mode. Then, the interruption indicator 153 on the control panel is turned on in step A14, and step A11 is entered.
If the copying machine is found to be in the interruption mode in step A12, the operation proceeds to step A15. In step A15, the copying conditions saved in step A13 are recalled, and the developing unit, and the exposure mode used immediately before the start of the interruption mode are reselected, to cancel the interruption mode. Then step A16 is entered, in which the interruption indicator 153 on the control panel is turned off. The operation then proceeds to step A11.
In step A11, the second developing unit 32b is checked for presence, in accordance with a developing unit presence signal responsive to the second developing unit 32b. If the second developing unit 32b is absent, step A17 is entered. In step A17, the first developing unit 32a is checked for presence in accordance with a developing unit presence signal responsive to the first developing unit 32a. If the first developing unit 32a is absent, step A18 is entered. In step A18, the color indicators 157 to 160 and the "ready-to-copy" sign 163 on the control panel are turned off to restore the stand-by mode. Thus, neither of the first and second developing units 32a and 32b is set in the machine, and the color indicators 157 to 160 are prohibited from color indication.
If the second developing unit 32b is found to be present in step A11, the operation proceeds to step A19. In step A19, the first developing unit 32a is checked for presence. If the first developing unit 32a is present, step A20 is entered, in which the color selection key 156 is checked for activation. If the color selection key 156 is on, step A21 is entered, in which the machine is checked to see if the second developing unit 32b is selected. If the second developing unit 32b is not selected, step A22 is entered. In step A22, the second developing unit 32b is selected, and the operation then proceeds to step 23. If the first developing unit 32a is found to be absent in step A19, steps A20 and A21 are skipped, and step A22 is entered. If the color selection key 156 is found to be off in step A20, steps A21 and A22 are skipped, and step A23 is entered.
If the first developing unit 32a is found to be present in step A17, or if the second developing unit 32b is found to be selected in step A21, the operation proceeds to step A24. In step A24, the first developing unit 32a is selected, and step A23 is then entered. Thus, if neither of the first and second developing units 32a and 32b is present, or if one of them is absent, selection of the absent developing unit or units is prohibited.
In step A23, the color of the selected developing unit 32a or 32b is indicated. Namely, the color of the developing agent stored in the selected developing unit 32a or 32b is identified by the discriminating code delivered from the developing unit, and the color indicator on the control panel corresponding to the identified color is lighted. If the identified color is black, for example, the black indicator 157 is lighted; if red, then the red indicator 158.
After the color indication, the operation proceeds to step A25. In step A25, the first and second developing units 32a and 32b are checked for the presence of developing agent, in accordance with signals from the developing agent shortage detecting units 117a and 117b. If both the first and second developing units 32a and 32b are found to contain their corresponding developing agents, step A26 is entered. In step A26, the respective developing agent absence indicators 140a and 140b of the first and second developing units 32a and 32b are turned off. The operation then proceeds to step A27.
If either or both of the developing units 32a and 32b are found to be short of developing agent in step A25, step A28 is entered. In step A28, the developing device 10 is checked, in accordance with a signal from the cover position detecting unit 135, to see if the hopper cover 131 is laid in position. If the hopper cover 131 is in place, step A26 is entered; if not, then step A29. In step A29, the developing agent absence indicators 140a and/or 140b (of the developing unit or units short of developing agent supply) are turned on, and step A27 is then entered. Thus, if the first and second developing units 32a and 32b are short of their corresponding developing agents G1 and G2, the developing agent absence indicators 140a and 140b beside the top openings 132a and 132b are lighted. The developing agent absence indicators 140a and 140b, cannot, however, be lighted when the hopper cover 131 is in place, that is, they can be turned on only when the hopper cover 131 is lifted.
In step A27, the selected developing unit is checked for the presence of developing agent. If the developing agent is present, step A30 is entered in which the developing agent absence sign 165 on the control panel is turned off. The operation then proceeds to step A31. If the selected developing unit is found to be short of the developing agent, in step A27, step A32 is entered, in which the developing agent absence sign 165 on the control panel is lighted. The operation then proceeds to step A31. Thus, the developing agent absence sign 165 is turned on only when the selected developing unit is short of its corresponding developing agent.
In step A31, the copying machine is checked for trouble. If the machine is found to be malfunctioning, it is troubleshooted; if not, step A33 is entered.
In step A33, the copying machine is checked to see if it is in a manual paper supply mode using the sheet-bypass guide 6. If the machine is found not to be in the manual supply mode, that is, if it is found to be in an automatic paper supply mode using the paper cassette 3, then step A34 is entered. In step A34, the paper cassette 3 is checked for the presence of sheets P1. If the sheets P1 are absent, the stand-by mode is restored; if present, step A35 is entered. If the machine is found to be in the manual paper supply mode in step A33, step A34 is skipped, and step A35 is entered.
In step A35, the developing device 10 is checked, in accordance with developing unit presence signals from the first and second developing units 32a and 32b, to see if either of the developing units 32a and 32b has been detached once. If either of the developing units is found to have been detached once, step A36 is entered. In step A36, the developing unit concerned is checked for secureness in attachment, in accordance with a signal from the cover position detecting unit 135. If the cover position detecting unit 135 detects that the hopper cover 131 is in place, the developing unit is judged to be securely attached.
When the secure attachment of the developing unit is ascertained, step A37 is entered. In step A37, the developing agent is removed from the surface of the sleeve of the developing unit detached by the processes in steps A3 to A6, and the stand-by mode is restored. Thus, if the developing unit is detached with the power on, the developing agent on the sleeve of the detached developing unit is removed after the developing unit is securely attached.
If neither of the developing units 32a and 32b is found to have been detached in step A35, step A38 is entered. In step A38, the copy key 151 on the control panel is checked for activation. If the copy key 151 is on, a copy mode as described later in detail is entered; if not, step A39. In step A39, the copying machine is checked to see if no key operation on the control panel has been performed for a prescribed time. If any key operation is found to have been performed during the prescribed time, the stand-by mode is restored; if not, step A40 is entered. In step A40, the machine is checked to see if it is currently in the interruption mode. If the machine is not found to be in the interruption mode, step A41 is entered. In step A41, the second developing unit 32b storing the black developing agent, and the automatic exposure mode are selected, the copy number is set to "1", and the stand-by mode is restored. Thus, if the copying machine is not operated for a prescribed time after a cycle of normal copying operation is ended, it is switched over to the standard-color or black-copy mode, and the automatic exposure mode.
If the copying machine is found to be in the interruption mode in step A40, step A42 is entered. In step A42, the copying conditions saved at the time of establishing the interruption mode are recalled, the interruption indicator 153 on the control panel is turned off, and the stand-by mode is restored. Thus, if the copying machine is not operated for the prescribed time after a copying operation is performed in the interruption mode, the mode enjoyed immediately before the start of the interruption mode is restored.
Referring now to the flow charts of FIGS. 18A to 18D, a copy mode will be described in detail. When it is detected in step B0 that the copy key 151 on the control panel is on, step B1 is entered. In step B1, the pole position shifting solenoid 109a or 109b of the selected developing unit is energized. Then comes step B2, in which the reversible motor 63 is rotated in a direction corresponding to the selected developing unit. The operation then proceeds to step B3, in which the blade solenoid 29 of the cleaning unit 13, discharge lamp 14, main motor 28, transfer power source 181 (transfer charger 11), separation power source 182 (separation charger 12), and developing bias power source 179 are energized or turned on. Then step B4 is entered, in which automatic paper feed from the paper cassette 3 is started. Subsequently, in step B5, the original table 2 is checked for position. If the original table 2 is not in the prescribed position, it is returned thereto in step B6. When the table 2 is thus restored, step B7 is entered.
In step B7, the exposure lamp 22 is turned on. Then step B8 is entered, in which the charging power source 180 (main charger 8) is turned on to start charging the photoconductive drum 7, and the original table 2 is advanced to start original scanning. The operation then proceeds to step B9, in which the aligning rollers 18 are rotated to feed the sheet P1 to the image transfer section 16. Then step B10 is entered.
In step B10, "1" is subtracted from the number currently indicated by the copy number display 155 on the control panel, and "1" is added to the current number in each of the total counter in the memory unit 175, and the copy counter, in the same memory unit 175, for the selected developing unit. The operation then proceeds to step B11, in which the charging power source 180 is turned off, to stop charging the photoconductive drum 7. Then step B12 is entered, in which the exposure lamp 22 is turned off. Subsequently, in step B13, the original table 2 is returned. Then step B14 is entered.
In step B14, the original table 2 is checked for position. If the original table 2 is found to have returned to the prescribed position, step B15 is entered. In step B15, the aligning rollers 18 are stopped from rotating, and the original table 2 is stopped from moving rearward. The operation then proceeds to step B16, in which the copying machine is checked to see if the prescribed number of copies is reached. If the prescribed number is reached, step B17 is entered.
In step B17, the selected developing unit 32a or 32b is checked, in accordance with a signal from its developing agent density detector 42a or 42b, to see if the developing agent density of the selected developing unit 32a or 32b is higher than the lower limit. If the developing agent density is higher than the lower limit, step B18 is entered; if not, then step B19. In step B19, the machine is checked to see if the developing agent has continuously been supplied for a prescribed time. If the continuous replenishment is not detected, step B17 is resumed for the repetition of the aforementioned operation. If the continuous developing agent supply for the prescribed time is detected, step B18 is entered; namely, in the automatic developing agent density control, there are provided a proper density level and the lowest density level that would not result in a change of the fluidity of the developing agent, and at the end of the copying operation, the developing unit drive and developing agent supply are continued until the density of the developing agent reaches the lowest level.
In step B18, the pole position-- - --shifting solenoid 109a or 109b, of the selected developing unit 32a or 32b, is deenergized. Then step B20 is entered in which the reversible motor 63 is stopped. The operation then proceeds to step B21, in which the blade solenoid 29, main motor 28, discharge lamp 14, transfer power source 181, separation power source 182, and developing bias power source 179 are deenergized or turned off, and the stand-by mode is restored.
If the set number of copies is not found to have been reached in step B16, step B22 is entered. In step B22, the developing agent is checked for life by checking the copy counter in the memory unit 175 for the selected developing unit to see if the current number in the copy counter has not reached the prescribed number. If the life of the developing agent is not ended, step B23 is entered.
In step B23, a color change request flag (mentioned later) is checked to see if there is a request for a change of color. If there is no such request (flag=0), step B4 is resumed for the repetition of the aforementioned operation. If there is a request for the a color change (flag=1), step B24 is entered. In step B24, the selected developing unit is changed. Then step B25 is entered, in which the pole position-- - --shifting solenoid of the previously selected developing unit is deenergized. The operation then proceeds to step B26, in which the reversible motor 63 is stopped. Then step B1 is resumed for the repetition of the aforementioned operation. Thus, if the developing is required to be changed during the copying operation, it is replaced with the other, after a current cycle of developing operation is ended, at the earliest.
If the life of the developing agent is found to be ended in step B22, step B27 is entered. In step B27, the copying machine is checked for the presence of any other developing unit of the same color. If there is no such developing unit, step B4 is resumed for the repetition of the aforementioned operation. If there is any other developing unit of the same color, step B28 is entered. In step B28, the developing unit of the same color is selected. The operation then proceeds to step B25. Thus, if the life of the developing agent in the developing unit being used is ended, the developing unit is replaced preferentially with another developing unit storing developing agent of the same color, if any.
Referring now to the flow charts of FIGS. 19A and 19B, the automatic interruption mode will be described in detail. The copying machine is set so that the automatic interruption is repeated at regular time intervals.
When the automatic interruption is started, step C1 is entered, in which the reversible motor 63 is checked for rotation. If the reversible motor 63 is found to be rotating, step C2 is entered, in which the integrating timer 139a or 139b, of the operating developing unit, is energized. The operation then proceeds to step C3, in which a flag A is checked for value. If the flag A is not "1", step C4 is entered, in which a timer A starts counting. Then, in step C5, the timer A is checked to see if it has counted for 5 seconds. If 5-second counting is detected, step C6 is entered, in which "1" is set in the flag A. The operation then proceeds to step C7. If the 5-second count is not detected in step C5, step C5 is maintained for 5 seconds.
If the flag A is found to be "1" in step C3, step C8 is entered. In step C8, the selected developing unit is checked for developing agent density, in accordance with a signal from the developing agent density detector 42a or 42b of the selected developing unit. If the developing agent density is lower than a prescribed level, step C9 is entered. In step C9, the developing agent supply roller 52a or 52b, of the selected developing unit, is driven for developing agent supply. The operation then proceeds to step C7. If the developing agent density is found to be higher than the prescribed level in step C8, step C9 is skipped, and step C7 is entered directly from step C8.
Thus, in the density check, the flag A is "0" immediately after the start of power supply, so that it is judged to be not "1" in step C3, and step C4 is entered. In steps C4 to C6 following step C3, "1" is set in the flag A within 5 seconds after the start of counting of the timer A. Thus, in the copying operation, the density check is achieved on the basis of the output of the developing agent density detector 42a or 42b, after the passage of a predetermined time (e.g., about 5 seconds) required for the flow of the developing agent to the detector 42a or 42b to stabilize, after the start of developing agent supply to the magnet roll 43a or 43b. In other words, the density check is performed after the developing agent flow is stabilized, and is therefore improved in reliability.
In step C7, the color selection key 156 on the control panel is checked for activation. If the color selection key 156 is on, step C10 is entered, in which "1" is set in the color change request flag. The operation then proceeds to step C11. If the color selection key 156 is found not to be on in step C7, step C10 is skipped, and step C11 is entered directly after step C7.
If the reversible motor 63 is found not to be rotating in step C1, step C12 is entered. In step C12, "0" is set in the flag A, the timer A is reset, and the integrating timer 139a or 139b is deenergized. Then step C11 is entered.
In step C11, the copying machine is checked to see if there is any request for the indication of the total number of copies (inputted in cipher through the ten-key array 154 on the control panel). If there is a request for the indication, step C13 is entered. In step C13, the current number in the total counter in the memory unit 175 is indicated by the copy number display 155 on the control panel. The operation then proceeds to step C14.
If no request for the indication of the total copy number is detected in step C11, step C15 is entered. In step C15, the copying machine is checked to see if there is any request for the indication of the number of copies made, by the use of the first developing unit 32a (inputted in cipher through the ten-key array 154). If there is a request for the indication, step C16 is entered. In step C16, the current number in the copy counter in the memory unit 175, corresponding to the first developing unit 32a, is indicated by the copy number display 155. The operation then proceeds to step C14.
If no request for the indication is detected in step C15, step C17 is entered. In step C17, the copying machine is checked to see if there is any request for the indication of the number of copies made by the use of the second developing unit 32b (input in cipher through the ten-key array 154). If there is a request for the indication, step C18 is entered. In step C18, the current number in the copy counter in the memory unit 175, corresponding to the second developing unit 32b, is indicated by the copy member display 155. The operation then proceeds to step C14.
If no request for the indication is detected in step C17, step 19 is entered. In step C19, the normal number of copies is indicated by the copy number display 155. The operation then proceeds to step C14, in which the copying machine is checked to see if there is any request for clearing of the number of copies for either of the developing units (input in cipher for the developing unit concerned through the ten-key array 154). If no request for clearing is detected, the automatic interruption mode is ended. If there is a request for clearing, step C20 is entered. In step C20, the current number in the copy counter in the memory unit 175, corresponding to the designated developing unit, is cleared, and the automatic interruption mode is ended.
In the present embodiment, as described in detail herein, the developing device is provided with two developing units, and a switch for alternatively driving the two developing units is provided on a control panel. Thus, there may be provided an image-forming apparatus which can form an image in an image-forming mode selected among a plurality of image-forming modes, without replacing cartridges including developing units.
In this image-forming apparatus, a copy mode for black, which is commonly used as a standard color, is automatically established when the power is turned on or if no operation is performed for a prescribed time after a copying operation, in a mode for any other color than black, is ended. Thus, the apparatus of this embodiment is very serviceable and easy to operate, requiring no key operation for restoring the black or standard-color copy mode.
If one or either of the first and second developing units is not set in the copying machine housing, it is prevented from being selected. Accordingly, there will not be caused such an operation error, where a copying operation will be started without a developing unit in the copying machine, and the operating efficiency will thus be improved.
If an interruption mode is established in the middle of a copying operation in a mode for a certain color other than black, the black or standard-color copy mode is automatically selected. Thus, a user, as an interrupter, need not perform any key operation for restoring the black copy mode. Moreover, the selection of the developing unit (or color selection) can be achieved even during the interruption mode, and that mode which has been enjoyed before the start of the interruption mode can automatically be restored when the interruption mode is canceled. Thus, the apparatus or copying machine is further improved in its convenience.
The copying machine is checked to see if either of the developing units has been detached with the power on. If a detachment is detected, the developing unit concerned is checked for secureness in attachment. If it is ascertained that the developing unit is securely attached, it is operated so as to remove any developing agent on its developing roller (sleeve). Accordingly, the developing agent cannot remain on the developing roller of the previously detached developing unit, after the developing unit is set in place, so that color mixing will never be caused in developing, through use of the other developing unit.
Furthermore, a developing agent storage portion of black developing means is made larger in capacity than that of color developing means. Thus, the selection between black and color developing processes can be achieved very easily, and the black developing process, which should be executed more frequently, can be accomplished without requiring very frequent developing agent supply.
Although the standard color has been described as being black in the above embodiment, it may be any other color than black.
In the embodiment described above, moreover, the present invention is applied to a two-color copying machine. It is to be understood, however, that the invention is not limited to this embodiment, and may be applied to any image-- - --forming apparatuses that can form images by means of developing units, such as facsimiles or so-called multicolor copying machines using three or more copy colors. | An image forming apparatus is provided with a developing device for developing a latent image formed on the surface of the photosensitive drum. The developing device includes a first developing unit for developing the latent image by use of a first color developing agent and a second developing unit for developing the latent image by use of a second color developing agent. The first and second developing units are selectively driven and devices for inserting/removing the first and second development units are also provided. The image forming apparatus has a selecting device for interrupting an image forming process which is in progress to automatically select an image forming process which uses the second developing unit. | 6 |
BACKGROUND OF THE INVENTION
This invention relates generally to the formation of signals having desired statistical characteristics and more particularly to a design for an integrated circuit chip to produce signals using an autoregressive model.
In various situations, it is desirable to produce an electrical signal or set of electrical signals having a particular frequency spectrum. One technique for producing signals with a desired spectrum is to use what is called an autoregressive model. With this technique, the signal is described in terms of autoregressive coefficients.
To produce a sample of the desired signal, the autoregressive coefficients are combined in a known fashion. The combination of these coefficients is described by an equation: ##EQU1## where
y(N) is the Nth, and current, sample of the generated signal;
q is an index of summation;
y(N-q) is a sample of the generated signal generated q samples before the current sample (for values of (N-q) less than zero, y(N-q) is defined to be zero);
a q is the qth autoregressive coefficient characterizing the desired signal;
b is a constant also determined as part of the calculation of autoregressive coefficients;
X(N) is the Nth sample of a function representing zero mean white noise with a unit variance; and
M is a constant representing the order of the autoregressive model.
The order of the autoregressive model, M, dictates how closely the spectrum of the generated signal approximates the desired spectrum. The higher the value of M, the closer the approximation. It should be noted, however, that the higher the value of M, the more autoregressive coefficients are required to evaluate Eq. 1. Since the signal is generated by some form of electronic circuitry, more coefficients generally require larger or more complicated circuitry.
The circuitry used to form the signal is called an "autoregressive model simulator". It is desirable for an autoregressive model simulator to be easily constructed, regardless of the order of the model. In some applications, it is desirable to generate several signals simultaneously. Thus, it would be desirable to have circuitry that could generate a plurality of signals.
SUMMARY OF THE INVENTION
With the foregoing background in mind, it is therefore an object of this invention to provide a simple circuit for implementing an autoregressive model simulator.
It is also an object of this invention to provide a simple circuit for an autoregressive model simulator capable of generating a plurality of signals.
It is yet another object of this invention to provide a design for an integrated circuit chip from which an autoregressive model simulator of any order can be constructed.
The foregoing and other objects of this invention are accomplished by an autoregressive model simulator constructed from a plurality of identical circuit elements. Each circuit element comprises a plurality of multipliers. The inputs to the multipliers are coupled to first in first out FIFO memories storing a set of autoregressive coefficients and past samples for each signal to be generated. The outputs of the multipliers are summed by adder elements. The sum is combined in an adder/subtractor with an external input representing a random signal.
In operation, the value at the top of each coefficient FIFO is moved to the bottom of the same FIFO after one sample of each output signal is computed. The value at the top of each FIFO storing past samples, except the last, is moved to the bottom of an adjacent FIFO. The simulator is thereby operated to ensure that the coefficients and the corresponding past samples for each signal are simultaneously at the tops of all the FIFOs.
BRIEF DESCRIPTION OF THE DRAWINGS
With the foregoing object of the invention in mind, the invention may be better understood by reference to the following detailed description and the accompanying drawings in which:
FIG. 1 is a block diagram of a fourth order autoregressive model simulator constructed according to the present invention;
FIG. 2 is a circuit diagram, greatly simplified, of the autoregressive model simulator of FIG. 1 constructed from integrated circuits;
FIG. 3 is a block diagram of an Integer Computing Element (ICE) integrated circuit used in the circuit of FIG. 2; and
FIG. 4A is a block diagram of the computing circuitry of a sixth order autoregressive model simulator constructed with ICE chips according to the present invention; and
FIG. 4B is a block diagram of the computing circuitry of an eighth order autoregressive model simulator constructed with ICE chips according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a block diagram of a fourth order autoregressive model simulator. As shown by Eq. 1, the autoregressive model simulator produces samples of a signal y(N) as N takes on values 0, 1, 2, 3 . . . .
In many applications, both the amplitude and phase of the signal y(N) are important. Here, y(N) consists of a real part y R (N) and an imaginary part y I (N) which together convey phase and amplitude information. Likewise, each autoregressive coefficient a q has a real part and an imaginary part a qR and a qI , respectively. X(n) also consists of a real and an imaginary part X R (N) and X I (N). Thus, y(N)=y R (N)+j y I (N) and a q =a qR +j a qI and X(N)=X R (N)+j XI(N). Equation 1 might therefore be written to describe the calculation of y R (N) and y I (N): ##EQU2##
The block diagram of FIG. 1 shows a circuit which implements Eqs. 2a and 2b. Values of bX I (N) and bX R (N) are provided as inputs to the circuit. Memories 100 1 . . . 100 4 store the real parts of the autoregressive coefficients, a qR , for q taking on values 1 . . . 4, respectively. Memories 102 1 . . . 102 4 store the imaginary parts of the autoregressive coefficients, a qI , for q taking on values 1 . . . 4, respectively. Memories 104 1 . . . 104 4 store the real part of y(N-q), y R (N-q), for q taking on values 1 . . . 4, respectively. Memories 106 1 . . . 106 4 store the imaginary part of y(N-q), y I (N-q) for q taking on values 1 . . . q, respectively.
Adder 120 computes the first summation term of Eq. 2a. Multipliers 112 1 . . . 112 4 multiply the values in memories 100 1 . . . 100 4 by the values in memories 104 1 . . . 104 4 , respectively. Thus, each multiplier 112 1 . . . 112 4 computes one term a qR y R (N-q) for q taking on values 1 . . . 4. The output of the multipliers 112 1 . . . 112 4 are summed by adder 120.
Adder 121 computes the second summation term of Eq. 2a. Multipliers 114 1 . . . 114 4 multiply the values in memories 102 1 . . . 102 4 by the values in memories 106 1 . . . 106 4 , respectively. Thus, each multiplier 114 1 . . . 114 4 computes one term a qI y I (N-q) for q taking on values 1 . . . 4. The output of the multipliers 114 1 . . . 114 4 are summed by adder 121. The outputs of adders 120 and 121 are added by adder 122. The output of adder 121 is negated by adder 122 as indicated in Eq. 2a. The term bX R (N) provided as an input is also added by adder 122. Adder 122 adds all the terms in Eq. 2a. Thus, the output of adder 122 is y R (N).
Adder 123 computes the first summation term of Eq. 2b. Multipliers 116 1 . . . 116 4 multiply the values in memories 102 1 . . . 102 4 by the values in memories 104 1 . . . 104 4 , respectively. The nodes labeled I are connected together, but the connection is not explicitly shown. Thus, each multiplier 116 1 . . . 116 4 computes one term a qI y R (N-q) for q taking on values 1 . . . 4. The output of the multipliers 116 1 . . . 116 4 are summed by adder 123.
Adder 124 computes the second summation term of Eq. 2b. Multipliers 118 1 . . . 118 4 multiply the values in memories 102 1 . . . 102 4 by the values in memories 106 1 . . . 106 4 , respectively. The points labeled R are connected together, but the connection is not explicitly shown. Thus, each multiplier 118 1 . . . 118 4 computes one term a qR y I (N-q) for q taking on values 1 . . . 4. The output of the multipliers 118 1 . . . 118 4 are summed by adder 124.
The outputs of adders 123 and 124 are added by adder 125. The term bX I (N) provided as an input is also added by adder 125. Adder 125 adds all three terms of Eq. 2b. Thus, the output of adder 125 is y I (N).
Eq. 1 describes what is often called an "infinite impulse response" or "recursive" filter. The value of y(N) produced for any value of N depends on the M preceeding values of y(N). In FIG. 1, memories 104 1 . . . 104 4 are interconnected such that the M (here 4) preceding values of y(N) are always stored. As seen in FIG. 1, when a new value of y(N) is produced, the value of Y R (N) is stored in memory 104 1 , since that value will represent y R (N-1) when the next value of y R (N) is computed. The value stored in memory 104 1 , previously representing y R (N-1) becomes y R (N-2) and is moved to memory 104 2 . In this way, the values stored in memories 104 2 and 104 3 are "rippled down" each time the value of N increases. Thus, memories 104 1 . . . 104 4 store the appropriate values for y R (N-1) . . . y R (N-4). In a similar fashion, memories 106 1 . . . 106 4 store the appropriate values of y I (N-1) . . . y I (N-4).
An additional feature of the present invention may also be seen by reference to FIG. 1. As previously described, it is desirable for an autoregressive model simulator to produce a plurality of different signals. From Eq. 1, it can be seen that for each signal, a different set of autoregressive coefficients, a 1 . . . a M , a different set of past outputs y(N-1) . . . y(N-M) and a different value of bX(N) is required. The computing circuitry 130 needed to implement Eq. 1 is otherwise the same.
The autoregressive model simulator of FIG. 1 is adapted to produce samples of S different signals. Memories 100 1 . . . 100 4 and 102 1 . . . 102 4 each contain S locations for storing S sets of autoregressive coefficients, one set for each signal to be generated. Memories 104 1 . . . 104 4 and 106 1 . . . 106 4 also have S locations for storing S sets of past values of y(N).
In operation, computing circuitry 130 is time multiplexed to produce S different signals. For example, in a first time interval, memories 100 1 . . . 100 4 and 102 1 . . . 102 4 are operated to provide the autoregressive coefficients for a first signal. Simultaneously, memories 104 1 . . . 104 4 and 106 1 . . . 106 4 are operated to provide past samples of the first signal. In that first interval, then, the output y(N) is the Nth sample of the first signal. In the next time interval, memories 100 1 . . . 100 4 , 102 1 . . . 1024, 104 1 . . . 104 4 , and 106 1 . . . 106 4 are operated to provide values needed to compute the Nth sample of the second signal. The operation of the memories continues in this fashion for each of the subsequent time intervals until a sample is produced for each of the S signals. The cycle then starts over with each memory operated to produce the next sample of the first signal.
Memories 100 1 . . . 100 4 , 102 1 . . . 102 4 , 104 1 . . . 104 4 , and 106 1 . . . 106 4 are here first in first out memories (FIFOs) to simplify the circuitry needed to produce time multiplexed samples of S signals. FIFOs are known in the art to operate such that values stored in memory are read out one at a time in the order they are stored into memory. The next value to be read out is said to be at the "top" of the memory. The value most recently stored in the FIFO is at the "bottom" of the memory.
In preparation for operation, the autoregressive coefficients for the first signal are applied on buses 132 and 134 from any known source. The autoregressive coefficients are then stored into memories 100 1 . . . 100 4 and 102 1 . . . 102 4 . The autoregressive coefficients for the remaining S signals are then stored into memories 100 1 . . . 100 4 and 102 1 . . . 102 4 in like fashion. Memories 104 1 . . . 104 4 and 106 1 . . . 106 4 could be loaded with initial values in a like fashion. Here, however, the initial values are all zero, and well known methods may be employed to set all the values stored in a digital memory to zero.
In a first time interval, the values of autoregressive coefficients for the first signal are at the tops of memories 100 1 . . . 100 4 and 102 1 . . . 102 4 . These are thus fed to computing circuitry 130 to compute a value of y(N). After a value of y(N) is computed for the first signal, the autoregressive coefficients at the tops of memories 100 1 . . . 100 4 and 102 1 . . . 102 4 are moved to the bottoms of the memories. The autoregressive coefficients for the second signal are thus at the tops of memories 100 1 . . . 100 4 and 102 1 . . . 102 4 to compute a value of y(N) for the second signal during the second interval.
When the autoregressive coefficients for the first signals are placed at the bottoms of memories 100 1 . . . 100 4 and 102 1 . . . 102 4 , the past values of y(N) for the first signal are written to the bottoms of memories 104 1 . . . 104 4 and 106 1 . . . 106 4 . After S time intervals, the autoregressive coefficients for the first coefficient will again be at the tops of memories 100 1 . . . 100 4 and 102 1 . . . 102 4 . The past values of y(N) for the first signal will simultaneously be at the tops of memories 104 1 . . . 104 4 and 106 1 . . . 106 4 .
In a like manner, the values needed to compute y(N) for the second signal are the tops of memories 100 1 . . . 100 4 , 102 1 . . . 102 4 , 104 1 . . . 104 4 and 106 1 . . . 106 4 during the second interval. These values are applied to computing circuitry 130 to produce a new value of y(N). The appropriate values are then written to the bottoms of the memories so they will next circulate to the tops of the memories in the same time interval.
The same pattern is repeated for all of the other S signals. Thus, use of FIFOs for memories as shown provides a simple circuit for producing time multiplexed samples of a plurality of signals.
Turning now to FIG. 2, a circuit for implementing the autoregressive model simulator of FIG. 1 using integrated circuit chips is shown. Standard elements of digital circuits such as power connections and control signals are not explicitly shown. However, one of skill in the art will realize that such elements are required.
Computing circuit 130 is shown to comprise four identical chips 220A . . . 220D. Here, chips 220A . . . 220D are called Integer Computing Elements (ICE) chips and are explained in more detail below in conjunction with FIG. 3. Suffice it to say here that ICE chips 220A . . . 220D produce the outputs y R (N) and y I (N) described above.
FIFO 200A is a single integrated circuit chip (IC) containing two FIFO memories configured like memories 100 1 and 100 2 (FIG. 1). FIFO 200B implements memories 100 3 and 100 4 (FIG. 1). FIFO 202A implements memories 102 1 and 102 2 (FIG. 1). FIFO 202B implements memories 102 3 and 102 4 (FIG. 1). FIFO 204A implements memories 104 1 and 104 2 (FIG. 1). FIFO 204B implements memories 104 3 and 104 4 (FIG. 1). FIFO 206A implements memories 106 1 and 106 2 (FIG. 1). FIFO 206B implements memories 106 3 and 106 4 . FIFOs 200A, 200B, 202A, 202B, 204A, 204B, 206A and 206B are each a separate IC such as are known in the art.
Multiplexers 222A and 222B are 4:1 multiplexers such as are known in the art. FIFOs 200A, 200B, 202A and 202B have two outputs (here each a digital word of 16 bits) each representing one autoregressive coefficient. As will be explained later, four 16 bit words are read into each ICE chip 220A . . . 220D. However, each ICE chip 220A . . . 220D has only one 16 bit input labeled H. Multiplexer 222A selects one of the four outputs at a time from FIFOs 200A and 200B for application to ICE chips 220A and 220D. Likewise, multiplexer 222A selects one of the four outputs at the time from FIFOs 202A and 202B for application to ICE chips 220B and 220C.
The inputs bX R (N) and bX I (N) are produced by noise chip 226. Here, noise chip could be one or a collection of chips using known techniques to generate digital samples of zero mean gaussian noise. Noise chip 226 takes as an input a parameter stored in noise variance FIFO 224. Noise variance FIFO 224 operates like one of the memories 100 1 . . . 100 4 (FIG. 1). Noise variance coefficients for each one of the S signals to be generated is stored in noise variance FIFO 224. The noise variance coefficients for each signal reaches the top of noise variance FIFO 224 in the same interval when the autoregressive coefficients for the same 15 signal reach the tops of memories 100 1 . . . 100 4 . Noise chip 226 generates a sample of a random signal with desired variance. Thus, samples of the input bX(N) for the plurality of signals are generated in a time multiplexed order.
FIG. 3 shows additional details of an ICE chip 220 representative of one of the ICE chips 220A . . . 220D. FIG. 3 shows a control input is applied to a decoder 300. Each output of decoder 300 is applied as a control signal to one of the elements of ICE chip 220. The control input is generated by a control circuit (not shown) which might contain a read only memory with the control inputs stored sequentially in it. One of skill in the art will recognize the control circuit (not shown) can be constructed in a variety of known ways to operate the ICE chips as described herein.
Inputs A, B, C and D are connected, as shown in FIG. 2 to one of the FIFOs 204A, 204B, 206A or 206B. Thus, one of the past values of the output y(N) are applied to inputs to A, B, C and D. That value is stored in one of the registers 304A, 304B, 304C or 304D.
As also shown in FIG. 2, the autoregressive coefficients stored in either FIFO 200A, 200B, 202A or 202B are applied to the H input of an ICE chip 220A . . . 220D via multiplexer 222A or 222B. As described above, multiplexers 222A and 222B apply the coefficients to input H sequentially such that each coefficient may be stored in one of the registers 302A . . . 302D.
Each of the multipliers 306A . . . 306D has as its inputs one past value of y(N) and one autoregressive coefficient. The outputs of multipliers 306A . . . 306D therefore make up four terms of one of the summations in Eqs. 2a and 2b. The outputs of multipliers 306A and 306B are summed by adder 308A. The outputs of multipliers 306C and 306D are summed by adders 308B. The output of adder 308A is applied to adder 308C. The output of adder 308B is applied as an input to adder 308C. The output of adder 308C represents the sum of all the products produced by multipliers 306A . . . 306D. In FIG. 1, the output of adder 308C corresponds to the output of adder 120, 121, 123 or 124, depending on which of the ICE chips 220A . . . 220D (FIG. 2) is represented by ICE chip 220 (FIG. 3).
The output of adder 308C is added to the input labeled E. As shown in FIG. 2, the input E represents the real part of the input bX R (N), the output of adder 120 (FIG. 1), the imaginary part of the input bX I (N) or the output of adder 123 (FIG. 1) depending on whether ICE chip 220 is used for ICE chip 220A, 220B, 220C or 220D, respectively. When ICE chip 220 is used for ICE chip 220B, the output of adder 308C must be subtracted from the input E. Adder 308D can be configured by control signal from decoder 300 to subtract. Thus, ICE chip 220 as shown in FIG. 3 is flexible enough to be used for any of the ICE chips 220A . . . 220D of FIG. 2.
ICE chip 220 might be used to provide an autoregressive model simulator of an order other than four as shown in FIGS. 1 and 2. FIG. 4a shows how a plurality of ICE chips 220'A . . . 220'F can be connected to make a sixth order autoregressive model simulator. FIG. 4A shows only the computing circuit 130. As previously described, computing circuit 130 is connected to memories storing autoregressive coefficients at the points labeled "coefficient input". The points labeled R, I and X are connected to like points designated R, I and X. The points labeled R are connected to a memory containing the real parts of the autoregressive coefficients. The points labeled I are connected to a memory containing the imaginary parts of the autoregressive coefficients. The points labeled X are connected to memories storing the real parts of two autoregressive coefficients and the imaginary parts of two autoregressive coefficients. Computing circuit 130 is also connected to memories storing past samples of y R (N) and y I (N) at the points indicated.
In a similar fashion, FIG. 4B shows ICE chips 220"A . . . 220"H connected to form an eighth order autoregressive model simulator. As shown, computing circuit 130 is connected to memories storing past samples of y R (N) and y I (N). Computing circuit 130 is also connected to inputs bX R (N) and bX I (N). The circuit 130 is also connected to memories storing autoregressive coefficients. The points labeled R 1 and R 2 are each connected to memories storing one-half of the real parts of the coefficients. The points labeled I 1 and I 2 are each connected to memories storing one half of the imaginary parts of the coefficients.
Having described this invention, it will now be apparent to one of skill in the art that various modifications could be made to the disclosed embodiments. The ICE chips might be combined to form autoregressive model simulators of orders other than disclosed. The layouts of the ICE chips might be modified to include other numbers of multipliers and adders. It is felt, therefore, that this invention should not be restricted to the disclosed embodiments, but rather should be limited only by the spirit and scope of the appended claims. | An autoregressive model simulator is disclosed. The simulator produces time multiplexed samples of a plurality of signals generated from autoregressive coefficients. The order of the autoregressive model is selected by the configuration of identical integrated circuit chips. The autoregressive coefficients for each signal and past samples of the signal are rotated through FIFOs in a manner which enables the simulator to be simply controlled. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to musical drums and in particular to marching timpani.
2. Description of the Prior Art
One form of drum comprises a tunable drum wherein tensioning devices are applied to the drum head to effect the pitch of the drum beat.
The use of kettle drums goes back many centuries. In approximately the 13th century, a small version of the kettle drum was arranged to be carried by the player as being fastened to a belt worn by the player. One application of such worn kettle drums was in connection with cavalry regiments.
More recently, mechanical tuning devices have been developed, including screw mechanisms. One substantial improvement in such mechanisms was made in the earlier part of the 19th century by providing means for simultaneously adjusting all of the tuning screws disposed around the circumference of the drum head. Other rapid tuning devices have been developed since that time for further improving the efficiency and rapidity of tuning changes. One important improvement in this respect was the use of a foot pedal permitting a substantial extension of the usefulness of such drums.
The conventional kettle drum utilizes a relatively deep shell with the tuning means extending downwardly either through the shell or about the shell. The control mechanism is conventionally mounted at the bottom of the shell and the tuning means includes manipulatable screws extending downwardly thereto from the counterhoop adjusting clamps.
SUMMARY OF THE INVENTION
The present invention comprehends an improved timpani which is adapted for marching use. More specifically, the present invention comprehends such a timpani construction comprising an annular shell defining an open upper end, the height of the shell being a fraction of the diameter thereof, a head secured across the upper end, a horizontal support extending across the shell below the upper end, a pivot device mounted to the support, a crank having a horizontal shaft and a handle at an outer end of the shaft accessible exteriorly adjacent the shell for manually rotating the shaft, means for pivoting the pivot device as the result of rotation of the shaft, and head adjusting means responsive to pivoting of the pivot device for adjustably tensioning the head.
Further more specifically, the improved head adjusting means may comprise a pivot device having a support portion disposed axially of the shell, a pivot shaft pivotally carried by the support for rotation about the shell axis, a radial arm on said pivot shaft defining a threaded through bore exposed radially from the shell axis, a drive shaft having a threaded portion threaded to the arm bore, means for causing axial fixed rotation of the drive shaft to effect threaded adjustment of the pivot shaft by the threaded portion of the drive shaft, and connecting means connecting the pivot device to the adjustable means for adjustably tensioning the head as an incident of the threaded adjustment of the pivot device.
Thus, the invention comprehends an improved compact marching timpani construction providing facilitated use as a marching timpani. The structure is extremely simple and economical while yet providing the highly desirable features discussed above.
BRIEF DESCRIPTION OF THE DRAWING
Other features and advantages of the invention will be apparent from the following description taken in connection with the accompanying drawing wherein:
FIG. 1 is a perspective view of a marching timpani embodying the invention worn by a player, a modified form of shell for use therein being illustrated in broken lines;
FIG. 2 is a fragmentary top plan view with portions broken away illustrating the construction thereof;
FIG. 3 is a fragmentary enlarged vertical section taken substantially along the line 3--3 of FIG. 2; and
FIG. 4 is a fragmentary vertical diametric section thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the exemplary embodiment of the invention as disclosed in the drawing, a marching timpani generally designated 10 comprises a flat disclike drum having an annular shell 11 and a head 12 secured across the shell by a plurality of adjustable tensioning clamps 13. As discussed above, the height of shell 11 may be a fraction of the diameter thereof. The tensioning clamps are of conventional construction well known to those skilled in the art and are adapted to be adjusted by means of longitudinal displacement of tensioning rods 14 connected one each to the different tensioning devices. The opposite end of each rod is connected to a connector, or pivoting device, generally designated 15, which is pivotally mounted on a depending shaft 16 secured by a connecting block 17 and suitable screws 18 to the midportion of a support channel 19 having its opposite ends 20 secured to inturned flanges 21 on the shell 11 by suitable means, such as bolts 22 and nuts 23.
As best seen in FIG. 3, connector 17 includes an axial pivot pin 24 having an enlarged lower end 25 carrying a support ring 26. Pivot connecting means generally designated 27 are pivotally mounted on the pin 24 and include an upper plate 28, a middle plate 29, and a lower plate 30. An annular spacer 31 is mounted on pivot pin 24 between plates 28 and 29, and a second annular spacer 32 is mounted on pivot pin 24 between plates 29 and 30.
Plate 29 is connected for pivotal movement on pivot pin 24 with plate 30 by a plurality of rod end pins 33 and plate 29 is connected for rotation on pivot pin 24 with plate 28 by a shaft end pin 34. Each of pins 33 and 34 is pivotally connected to the respective plates to provide a floating connection thereto.
Tensioning rods 14 are connected one each to the different rod end pins 33. A tensioning shaft 35 has a threaded end 36 threaded to pin 34. A pair of collars 37 and 38 are provided on threaded portion 36 to limit the threaded movement of the shaft through the pin 34 in opposite longitudinal directions.
The opposite end 39 of shaft 35 is journaled by means of suitable bearings 40 carried on a support 41 secured to channel end 20 by means of a plurality of screws 42. Shaft end 39 may extend outwardly through a suitable opening 43 in shell 11 and is provided at its distal end with a manually operable handle 44 for effecting rotation of the shaft 35 about its longitudinal axis, and thereby threading of the shaft through pin 34. Bearing 40 maintains the shaft against axial displacement and, thus, such threading effects a pivoting of the connecting means 27 about the pivot pin 24. As shown in FIG. 4, the handle may be secured to shaft end 39 by a suitable thumbscrew 45.
Thus, the tuning of the timpani may be effected by a simple manual operation of handle 44 by the player. As shown in FIG. 1, the handle is disposed in a convenient position to be readily manipulated by the player when desired. As the tensioning rods 14 extend generally parallel to the flat plane of head 12 and the tensioning shaft 35 similarly extends parallel thereto, the entire timpani may have a minimal height dimension and effectively comprise a disclike structure, as best seen in FIG. 1. Thus, to effect the desired tuning of the timpani, the player merely rotates handle 44 to provide the desired tension to the devices 13 by the pivoting of the connecting means 27 to which the tensioning rods 14 are connected so that all tensioning devices 13 are concurrently adjusted.
To provide improved stability of the connector 15, collar 26 may be provided at the end of a support bar 46 also connected to support 41. To minimize the weight of the timpani, the channel support 19 may be provided with a plurality of holes 47, as best seen in FIG. 2.
An automatic tuning gauge device may be provided in association with the timpani 10 providing further improved facilitated tuning of the head when desired. More specifically, as seen in FIGS. 2 and 3, the automatic tuning gauge device generally designated 48 comprises an indicator plate 49 having indicia 50 indicating different selectable pitches. An indicator arm 51 is secured to a pivot shaft 52 by suitable wingscrew 53. Plate 49 is secured to the shell by a plurality of standards 54 and pivotally carries shaft 52.
As best seen in FIG. 2, shaft 52 is provided at its distal end with an enlarged head 55 connected to a transfer shaft 56 by a universal connector 57.
Transfer shaft 56, in turn, is pivotally connected to a pivot plate 58 which is pivotally mounted to channel 19 by suitable pivot pins 59. Pivot plate 58 is further connected through a connecting rod 60 to a universal connector 61 secured to plate 30 as by nut 62.
Thus, disposition of selector arm 51 in any of the preselected dispositions identified by the indicia 50 may be effected by a corresponding rotation of pivot head 55 from plate 30 through the interconnecting means 56, 57, 58, 59, 60 and 61.
As best seen in FIGS. 1 and 2, the automatic tuning gauge device 48 is mounted to the shell closely adjacent handle 44 and while extending to the interior of the timpani under the shell, the lower end 63 of which, as seen in FIG. 4, is open, the effective downward extension of the device is effectively minimized so that the entire timpani remains essentially a disclike structure having effectively minimum height for facilitated use by a marching drummer. As shown in FIG. 1 in broken lines, the shell may alternatively comprise a bowl-shaped shell having a conventional hollow bottom 64 provided with floor-engaging supports 65.
Thus, the present invention comprehends an improved marching timpani which eliminates the deep kettle construction and vertical reinforcing struts which have been considered indispensable in marching bands heretofore. The present invention utilizes extremely simple and economical structure arranged in a substantial planar configuration providing a highly rigid configuration permitting desirable accurate tuning of the timpani head while yet eliminating the costly and relatively heavy construction of the conventional marching timpani.
The foregoing disclosure of specific embodiments is illustrative of the broad inventive concepts comprehended by the invention. | A machine-tuning marching timpani having an adjusting apparatus arranged in a thin, generally planar configuration permitting the elimination of the conventional deep shell portion of such timpani. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to fluorinated compositions which impart oil and water repellency to synthetic fibers, particularly polyester and nylon fibers, and thus function as anti-soil agents. In particular, this invention relates to fluorinated aromatic carbamates which are derived from fluorinated alcohols and multi-ring aromatic isocyanates.
DESCRIPTION OF THE PRIOR ART
Compounds containing fluorinated groups are broadly known for use as anti-soil agents for synthetic fibers. Fluorinated polyacrylates are disclosed in U.S. Pat. No. 3,171,861, U.S. Pat. No. 3,547,861 and U.S. Pat. No. 3,818,074. These compositions are generally not suitable for application to fibers prior to manufacture of textile fabric or prior to the dyeing of such fabric. In U.S. Pat. No. 3,171,861 it is indicated that the fluorinated alcohol starting materials can be reacted with isocyanates to form carbamates. However, the only carbamate prepared is one based on toluene diisocyanate (Example 10). In U.S. Pat. No. 3,646,153 a variety of fluorinated compositions are disclosed, including substituted ureas of the formula ##STR2## wherein R is alkyl, alkylene, aryl, aralkyl or aralkylene (see col. 4, line 56et seq).
Fluorinated carbamates, derived from the reaction of perfluoroalkanols with isocyanates, are disclosed in U.S. Pat. No. 3,657,320. Typical of these is the compound having the formula ##STR3## which is shown in Example 8 of said patent. Fluorinated carbamates are also disclosed in J54-133,485. Specifically, a water soluble dispersion of the compounds ##STR4## is shown in Example 9 of said application.
In U.S. Pat. No. 3,484,281 there is broadly disclosed a wide range of possible fluorinated carbamates. Typical of these are the compounds of the formula ##STR5## which are disclosed in Examples 3 and 4 (fifth compound in list) respectively. Also disclosed in a list of possible isocyanate starting materials is the compound ##STR6## which is designated J in Table III. However, this isocyanate, as well as five others in the Table, are not mentioned again in the specification, nor are any fluorinated derivatives of them prepared or evaluated.
In Japanese Pat. No. J46-348 there is generally disclosed soil-repellent carbamates of the formula
[R.sub.f ]--X--CONH--[A]--NHCO--[Y]
wherein R f is a fluorinated hydrocarbon, X is preferably --O--, --S--, or --NR--, A is a diisocyanate residue (e.g. toluene diisocyanate) and Y is a stabilizing organic residue (e.g. phenoxy). A typical compound has the formula ##STR7## as shown in Example 1 of said patent. It appears that the compounds containing the stabilizing group Y are considered preferable to those having a free isocyanate group or where Y is --X--R f .
SUMMARY OF THE INVENTION
Applicants have discovered a novel group of fluorinated aromatic carbamates which have excellent anti-soiling properties, durability and resistance to laundering (wash-fastness) when incorporated in polyester and nylon fibers. The compounds of the present invention may be depicted by the formula (I) ##STR8## wherein R f is a fluorinated radical of the formula --W(C n F 2n )Y wherein W has from 1 to 10 carbon atoms and is selected from alkylene and W'--Z--(W") b where W' and W" are alkylene, Z is O, S, NHCO, or N(R)SO 2 wherein R is H or lower alkyl, and b is 0 or 1, Y is hydrogen, fluoro, or perfluoroalkoxy of 1 to 6 carbon atoms, and n is 2 to 20. In the above formulation it is intended that the fluorinated radical R f may be straight, branched or cyclic in any of its alkylene or perfluoroalkylene chains, and lower alkyl means alkyl of 1 to 4 carbon atoms.
Also encompassed within the present invention are compositions containing at least 10% of the above-identified compound (I) in admixture with from 90 to 5% of a compound of the formula (II) ##STR9## and optionally including from 0 to 30% of isomers and homologues of these two compounds.
The subject compounds have an excellent affinity for polyester and nylon fibers and may be incorporated with the raw or partially finished fiber by several methods. In one method the additive may be melt blended with the resin then extruded to form a fiber. In a second method the fiber may be treated with a solution, dispersion or emulsion of the additive in liquid medium, typically a solution in organic solvent or an aqueous emulsion. Either method is generally followed by subsequent heat treatment or annealing of the fiber.
The present compounds are sufficiently compatible with the resin that they become an integral part of the fiber, yet the incompatibility imparted by the fluorinated groups, and the mobility of the compounds, is sufficient to concentrate the compounds at the surface of the fiber, making the fiber hydrophobic and oleophobic. Once incorporated into the fiber surface, the present compounds resist being abraded or washed away because of the low solubility of the compounds in aqueous soap solutions and dry cleaning solvents. The present compounds also allow satisfactory dyeing of the treated fiber, or may be applied together with a dyestuff from the same batch.
The present invention also includes polyester and nylon fibers, especially those derived from polyethylene terephthalate (PET) and nylon-6 and nylon-66, which have incorporated therewith the compound or composition as defined above, and a process for producing such fibers which comprises contacting the fiber with a liquid emulsion, dispersion or solution containing the compound or composition as defined above, and thereafter heat treating or annealing the fiber to impart oil and water repellency.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Compounds falling within the above-identified general formula that are preferred are those wherein R f is W(C n F 2n )Y wherein W is alkylene of 2 to 6 carbon atoms, n is 2 to 12 and Y is hydrogen, fluoro, or perfluoroalkoxy of 1 to 6 carbon atoms. Especially preferred are those compound wherein R f is selected from --CH 2 CH 2 (CF 2 ) g CF 3 or --CH 2 CH 2 (CF 2 ) h OCF(CF 3 ) 2 wherein g is 5 to 11 and h is 4 to 10. Most preferred are compounds of formula I wherein R f is --CH 2 CH 2 (CF 2 CF 2 ) j CF 2 CF 3 and j is 2 to 5.
The compounds of the present invention may be readily prepared by reaction of 2,4-bis(p-isocyano benzyl)phenyl isocyanate ##STR10## with the selected fluorinated alcohol (R f -OH) to form the corresponding carbamate. The reaction of isocyanates with alcohols is well-known in the art and this reaction proceeds accordingly. Commercially available mixtures of polyisocyanates containing at least 10% of the above-described tri-isocyanate may be advantageously employed to produce the soil repellent carbamate compositions of the present invention upon reaction with an equivalent of fluorinated alcohol (i.e. sufficient alcohol to esterify all of the isocyanate groups).
The fluorinated radicals R f which may be present in the compounds of this invention are derived from the corresponding fluorinated alcohols (R f -OH) which are known in the art and described in U.S. Pat. No. 3,171,861, U.S. Pat. No. 3,514,487, U.S. Pat. No. 3,646,153, U.S. Pat. No. 3,697,564, U.S. Pat. No. 4,209,610 and 4,219,681, all of which are incorporated herein by reference.
Typical of these are fluorinated alcohols of the formula HO--W(C n F 2n )Y wherein W has from 1 to 10 carbon atoms and is selected from alkylene and W'--Z--(W") b where W' and W" are alkylene, Z is O, S, NHCO, or N(R)SO 2 wherein R is H or lower alkyl, and b is 0 or 1, Y is hydrogen, fluoro, or perfluoroalkoxy of 1 to 6 carbon atoms, and n is 2 to 20. The preferred fluorinated alcohols, because of their commercial availability, are the perfluoroalkylethanols and omega-perfluoroisopropoxy-perfluoroalkyl ethanols having two to twelve carbon atoms in the perfluoroalkyl groups, as well as the propanol homologues thereof. Most preferred are the perfluoroalkyl ethanols having six to twelve carbon atoms in the perfluoroalkyl groups, and mixture thereof.
The soil-repellent compounds of the present invention may be incorporated into polyester or nylon fibers using several known methods. In one method the compound is blended with the resin prior to being extruded into fibers. In another method, the compound may be applied to the fiber by absorption from a liquid medium, for example as a solution in an organic solvent or as an emulsion or dispersion in aqueous medium. In either method the fibers are generally annealed at elevated temperatures after treatment. Typically the compounds are incorporated in the fibers in an amount of from about 0.1 to 1% by weight and the treated fibers are annealed at temperatures of about 100° to 220° C. for about 1 to 240 minutes to impart the desired soil repellency. Further details of the above methods are disclosed in U.S. Pat. No. 4,209,610 and U.S. Pat. No. 4,219,625 which are incorporated herein by reference.
The invention may be described in greater detail by the following examples in which the parts and percentages are by weight. In each of the examples the fluorinated alcohol employed is a mixture of perfluoroalkyl ethanols having six to twelve carbon atoms in the perfluoroalkyl group. The composition prepared in each Example is a mixture of the compounds of formula I and formula II as previously depicted, the percentages of which are stated for each example (based on analysis of isocyanate by gas chromatography). Where the stated percentages do not total 100%, the remainder of the composition comprises primarily isomers and homologues of I and II, as well as a small amount of other impurities carried over from the starting materials.
EXAMPLE 1
In a 500 ml 4-necked flask was added 6.58 g (0.02 mole) 2,4-bis(p-amino benzyl) aniline (DuPont BABA) and 150 ml toluene. The mixture was heated to 90° C. to effect solution and HCl gas added subsurface until excess had been added. The slurry was well agitated. Eighty-eight ml of 12.5% phosgene in toluene was added subsurface over one hour keeping the temperature above 130° C. The mixture was stirred one hour longer and then purged with nitrogen to remove excess phosgene. The mixture was filtered to remove unwanted solids, an equivalent amount of perfluoroalkylethanol was added, and the mixture refluxed until the G.C. analysis showed no further reaction of the alcohol. the solvent was removed by steam distillation to yield 18.6 g of an off-white solid. Assay: I--90%; II--6%.
EXAMPLE 2
In a 100 ml 3-necked flask was added 22.9 g perfluoroalkylethanol (0.05 equiv.) and 6.75 g (0.05 equiv.) polyisocyanate Lupranate M-20 (BASF). The mixture was heated to 85° C. and after three hours 20 ml of N-methylpyrrolidone was added to the thick solution. The mixture was heated another three hours at 85° C. until no further reaction took place as evidenced by the G.C. analysis for alcohol. The mixture was poured into 400 ml ice water, washed and filtered to give 28 g of light tan solid. Assay: I--34%; II--60%.
EXAMPLE 3
In a 100 ml 3-necked flask was added 6.75 g (0.05 equiv.) polyisocyanate Mondur MRS (Mobay) and 22.9 g perfluoroalkylethanol (0.05 equiv.). The mixture was heated at 85° C. for 1.5 hours. Ten ml of N-methylpyrrolidone was added and the mixture heated ten hours longer. The reaction was worked up as in Example II to yield a light tan solid. Assay: I--19%, II--50%.
EXAMPLE 4
Chlorobenzene (400 ml) was added to polyisocyanate Hylene M-50 (250 g; 0.5 mole) and heated to 40° C. while stirring. Then 450 g (1 mole) perfluoroalkylethanol was added and the mixture heated to 85° C. and held for four hours. The chlorobenzene was removed by steam distillation and the residual material filtered and dried under vacuum to yield 513 g of yellowish solid. Assay: I--23%; II--72%.
EXAMPLE 5
Equal parts of the composition of Example 4 and the dicarbamate of Comparative Example B were thoroughly blended to yield a composition having Assay: I--11%; II--86%.
EXAMPLE 6
A blend of 11 g of the composition of Example 1 and 89 g of the dicarbamate of comparative Example B was prepared, yielding a composition of Assay: I--10%; II--90%.
COMPARATIVE EXAMPLES ##STR11##
In a 100 ml flask was added 4.49 g of 97% toluene di-isocyanate(0.025 mole), 22.9 g (0.05 mole) perfluoroalkylethanol and 10 ml N-methylpyrrolidone. The mixture was heated at 70° C. for eight hours and drowned into ice water. After washing to remove solvent, the material was filtered and dried under vacuum, yielding 23 g of off-white powder. ##STR12##
In a 100 ml 3-necked flask was added 22.9 g perfluoroalklethanol (0.05 mole) which was heated to 85° C. To this was added 6.25 g (0.025 moles) 4,4'-methylene di-phenyl isocyanate Mondur M, Mobay). The reaction temperature was increased to 130° C. and held for one hour. On cooling 27 g of a white solid was obtained.
Application of Compounds to Fiber
Each of the compounds prepared in Examples 1 to 5 and Comparative Examples A and B were applied to fiber by dissolving the compound in acetone and applying it to nylon fabric through a padder. The concentration of compound in solution was adjusted so that pick up was 0.25% compound compared to the weight of the fabric. After drying at room temperature, the fabric was cured (annealed) at 140° C. for 30 minutes.
The treated fabrics were then subjected to AATCC Test 61-1968 Wash IIA or IIIA using a launderometer from Atlas Electric Company to simulate five home launderings at medium or high temperature settings. The washed fabric was evaluated for oil repellency according to AATCC Test 118-1975, the rating scale running from 0-8 with increasing numbers indicating greater repellency. Each fabric was also tested before washing as well as after the wash tests. For long term washfastness the more rigorous IIIA Test was carried out repeatedly, each repeat simulating five home launderings at high temperature. The results of the testing for oil repellency are shown in Table I.
TABLE I__________________________________________________________________________ OIL REPELLENCY Before After IIA After IIIA WashExampleComposition Washing Wash 1 × 2 × 3 × 4 × 5 ×__________________________________________________________________________1 I - 90% 6 6 6 6 6 6 6II - 6%2 I - 34% 6 6 6 6 6 6 6II - 60%3 I - 19% 6 6 6 6 6 6 6II - 50%4 I - 23% 6 6 6 6 6 6 6II - 72%5 I - 11% 6 -- 6 5 4 3 2II - 86%6 I - 10% 6 3 1 0 -- -- --II - 90%A toluene 0* 0 -- -- -- -- --dicarbamateB II - 100% 6 0** 0 0 -- -- --__________________________________________________________________________ *Oil repellency measured 5 after padding and drying, 0 after annealing. **In one test a 3 was obtained, but this result could not be repeated. | Multi-ring fluorinated carbamates are disclosed which have excellent anti-soiling properties, durability and resistance to laundering. The compounds are represented by the formula ##STR1## wherein R f is a fluorinated radical. Compositions containing at least 10% of such compounds are also disclosed, as well as polyester and nylon fibers having such compounds incorporated therein. | 3 |
TECHNICAL FIELD
[0001] The present invention generally relates to methods and devices for controlling an electric motor, and more particularly relates to a controller and associated drive assembly for controlling a brushless direct current (BLDC) motor.
BACKGROUND
[0002] Electric motors are used in many application areas, such as utilities, manufacturing, military, medicine, transport, and so forth. One type of electric motor in general use is known as a brushless direct current (BLDC) motor. In a BLDC motor, the stationary outside portion (stator) is typically composed of electromagnetic windings corresponding to the electrical phase configuration of the motor, and the rotating inner portion (rotor) is typically composed of two or more permanent magnets of opposite magnetic polarity. The stator windings are generally electrically connected to a controller/driver unit, where the controller typically provides commands to the driver to generate poly-phase input currents in the stator windings. A BLDC motor driver does not require brushes or a commutator, and is therefore relatively maintenance-free, with a typically lower level of generated electrical noise.
[0003] One conventional type of BLDC motor driver includes a series of Insulated Gate Bipolar Transistors (IGBT's) electrically connected to the phase windings of the BLDC motor. For a three-phase BLDC motor, a conventional driver typically includes six IGBT's arranged in three half-bridges, where each half-bridge can generate a drive for one phase of the motor. As the rotor permanent magnets approach the stator electromagnetic windings of opposed polarity, sensors are typically used to signal the angular position of the rotor to the controller, which can then command the driver to cause the input currents in the stator windings to switch their magnetic field polarities. In this manner, a rotating magnetic field can be generated by the current flows through the stator windings. For a three-phase motor, the three current phases are typically switched in sequence, as dictated by the angular position of the rotor.
[0004] The speed of a BLDC motor is generally controlled by a pulse width modulation (PWM) technique, where the driver controls the average currents in the stator windings by generating “on” and “off” states for the input voltage signals to the stator windings. That is, the duty cycle of the input voltage pulse signals can be used as a controlling factor for the average current in the stator windings.
[0005] The upper speed capability of a conventional BLDC motor driver is typically limited to the switching speed of the IGBT elements in the half-bridge circuits used to drive the stator windings. For example, a standard driver with six IGBT's can typically drive a three-phase motor, using two IGBT's per phase, with a maximum switching frequency of approximately 20 kHz, assuming the maximum IGBT current is not required for more than a few minutes. As such, conventional BLDC motor drivers using IGBT switching elements are generally limited to relatively low frequency (about 20 kHz maximum) and low power (about one horsepower maximum) applications.
[0006] While other switching devices with higher frequency capabilities are available, their cost is typically many times higher than the cost of a standard IGBT, which makes the costly high frequency devices generally undesirable for production applications. Furthermore, as motor technology advances, there is an increasing demand for drivers that are capable of operating at higher frequencies and higher power levels. For example, there are current applications requiring an operating frequency in the range of 62.5 kHz, with power levels ranging from approximately 2 to 21 horsepower. Therefore, there is a need for a scalable type of driver to operate over a range of frequencies and power levels. Moreover, this type of scalable driver could be suitable for production applications if the switching elements were standard low-cost components, such as IGBT's.
[0007] Accordingly, it is desirable to provide a controller/driver for BLDC motor applications with scalable frequency and power capabilities. In addition, it is desirable to implement the scalable driver with low-cost components for production applications. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description and the appended claims, taken in conjunction with the accompanying drawings and the foregoing technical field and background.
BRIEF SUMMARY
[0008] According to various exemplary embodiments, devices and methods are provided for scaling a BLDC motor control system in both frequency and power. One control system embodiment includes a drive assembly in electrical communication with the phase windings of a BLDC motor, where the drive assembly contains a plurality of half-bridge assembly groupings. Each half-bridge assembly grouping is made up of half-bridge assemblies containing switching elements capable of operating at a first frequency and a first current level. The control system typically includes a processor in electrical communication with the drive assembly, where the processor is configured to control the operation of the switching elements in the half-bridge assemblies. Each grouping of the half-bridge assemblies is typically configured to generate pulse-width-modulated (PWM) signals into a respective phase winding of the BLDC motor at a second frequency that is higher than the first frequency. In addition, multiples of the half-bridge assembly groupings can be configured to generate a second current level in their corresponding phase windings that is greater than the first current level.
[0009] The second (composite) frequency of the PWM signal into a phase winding is generally equal to the product of the first frequency and the number of half-bridge assemblies in a grouping electrically connected to the phase winding. Similarly, the second (composite) current level of the PWM signal into a phase winding is generally equal to the product of the first current level and the number of multiple groupings of half-bridge assemblies in electrical communication with the phase winding.
[0010] The multiple groupings of half-bridge assemblies are typically connected to corresponding multiple “IN_HAND” windings for each phase. The “IN_HAND” windings are generally made up of two or more approximately identical coils wrapped around the same phase winding core. As a result, the common electromagnetic field around the “IN_HAND” windings has the effect of forcing approximately equal current sharing between the switching elements of the corresponding half-bridge assemblies.
[0011] A particular benefit of the disclosed exemplary embodiments of a BLDC motor control system is that both frequency and power scaling can be achieved with standard low cost switching elements, such as insulated gate bipolar transistors (IGBT's). This benefit is due to the exemplary frequency and power sharing circuit configurations of the half-bridge assemblies described herein.
[0012] One exemplary method of scaling both frequency and power in a BLDC motor controller comprises the steps of:
a) sequentially activating a grouping of half-bridge assemblies in the controller driver to generate an output signal to a respective phase winding of the BLDC motor at a frequency greater than the frequency capability of a single one of the half-bridge assemblies; b) combining a plurality of half-bridge assembly groupings in the controller driver to generate an output current level into respective phase windings that is greater than the current capability of a single one of the half-bridge assembly groupings; and c) equalizing the current share in each of the half-bridge assembly groupings by forcing current sharing in the respective phase windings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The present invention will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and
[0017] FIG. 1 is a block diagram of an exemplary control system for a BLDC motor;
[0018] FIG. 2 is a schematic diagram of an exemplary drive assembly for a BLDC motor;
[0019] FIG. 3 is a schematic diagram of an exemplary switching element configuration for a BLDC motor drive assembly;
[0020] FIG. 4 is a timing diagram of an exemplary switching element configuration for a BLDC motor drive assembly;
[0021] FIG. 5 is a timing diagram of an exemplary composite switching element configuration for a BLDC motor drive assembly;
[0022] FIG. 7 is a simplified block diagram of the exemplary configuration of FIG. 6 ;
[0023] FIG. 8 is a schematic diagram of a “Two-In-Hand Winding” configuration; and
[0024] FIG. 9 is a block diagram of an exemplary “IN_HAND” wound BLDC motor drive assembly configuration.
DETAILED DESCRIPTION
[0025] The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description.
[0026] Various embodiments of the present invention pertain to the area of scaling the frequency and power capabilities of controller/drivers for BLDC motors. Combining multiple configurations of half-bridge assembly groupings in the controller/drivers enables the composite output frequency and power levels of the controller/drivers to exceed the limitations of the individual components used in the driver half-bridge assemblies. As such, the frequency and power scalability of the controller/drivers can be achieved with standard low-cost components.
[0027] According to an exemplary embodiment of a system for controlling a BLDC motor 10 connected to a load 12 , as shown in FIG. 1 , a controller 30 provides drive signals to motor 10 and receives feedback signals from motor 10 . Controller 30 includes a drive assembly 40 in electrical communication with a processing element 50 , which maybe any type of microprocessor, microcontroller, or other computing device capable of executing instructions in any computing language. A conventional power supply 20 provides power for the various components of controller 30 .
[0028] Drive assembly 40 typically receives DC power from power supply 20 , and is generally configured to produce pulse-width-modulated (PWM) output signals to BLDC motor 10 . The PWM signals typically develop an average current relationship in BLDC motor 10 , as is known in the art. In order to maintain an appropriate PWM input to BLDC motor 10 , processing element 50 typically receives feedback from BLDC motor 10 , consisting of rotor magnetic field orientation information obtained from such devices as magnetic field sensors (e.g., Hall Effect Sensors) or position sensors (e.g., encoders or resolvers).
[0029] An exemplary embodiment of a frequency scaled driver configuration is shown in FIG. 2 . In this embodiment, BLDC motor 10 is configured as a three-phase motor, with phase windings 90 corresponding to each phase. However, BLDC motor 10 can be configured with any number of phases and corresponding phase windings without departing from the spirit and scope of the present invention.
[0030] Drive assembly 40 is shown with n groupings 100 of half-bridge assemblies 60 (H 1 , H 2 , H 3 ) in FIG. 2 . In this embodiment, each designated grouping 1 through n is connected to each phase winding 90 . In order to accomplish frequency scaling, as will be described below, three half-bridge assemblies 60 are included in each grouping 100 , with designations H 1 , H 2 , H 3 . Each half-bridge assembly 60 is shown connected to a respective output node 101 that is connected to its respective phase winding 90 . In the FIG. 2 example, half-bridge assemblies 60 /H 1 from each grouping 100 are connected to node 101 of output A, half-bridge assemblies 60 /H 2 from each grouping 100 are connected to node 101 of output C, and half-bridge assemblies 60 /H 3 from each grouping 100 are connected to node 101 of output B.
[0031] Another exemplary embodiment of drive assembly 40 is shown schematically in FIG. 3 . In this embodiment, half-bridge assemblies 60 are arranged in a slightly different manner than in FIG. 2 . That is, H- 1 is connected to output A, H- 2 is connected to output B, and H- 3 is connected to output C. Other wiring configurations may also be used, as will be described later, without departing from the spirit and scope of the present invention.
[0032] In the exemplary embodiment shown in FIG. 3 , each half-bridge assembly 60 includes two switching elements 70 connected in series, with a node 80 between the switching elements. Insulated gate bipolar transistors (IGBT's) are typically used as switching elements in this type of application, and are generally available at a relatively low cost. As indicated in FIG. 3 , the collector and emitter of each IGBT switching element are electrically connected to power supply 20 ( FIG. 1 ), and the gate of each IGBT is electrically connected to processing element 50 ( FIG. 1 ). The gate connections are not shown for clarity. In addition, each half-bridge assembly 60 of FIG. 3 can further include any one of a number of other electrical components, as is known in the art. For example, each switching element 70 of each half-bridge assembly 60 can be electrically connected to a fast recovery epitaxial diode (FRED).
[0033] Each switching element 70 can operate at a frequency that does not exceed a predetermined maximum switching frequency, which is typically based on its maximum allowable power dissipation value. For example, when the switching elements comprise IGBT's, each switching element is typically limited to a maximum operating frequency of approximately 20 kHz. In a conventional BLDC driver, only one half-bridge assembly 60 is typically connected to each output node 101 , such that only one half-bridge assembly 60 is electrically connected to each phase winding 90 of BLDC motor 10 . In this type of standard configuration, the maximum output frequency of a driver using IGBT's will generally be limited to approximately 20 kHz, as previously noted. In order to achieve higher output frequencies with the same type of low-cost switching elements, a plurality of half-bridge assemblies can be used, as indicated by the groupings of three half-bridge assemblies (H- 1 , H- 2 , H- 3 ) in FIGS. 2 and 3 .
[0034] FIG. 4 illustrates a timing diagram of the two switching elements 70 of a single half-bridge assembly 60 connected to a respective phase winding 90 of a conventional three-phase BLDC motor 10 , with each switching element 70 operating at a frequency f s . As illustrated, the first and second switching elements 70 are typically operated in the ‘on” and “off” states during the same frequency period (f s ), with the second switching element switched in a staggered manner with respect to the first switching element, as shown in timing diagrams a and b. Thus, each half-bridge assembly 60 is generally capable of providing a PWM output to its respective phase winding 90 , as shown in timing diagram c, at a frequency f p , that does not exceed, and is generally equal to, the operating frequency f s of each switching element 70 .
[0035] The exemplary embodiments of FIGS. 2 and 3 disclosed herein provide a plurality of groupings of half-bridge assemblies 60 that are configured to produce a composite scaled frequency output to each phase winding 90 , as illustrated in the timing diagrams of FIG. 5 . In this embodiment, the number of groupings n is equal to three, such that there are three half-bridge assemblies connected to a respective output node 101 (e.g., all H 1 's to a first node, all H 2 's to a second node, and all H 3 's to a third node) to provide a PWM output (e.g., output A, B or C) to a respective phase winding 90 of a three-phase BLDC motor 10 .
[0036] As illustrated in FIG. 5 , the first and second switching elements 70 of each grouping are operated in the same manner as previously described for a single half-bridge assembly 60 in FIG. 4 , where f s is the operating frequency of each switching element 70 . However, in this exemplary embodiment, the switching elements of each grouping are staggered in time relative to the switching elements in the other groupings, as indicated in timing diagrams a through f. As a result, the composite frequency f p , as shown in timing diagram g, generated from the combination of three half-bridge assemblies 60 being connected to a single phase winding 90 , is generally equal to n×f s , or in this embodiment, f p =3×f s . Therefore, if IGBT's are used as switching elements for this exemplary embodiment of three groupings, a maximum frequency of approximately (3×20)=60 kHz can be achieved.
[0037] In general, the efficiency of a typical switching element can be increased if it is operated below its maximum frequency. As such, a driver with a plurality of groupings of half-bridge assemblies can be operated below the maximum switching frequency of its switching elements while still achieving a higher composite output frequency, since the output frequency is typically the product of the switching element operating frequency and the number of groupings. Accordingly, the exemplary embodiments of FIGS. 2 and 3 can be used for both frequency scaling and for efficiency improvement.
[0038] Another alternative exemplary embodiment of a plurality of half-bridge assemblies 60 is shown schematically in FIG. 6 . In this embodiment, each half-bridge assembly 60 connected to the same output (A, B or C) belongs to a different grouping 102 . That is, the three H- 1 assemblies are all connected to output A, but are each configured within a different grouping (1, 2, . . . n). In this embodiment, n=3, to correspond with the number of phase windings 90 . In similar fashion, all H- 2 assemblies are connected to output B, and all H- 3 assemblies are connected to output C. This same configuration is shown in simplified block diagram form in FIG. 7 , where three half-bridge assemblies H- 1 are connected to phase winding 90 at output A, three half-bridge assemblies H- 2 are connected to phase windings 90 at output B, and three half-bridge assemblies H- 3 are connected to phase winding 90 at output C. Groupings 1 , 2 and 3 are configured as in FIG. 6 , with each grouping containing three half-bridge assemblies (H- 1 , H- 2 , H- 3 ).
[0039] It should be noted that the exemplary embodiments disclosed herein are merely illustrative of various methods of arranging the half-bridge assemblies according to various embodiments of the present invention. In this regard, the half-bridge assemblies can be physically located in any one of a number of different manners with respect to one another, without departing from the spirit and scope of the present invention. Moreover, various multiple half-bridge assembly configurations are available commercially, such as the model 4357 3-phase motor drive including three half-bridge assemblies, manufactured by M.S. Kennedy Corp. of Liverpool, N.Y.
[0040] The exemplary embodiments of pluralities of half-bridge assemblies previously described herein are configured to achieve frequency scaling, but their power capability is still limited to that of a single half-bridge assembly switching element. Therefore, to meet the desired objectives of frequency and power scaling, additional half-bridge assemblies can be combined in power sharing configurations to achieve both frequency and power scaling.
[0041] One exemplary embodiment for power sharing is based on the technique known as “In-Hand” winding, which is illustrated in FIG. 8 . In this example, two essentially identical coils ( 802 , 804 ) are wound on a common core 806 to form a “Two-In-Hand” phase winding 800 , which can represent one phase winding of a poly-phase BLDC motor. The term “In-Hand” derives from the typical practice of winding these coils by hand, in order to ensure their equal sharing of the electromagnetic field developed in the phase winding 800 when current flows through the coils 802 , 804 . Each coil is separately connected to one or more half-bridge assemblies, depending on the particular configuration of the motor drive assembly. In the FIG. 8 illustration, only one half-bridge assembly ( 808 , 810 ) is connected to each coil ( 802 , 804 , respectively), but other configurations may include multiple combinations of half-bridge assemblies, as will be further described below.
[0042] Exemplary half-bridge assemblies 808 and 810 are typically activated in tandem by a controller (not shown) in order to combine their current generating capabilities in coils 802 and 804 . The resulting electromagnetic field that is generated in phase winding 800 has the effect of forcing an equalization of the amount of current flowing in each of the coils 802 , 804 . This type of forced current sharing tends to act as an equalizing current control on each half-bridge assembly 808 , 810 , even though their voltage outputs may be somewhat unequal due to minor differences in their respective operating characteristics. Thus, by “paralleling” the currents of half-bridge assemblies 808 and 810 in coils 802 and 804 of phase winding 800 , an effective doubling of current capability can be realized.
[0043] The concept of “In-Hand” winding can be applied to a poly-phase motor, such as the three-phase configuration 902 shown in FIG. 9 . In this exemplary embodiment, power scaling can be achieved by paralleling pairs of half-bridge assemblies connected to respective “Two-In-Hand” windings for each of the three phases. In the exemplary arrangement of FIG. 9 , three half-bridge assemblies HA 1 are connected to one of the “Two-In-Hand” windings on phase A, and three half-bridge assemblies HA 2 are connected to the other “Two-In-Hand” winding on phase A. In similar fashion, half-bridge assemblies HB 1 and HB 2 are connected to their respective “Two-In-Hand” windings on phase B, and half-bridge assemblies HC 1 and HC 2 are connected to their respective “Two-In-Hand” windings on phase C.
[0044] In a typical operational embodiment, the three half-bridges HA 1 are sequentially activated to produce an output current to the corresponding In-Hand winding of phase A at a frequency approximately three times the operating frequency of each half-bridge HA 1 , as previously described in the timing diagram of FIG. 5 . The three half-bridges HA 2 are activated in synchronism with the three half-bridges HA 1 to produce an essentially identical output current to the other In-Hand winding of phase A, with regard to both frequency and amplitude. As such, the combined outputs of three half-bridges HA 1 and three half-bridges HA 2 provide an electromagnetic field to phase A that is scaled upward in both frequency and power.
[0045] In similar fashion, half-bridge assemblies HB 1 and HB 2 provide scaled frequency and power to phase B, and half-bridge assemblies HC 1 and HC 2 provide scaled frequency and power to phase C. The drive signals for the 18 half-bridge assemblies in this exemplary embodiment are generated by a processor, such as processing element 50 in FIG. 1 , and can be distributed to the half-bridge assemblies via a device such as a Field Programmable Gate Array (FPGA), which is not shown for clarity. As stated previously, other embodiments of half-bridge assemblies and phase windings can be configured in various ways without departing from the spirit and scope of the present invention.
[0046] Accordingly, the shortcomings of the prior art have been overcome by providing an improved method and apparatus for scaling both frequency and power capabilities of a controller for BLDC motors. Sequential triggering of a plurality of half-bridge assemblies enables frequency scaling, and paralleling half-bridge assembly drivers connected to respective multiple phase windings enables power scaling as well. The disclosed exemplary frequency and power sharing techniques allow the use of standard low-cost components for the switching elements, and also enable the switching elements to operate at relatively high efficiencies.
[0047] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiment or exemplary embodiments. It should be understood that various changes can be made in the function and arrangement of elements without departing from the scope of the invention as set forth in the appended claims and the legal equivalents thereof. | Methods and apparatus are provided for frequency and power scaling a drive assembly for a brushless direct current (BLDC) motor. The apparatus comprises multiple groups of half-bridge switching element assemblies connected to respective “In-Hand” phase windings of the BLDC. Each group of half-bridge assemblies receives time sliced commands from a processor so that the resultant frequency of the output drive signal can be higher than the frequency capability of an individual switching element. By effectively paralleling groups of half-bridge assemblies connected to respective In-Hand phase windings, the current delivered to the phase windings can be greater than the individual current capability of the switching elements in the half-bridge assemblies. The electromagnetic field generated in the “In-Hand” phase windings forces essentially equal current sharing in the respective driver switching elements. The disclosed techniques enable frequency and power scaling of motor drive assemblies using standard low-cost components. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an orientation system for well kickover tools and more particularly to an orientation system which orients the kickover tool into an aligned position so that it cannot articulate into the side pocket of a side pocket mandrel when the tool is lowered but orients the tool so that it can be articulated into the side pocket when the tool is raised.
2. The Prior Art
A major problem in the operation of kickover tools arises when the well is deviated at a substantial angle. In a deviated string of tubing the side pocket of a side pocket mandrel may be positioned above the central axis of the tubing or it may be positioned below the central axis of the tubing. If the side pocket is located above the central axis of the tubing, the kickover tool must be powerful enough to resist the force of gravity and kick up into the side pocket. On the other hand, when it is desired to bypass a side pocket mandrel which has its side pocket below the central axis of the tubing, the kickover tool must maintain its aligned condition and not drop down into the side pocket.
U.S. Pat. No. 2,942,671 to Schramm attempts to solve these problems by locating an orienting sleeve with a single orienting guide surface in the side pocket mandrel and by providing the kickover tool with an orienting key. In a string of tubing, the orientation of the orienting sleeve in each of several side pocket mandrels is different. The disclosed kickover tool will only articulate in one direction. When the tool is lowered in the tubing the orienting key engages the orienting sleeve guide surface to orient the tool. If it is desired to by-pass the side pocket of a particular side pocket mandrel, the tool carrier of the kickover tool will be oriented to impinge against the wall of the mandrel, but if it is desired to kick the kickover tool into the side pocket, the kickover tool will be oriented to articulate into the side pocket. With the Schramm system the various orientations of the orienting sleeve require the keeping of precise records as well tools may be run a substantial time after the tubing is set. Also the system requires a large inventory of different mandrels as well as different kickover tools.
U.S. Pat. No. 2,948,341 to Fredd discloses an orienting sleeve with orienting guide surfaces at both ends. The kickover tool is oriented for articulation into the side pocket by the guide surfaces both when the tool is lowered through the tubing and when the tool is raised in the tubing to be articulated into the side pocket. No provision is made to prevent the tool from falling into a side pocket while it is being lowered in the tubing.
U.S. Pat. No. 3,727,683 to Terrel, et al discloses a kickover tool orienting system comprising an orienting sleeve with orienting guide surfaces at both ends, two orienting keys on the kickover tool, and a side pocket mandrel wherein the side pocket is located in alignment with the upper tubing bore while the bore of the mandrel is not aligned with the upper tubing bore. The Terrel, et al system has several disadvantages: First, the arrangement of the two orienting keys on the kickover tool increases the likelihood that the tool will become hung up in the tubing before it is desired to set the tool. Second, with the side pocket being aligned with the upper tubing bore and the mandrel being non-aligned, the possibility of other articles engaging the side pocket when they are lowered through the tubing is increased. Further the non-aligned bore through the mandrel will prevent running of some tools such as a wash pipe.
OBJECTS OF THE INVENTION
It is an object of this invention to provide a kickover tool orienting system that can orient the kickover tool in different orientations as the tool is moved in different directions, even though the kickover tool has a single orienting key.
It is an additional object of this invention to provide a kickover tool orienting system that utilizes a single kickover tool having a single orienting key and a single form of side pocket mandrel in which the tool is oriented away from the pocket when running in and oriented to register with the pocket when the tool is raised in a well.
Another object is to provide a kickover tool with a single key which will pass obstructions when running in the hole but will cooperate with orienting means to orient the tool when moving in both directions in a tubing and in which the setting shoulder of the key becomes inoperative upon application of a selected force.
Another object is to provide a side pocket mandrel having a pair of orienting means spaced angularly in the mandrel to differently orient a kickover tool with a single orienting key as it passes through the mandrel in opposite directions.
These and other objects and features of advantage of this invention will become apparent from the drawings, the claims and the detailed description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings wherein like numerals indicate like parts, and wherein an illustrative embodiment of this invention is shown,
FIG. 1 is a longitudinal view partially in section and partially in elevation showing a side pocket mandrel with its associated orienting means and a kickover tool being lowered through the mandrel,
FIG. 2 is a longitudinal view partially in section and partially in elevation of a side pocket mandrel with its associated orienting means and a kickover tool being articulated into the side pocket of the mandrel,
FIG. 3 is a vertical view in section of a portion of a side pocket mandrel and its associated orienting means,
FIG. 4 is a vertical view in section taken along line 4--4 of FIG. 3.
FIG. 5 is a longitudinal view partially in section and partially in elevation of a portion of a kickover tool and its orienting key, and
FIG. 6 is a longitudinal view partially in section and partially in elevation of a continuation of the view of the kickover tool shown in FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A tubing string 10 is normally run with a plurality of side pocket mandrels, such as mandrel 12, at spaced points along the tubing 10 when the well is to be equipped for gas lift and other purposes. The tubing 10 will be in a casing of a well for producing fluids. For simplicity of illustration, the well casing and well are not shown.
The side pocket mandrel 12 may take any desired form, such as the conventional mandrel shown, except for the orienting means 14. The mandrel 12 will have means, such as threads 16, at its upper and lower extremities for connection to the well tubing 10. Through the mandrel 12 will be a bore 18 through which well operations will be conducted. In the side pocket of the mandrel 12 will be means for receiving well flow control equipment such as valves. The receiving means may be a suitable valve receiver 20 and a shoulder 22 to cooperate with a suitable latch which will maintain the well flow control equipment in the side pocket of the mandrel 12.
Located in one of the end bores of the mandrel 12 will be the orienting means 14. The location of the orienting means 14 within the mandrel 12 and the location of the orienting key on the kickover tool should be such that the orienting key engages the orienting means 14 before the kickover tool can articulate into the side pocket of mandrel 12. If the orienting means 14 is in the upper bore of mandrel 12 and the orienting key is on the upper portion of a guideless kickover tool, then the tool should be short enough so that it cannot articulate into the side pocket before the key engages the orienting means. On the other hand, if the orienting means 14 is located in the bottom bore of the mandrel 12 and the orienting key is on a riding guide which extends below the tool carrier of the kickover tool as in McGowen U.S. Pat. No. 3,827,489, the guide should be long enough so that the key engages the orienting means 14 before the tool can articulate into the side pocket.
The orienting means 14 performs two orienting functions. First, when the kickover tool is being lowered in the tubing, the orienting means 14 orients the tool so that it cannot articulate into the side pocket of mandrel 12. Second, when the kickover tool is being raised in the tubing, the orienting means 14 orients the tool so that it can articulate into the side pocket of mandrel 12. To perform the two orienting functions, the orienting means 14 itself has two orienting means 24 and 26 so positioned with respect to each other that a kickover tool with a single orienting key will be oriented as indicated.
The orienting means is preferably provided by an annular elongate sleeve 14 in mandrel 12 having an axis coincident with the axis of mandrel 12. So that sleeve 14 does not reduce the effective diameter of the tubing, the bore portion of mandrel 12 in which sleeve 14 is located preferably has an internal diameter slightly in excess of the internal diameter of the tubing 10 and the sleeve 14 has an internal diameter equal to the internal diameter of the tubing 10. The upper and lower surfaces of sleeve 14 comprise the two orienting means 24 and 26 respectively. The upper surface 24 extends downwardly and toward the side pocket at a substantial angle and functions to orient a kickover tool into a position so that it cannot articulate into the side pocket of mandrel 12 on downward movement of the tool through the tubing 10. The lower surface 26 extends upwardly and away from the side pocket and functions to orient a kickover so it can articulate into the side pocket on upward movement of the tool. Thus in performing their respective orienting functions, the upper surface 24 provides a downwardly directed mule shoe guide surface while the lower surface 26 provides an upwardly directed mule shoe guide surface. The upper and lower surfaces 24 and 26 are engageable by a locator key of a kickover tool.
Once a kickover tool with a single locator key has been oriented in the desired orientation by either of the upper and lower surfaces 24 and 26 of sleeve 14, means are provided to maintain the kickover tool in the prescribed orientation as the key passes through the sleeve 14. Orientation maintaining means 28 engages the locator key of the kickover tool to maintain the kickover tool in a position where it is unable to articulate into the side pocket of mandrel 12, and orientation maintaining means 30 engages locator key to maintain the tool in a position where it can articulate into the side pocket. Orientation maintaining means 28 may be a vertical slot through sleeve 14 extending downwardly from the lower-most portion of the upper mule shoe guide surface 24. Similarly, orientation maintaining means 30 may be a vertical slot through sleeve 14 extending upwardly from the upper-most position of the lower mule shoe guide surface 26. In FIG. 3 one surface of vertical slot 28 is shown as 28a and one surface of vertical slot 30 is shown as 30a. Vertical slot 28 terminates before it reaches lower surface 26 so that a complete orienting means is provided by lower surface 26. Otherwise the possibility exists that when the tool is being raised through the tubing the locator key will not engage the lower surface 26 but will pass through sleeve 14 through slot 28. To prevent the orienting key from hanging up on the termination of slot 28, vertical slot 28 terminates at its lower-most end in chamfered surface 32. Vertical slot 30 is shown, in FIG. 3, terminating at its upper-most end in a downwardly directed stop shoulder 34. Stop shoulder 34 is square or normal to the axis of the sleeve 14, and provides means to engage the locator key of the kickover tool, in a manner to be hereinafter explained, to articulate the tool into the side pocket of side pocket mandrel 12.
Although the upper and lower orienting surfaces 24 and 26 are shown as being parallel, and vertical slots 28 and 30 are shown as being in opposite sides of orienting sleeve 14, it is to be understood that the alignment of these surfaces and slots can be any alignment that will permit the surfaces and slots to perform their orienting functions and the slots need not be 180 degrees apart. The upper orienting surface 24 with its vertical slot 28 is oriented a sufficient angular distance from the lower orienting surface 26 with its vertical slot 30 so that when a kickover tool with a single locator key is lowered through the tubing 10 the engagement of the locator key with upper surface 24 and vertical slot 28 orients the kickover tool to impinge the tool carrier along the bore wall of side pocket mandrel 12. When the tool is raised through the tubing 10 the engagement of the locator key with lower surface 26 and vertical slot 30 orients the kickover tool to permit articulation of the tool carrier into the side pocket of mandrel 12.
To provide a kickover tool that cannot articulate into the side pocket of mandrel 12 after its locator key has been oriented by first orienting means 24 of orienting means 14 when the tool is being lowered in the tubing 10, and yet which can articulate into the side pocket after its locator key has been oriented by the second orienting means 26 when the tool is being raised, a modified version of the kickover tool disclosed in U.S. Patent Application Ser. No. 454,727 filed Mar. 27, 1974 now U.S. Pat. No. 3,876,001 issued Apr. 8, 1975 may be used. The kickover tool illustrated herein is identical to the tool described in said application except for the design of the locator key. Said patent application is incorporated herein by reference for all purposes and reference thereto may be made for a detailed description of the tool and its operation.
The kickover tool has a housing 40 which is attached at its upper end to a sub 42 for connection with wire line tools or pump down equipment 44 in the conventional manner. To articulate the tool, the housing 40 slidably carries a plunger element 46. Pivotally mounted, at pivot joint 60, on one of the housing 40 and the plunger element 46 is a tool carrier 48. Carried by the other of the housing 40 and the plunger 46 is a locator key 50. The tool carrier 48, is the member of the kickover tool that is articulated into the side pocket of mandrel 12. Since the function of the articulated kickover tool is to run or retrieve well equipment from valve receiver 20 of mandrel 12, tool carrier 48 has at its lower end connecting means, such as pivot joint 52, for attachment to an adaptor 54 which runs or retrieves tool 56.
The housing 40, the plunger element 46, the tool carrier 48, and the pivot joint 60, which connects the tool carrier 48 to one of the housing 40 and the plunger 46, cooperate to perform two functions. First, they only permit the tool carrier 48 to articulate in one direction; e.g., the tool carrier 48 has only one degree of freedom. Second, they operate to articulate the tool carrier 48. With a pivot pin 60 connecting the housing 40 and the carrier 48, the carrier 48 could swing in two directions. Limit means prevent the tool carrier 48 from swinging in one of those directions. The housing 40 has a lower, downward facing surface 62 to engage an upper, upward facing surface 64 of the carrier 48. The abutment of these two surfaces prevents the carrier 48 from being articulated in one direction beyond the aligned relationship of FIG. 1, but permits it to be articulated in the other direction to the FIG. 2 position. To articulate the carrier, the plunger 46 has an abutment surface 66 at its lower end which engages a complementary abutment surface 68 at the upper end of the tool carrier 48. In order for engagement of surface 66 with surface 68 to articulate the carrier 48, the point of engagement of surfaces 66 and 68 is laterally spaced from pivot joint 60. With such an arrangement upward movement of the housing 40, relative to the plunger 46 results in surfaces 66 and 68 engaging to pivot or articulate the tool carrier 48 about pivot joint 60 into its kicked over, articulated position. It should be apparent that if the carrier 48 is pivotally joined to the plunger 46, surfaces on the plunger 46 and the carrier 48 would cooperate to limit the carrier's articulation to one direction while surfaces on the housing 40 and the carrier 48 would articulate the carrier 48 when the housing 40 is moved upward with respect to the plunger 46.
To provide for the upward movement of the housing 40 relative to the plunger 46, a locator and orienting key 50 is carried by the plunger 46. To prevent the key 50 from hanging up on obstructions, such as tubing couplings, as the tool is being lowered or raised in the tubing 10, and at the same time to permit the key 50 to perform its orienting and locating functions, the key 50 has means for resiliently urging a portion thereof to project beyond the outer surface of the housing 40 and yet which permit the key to be retracted within the housing 40. To accomplish these functions, key 50 is located in a window recess 70 of the plunger and housing 40. The key 50 is pivotally joined at one end to the plunger 46 by pin 72. Means for resiliently urging the key outward while permitting the key to be retracted within the recess 70 are provided by spring 74. The key 50 is provided with means to engage the orienting means 14. The engaging means on the key 50 may be a lower downward facing stop shoulder 76 and an upper upward facing abutment shoulder 78 both of which are on the portion of the key 50 projected beyond the housing 40. These shoulders extend perpendicular to the axis of the housing 40. Abutment shoulder 78 also engages the downward facing stop shoulder 34 in the sleeve 14 to permit movement of the housing 40 relative to the plunger 46 to articulate the kickover tool. Although it is necessary for stop shoulder 76 and abutment shoulder 78 to project far enough beyond the housing 40 so that they will engage the orienting means 14, it is also desirable that the key 50 have means for retracting it into recess 70 to pass other shoulders and obstructions in the tubing. For downward movement through the tubing, the retracting means is a lower chamfered surface 80 extending from lower stop shoulder 76 to the outer projecting edge 84 of the key 50. Chamfered surface 80 will ride over any obstructions in the tubing, forcing the key 50 to retract into the recess 70. The relationship of the width of the wall of sleeve 14 and chamfer 80 is selected such that with key 50 engaging the bore wall of mandrel 12 the shoulder 76 will engage the mule shoe guide surface 24. For upward movement through the tubing, the retracting means can be provided by having pin 72, which joins the key 50 to the plunger 46, be a shear pin in the conventional manner. Sufficient force will shear pin 72 and force key 50 into recess 70. A preferred alternative upward retracting means can be provided by chamfered surface 86 on key 50 and by having the abutment shoulder 78 be an abutment member 88 pivotally mounted on the upper portion of key 50 by pivot pin 90 and shear pin 92. Upward force will shear pin 92 and permit the abutment member 88 to swing inside recess 70. Chamfered shoulder 86 will retract the key into recess 70. To prevent abutment member 88 from swinging to the left of the position shown in FIG. 5 stop means, such as pin 94, are provided.
When the kickover tool is run downward through the tubing, chamfered surface 80 of key 50 will ride over any obstructions to retract the key into the recess 70 until the tool is run through the orienting means 14. Then shoulder 76 of the key 50 engages the upper guide surface 24 of the orienting means. Upon upward movement of the tool through the tubing 10, abutment shoulder 78 first engages the lower guide surface 26 of the orienting means and then engages stop shoulder 34. Further upward movement of the wireline tool or pump down equipment 44 will result in upward movement of the housing 40 relative to the plunger 46 as upward movement of the plunger 46 will be restricted. This relative movement of the housing 40 and plunger 46 will articulate the carrier 48 as aforementioned. The tool is then lowered to position or to remove a well tool 56 in the side pocket. Thereafter an upward force will retract the key 50 into recess 70 and permit the kickover tool to be removed from the tubing 10. It is apparent that if the plunger 46 had been pivotally attached to the carrier 48 instead of the housing 40; attaching the key to the housing 40 instead of the plunger 46, in the manner above-provided, will permit the tool to operate under the same principles as described.
The overall operation of this invention can now be appreciated. A kickover tool, as described, is run through a string of tubing 10. The tubing has several side pocket mandrels 12 located therein; each side pocket mandrel 12 having an orienting means 14. Chamfered surface 80 retracts key 50 into recess 70 of the tool so that the tool is not hung up when it is lowered through the tubing 10. When the tool is being lowered through a side pocket mandrel 12, stop shoulder 76 of the key 50 engages the first, upper guide means 24. The upper downwardly directed mule shoe guide surface 24 orients the key 50, and thus the tool, until the key 50 can slide down vertical slot 28. By passing down through vertical slot 28 the key 50, and thus the tool, maintains its orientation as it passes through the orienting means 14. The orientation provided to the tool by the engagement of the orienting key 50 with the first upper orienting means 24 is such that the tool carrier 48 cannot articulate into the side pocket of mandrel 12. In this manner the tool is lowered through the tubing to any desired depth. The tool is then pulled upward in the tubing to articulate it. When the tool reaches the side pocket mandrel 12, abutment shoulder 78 engages the lower guide means 26. This upwardly directed mule shoe guide surface 26 orients the key 50 until the key 50 can run up into vertical slot 30. The orientation provided to the tool by the engagement of key 50 with the lower guide surface 26 is such that the tool carrier 48 can now be articulated into the side pocket of mandrel 12. The key moves up in slot 30 until abutment shoulder 78 of the key 50 comes in contact with stop shoulder 34. Further upward movement of the wire line tool or pump down equipment 44 results in the plunger 46 remaining stationary and the housing 40 being pulled upward with respect to the plunger 46. Lower surface 66 of the plunger 46 and upper surface 68 of the tool carrier 48 engage to articulate the carrier into the side pocket.
The well tool 56 is landed in side pocket 20 in a conventional manner and the attaching means releases the well tool 56. The kickover tool can now be raised to remove it from the tubing. Upon upward movement of the kickover tool, abutment shoulder 78 again engages stop shoulder 34. A substantial force shears pin 92 of the abutment member 88 permitting the abutment member 88 to swing into recess 70 and permitting chamferred surface 86 to retract key 50 into recess 70. When the tool carrier 48 comes into contact with the upper bore of side pocket mandrel 12, a force is exerted on the tool carrier which causes it to pivot about pivot joint 60, and causes its upper surface 68 to engage the lower surface 66 of the plunger 46 thus slidably moving the plunger with respect to the housing 40 so that the tool carrier 48 once again resumes its aligned and locked position as explained in said aforementioned application. The kickover tool is thus removed from the tubing 10 without the carrier arm 48 dragging against the tubing wall all the way to the surface.
When a well tool is retrieved from the side pocket, a similar operation is followed except that a different attachment is secured to the lower end of the adaptor 54. The attachment is run into a position where it can attach itself to the upper end of a well tool in the side pocket.
From the foregoing it can be seen that the objects of this invention have been attained. An orienting system for a kickover tool has been provided which permits the orienting means to have a single orientation within all side pocket mandrels which may be run in the well tubing even though the kickover tool has only one locator key. When the kickover tool is being lowered through the tubing, it is oriented to prevent its engagement with the side pocket of any side pocket mandrel; but when it is raised in the tubing, it is oriented to be kicked over into the side pocket.
It will be apparent that the relationship of the key 50 and slot 30 are selected relative to the kickover tool and side pocket to permit articulation of the tool carrier into the side pocket. The slot 28 is angularly spaced from slot 30 at any desired relationship which will prevent such articulation. While the slots are shown 180 degrees apart other relationships will obviously prevent the tool carrier from entering the side pocket.
While the kickover tool design of said application 454,727 as modified herein is preferred, other designs may be used. For instance, with this invention it is not necessary to lock the body 40 and tool carrier 48 in aligned position while running in or to prevent movement of the tool carrier except in one direction from aligned position as dictated by shoulders 62 and 64. If the orientation going into the well is say 90° from the side pocket instead of 180° as shown, the side walls of the mandrel hold the tool carrier aligned and it cannot swing into a position to engage the side pocket even if allowed to swing in both directions from aligned position.
The foregoing disclosure and description of the invention are illustrative and explanatory thereof and various changes in the size, shape and materials, as well as in the details of the illustrated construction, may be made within the scope of the appended claims without departing from the spirit of the invention. | An orienting system for a kickover tool to permit the installation and/or removal of well equipment from a side pocket mandrel. The system includes a double orienting means to position the kickover tool in a non-aligned position as the tool moves downwardly and in an aligned position as the tool moves upwardly and a single key on the kickover tool to engage each of the orienting means. This abstract is neither intended to define the invention of the application which, of course, is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of international patent application no. PCT/GB00/02023, filed May 25, 2000 designating the United States of America, the entire disclosure of which is incorporated herein by reference. Priority is claimed based on United Kingdom patent application no. GB 9914610.9, filed Jun. 23, 1999.
BACKGROUND OF THE INVENTION
[0002] This invention relates to centrifugal separators for separating solid contaminants from a liquid supplied thereto at elevated pressure and in particular relates to operating and maintaining such a centrifugal separator with respect to a machine in which said liquid is contained and flows.
[0003] United Kingdom patent specification no. GB-A-2311239 describes a self-powered centrifugal separator, that is, one having a separation rotor which is rotated by the pressure of the liquid supplied to and cleaned thereby, having such a separator rotor contained in a housing defined by separable base and cover parts and discusses the potential problems of inadvertent removal of the cover from the base. The patent specification proposes the inclusion of valve means to divert the elevated pressure supply within the separator to permit such removal without interrupting the supply per se and, also, the provision of a mechanical interlock between a manually operated handle of the valve means and the housing cover which impedes said removal until the valve means is operated to divert the liquid supply from the separation rotor.
[0004] As discussed therein, it is a feature of that and other designs of centrifugal separator that the liquid is supplied at elevated pressure to the separation rotor through an axle on which the rotor is mounted for rotation and which axle is disposed between the base and usually also the cover.
[0005] The supply is often arranged to exert an axial force on the rotor to overcome gravity so that the cover not only defines a housing to contain liquid discharged from the rotor but also serves to constrain/retain the rotor axially when supplied with liquid and subjected to such axial force.
[0006] It has been found that inadvertent removal of the cover without shutting off the elevated pressure supply to the rotor risks having the rotor itself being lifted from the base by the applied pressure and detached, and indeed launched as a projectile, as well as uncontrolled discharge of the liquid.
[0007] Whereas the construction of centrifugal separator described in the aforementioned patent specification, that is, the separator rotor being mounted on an elongate stationary spindle fixed to the base, makes it possible for the supply pressure per se to lift the rotor completely clear of the spindle the instant that the cover is separated from the base, it will be appreciated that there are many other configurations of axle means for mounting such separation rotor between base and cover which may be more susceptible to such detachment of the rotor by supply pressure. Particularly susceptible is the type of rotor mounting arrangement in which the rotor is located and mounted with respect to each of the base and cover parts by relatively short stub-axle engagement and in which, if the cover is inadvertently removed, there is little to keep the rotor, particularly if spinning, from instantaneously detaching completely from the base.
[0008] In some centrifugal separator designs, it may not be possible to provide a valve arrangement in the separator itself to interrupt the liquid supply to the rotor or rotor mounting means, not only increasing the risk of inadvertent removal of the cover but also making it more difficult to provide a physical interlock against cover removal. Furthermore, even when such a valve for interrupting the liquid supply to the rotor mounting means is provided within the separator, it may be inappropriate to arrange for a manual interlock which prevents removal of the cover, or impracticable because of the necessity to manually overcome the interlock each time the valve means is operated, and even when it is intended to remove the cover.
SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide an improved centrifugal separator with an arrangement for hindering unintentional ejection of the separator rotor.
[0010] Another object of the invention is to provide a centrifugal separator with a simple and unobtrusive means of guarding against inadvertent cover removal.
[0011] According to the present invention a centrifugal separator of solid contaminants from a liquid supplied thereto at elevated pressure comprises a housing having a base part and a cover part releasably secured with respect to each other and containing a separation rotor, the separation rotor being contained between the base and cover being mounted with respect thereto by spindle means, rotatable about an axis extending between the base and cover and displaceable along the axis limited by said base and cover, the centrifugal separator being characterized by rotor restraining means comprising a restraining surface forming part of, or carried by, the rotor extending radially and circumferentially of the rotor and facing away from the base, and abutment means carried by the base, having an abutment surface overlying the restraining surface at or beyond said limit of axial displacement of the rotor from the base permitted by the cover, operable to prevent further axial displacement of the rotor away from the base in the absence of limitation by the cover.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The invention will be described in further detail hereinafter with reference to illustrative preferred embodiments shown in the accompanying drawings in which:
[0013] [0013]FIG. 1( a ) is a sectional elevation through a centrifugal separator in accordance with the present invention including a first embodiment of rotor restraining means having an abutment constructed as a flanged, circumferentially complete tubular body;
[0014] [0014]FIG. 1( b ) is a partly cut-away, perspective view of the rotor restraining means of FIG. 1( a ), and
[0015] [0015]FIG. 2 is a perspective view of the abutment of a second embodiment of rotor retraining means, in which the abutment is constructed in the form of flanged, circumferentially discontinuous fingers.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0016] Referring to FIG. 1( a ), a centrifugal separator 10 comprises a base part 12 and a cover part 14 releasably secured with respect thereto to define a housing enclosure for a separation rotor 16 .
[0017] The base part 12 is a machined casting having a mounting region 18 , liquid supply duct 20 , of relatively small cross-section, and a drain duct 22 , of relatively large cross-section, which leads to an upwardly facing collection region 24 .
[0018] The cover part 14 encloses the rotor and collection region, being supported on the base 12 by way of outwardly projecting sealing flanges 14 1 and 12 1 on each respectively and between which is disposed a sealing element 26 . The sealing flanges are tapered convergingly in a radial direction and surrounded by a correspondingly profiled, circumferentially discontinuous clamping ring arrangement 28 which is operable, by radial contraction, to provide significant axial force between the flanges and on the sealing element to secure the cover part with respect to the base part.
[0019] The separation rotor 16 comprises an annular container 30 of two axially conjoined parts, somewhat similar to the housing. A first component part 32 is disposed adjacent the base 12 and a second component part 34 is disposed adjacent the cover, each being of generally tubular form closed at one end and open at the other, complementing and joined to each other at a peripheral seam 36 which defines a flange extending radially outwardly of, and circumferentially about, the peripheral wall of the rotor between its ends, the flange having an upper surface 36 1 discussed below.
[0020] The separation rotor is substantially symmetrical about a longitudinal axis 38 thereof for rotation thereabout, and to this end, the separator 10 also includes, on said axis, rotor mounting spindle means 40 comprising a spindle 42 extending through, and fixed with respect to, the container 30 . The spindle extends axially beyond the ends the container in the form of relatively short, effective stub axles, to effect at the lower end a first stub axle 44 and at the upper end a second stub axle 46 . The first stub axle part locates in a bearing 48 in the base 12 and the second stub axle locates in a bearing 50 in the cover 14 , defining first stub axle means and second stub axle means respectively. The lower end of the spindle is stepped at 52 and with the bearing 48 effects a thrust bearing which inter alia limits axial displacement of the rotor in a downward direction towards the base. The upper end of the spindle carries a thrust bearing bush 54 which is able to bear against the cover and inter alia limit axial displacement of the rotor in an upward direction away from the base, that is, defines a rotor displacement limit. In normal circumstances there is a small amount of axial displacement, or end float, permitted.
[0021] The bearing 48 is disposed in a recess 56 in the base 12 which forms a continuation of the supply duct 20 , and the spindle 42 has a supply feed passage 60 , extending part way therealong from an open lower end 62 in the recess 56 , which forms a further continuation of the supply duct 20 . The passage terminates at a cross-drilling 64 which communicates with an annular feed chamber 66 of the rotor leading into the container space 68 . A separate annular chamber 70 directs liquid from the container space to a plurality of discharge apertures 72 which in turn communicate with the discharge region 24 of the housing.
[0022] As an alternative to the more common arrangement of using reaction to emission of the liquid from the discharge apertures via flow constricting nozzles to drive the rotor in rotation, the rotor 16 may be driven by an external turbine arrangement 74 comprising an array of vanes or buckets 76 , carried by the spindle 42 , and a fixed jet 78 disposed to direct liquid tapped from the supply ducts 20 , or from some other source, against the vanes.
[0023] The supply duct 20 also, optionally, contains valve means 80 comprising a valve body 82 rotatable about an axis 84 , normal to the duct, by operation of handle 86 . The valve body has a T-shape through passage and is operable upon rotation to redirect liquid flow along duct 20 by way of diversion passage 88 into the drain duct 22 .
[0024] The centrifugal separator structure thus so far described, and its operation, is essentially conventional; liquid supplied at elevated pressure to duct 20 passes through valve means 80 and into the spindle passage 60 , passing therefrom via the container and discharge apertures 72 to the drain duct 22 . Some of the liquid is directed by way of nozzle 78 to impinge upon the spindle-mounted vanes 76 to spin the rotor and permit centrifugal separation of solid contaminants from the liquid that passes through the container space. It will be appreciated that the rotor, full of liquid has a significant weight and to minimise the downward thrust force on the lower bearing 48 , the liquid supply pressure is used to exert an axial lifting force on the spindle to compensate therefor.
[0025] In normal operation, the valve means 80 , or an external equivalent (not shown), would be operated to prevent the supply liquid flow from reaching the rotor spindle before the clamping ring arrangement 28 is released and the cover is lifted from the base and the upper (stub axle) part of the spindle means. It will be understood that if the clamping ring arrangement were to be released without closing the valve, the axial force exerted by the supply pressure on the rotor and cover would lift them away from the base and, in addition to turning one or both into projectiles, would permit the liquid to discharge at high pressure and volume over surrounding machinery and/or personnel, and possibly starving the machinery of needed lubricant liquid with consequential damage thereto.
[0026] Referring also to FIG. 1( b ), in accordance with the present invention the centrifugal separator 10 is provided with rotor restraining means indicated generally at 90 . The restraining means is in two parts. One part comprises a restraining surface forming part of, and extending circumferentially of, the rotor, and facing away from the base. This surface is provided by the aforementioned upper flange surface 361 of the rotor seam 36 . The other part comprises abutment 91 , carried by the base 12 , having an abutment surface 92 overlying the restraining surface 361 beyond the normal limit of axial displacement of the rotor from the base (end float) permitted by the cover. The abutment 91 comprises a tubular, that is, circumferentially continuous, body part 93 having, at a first end 94 , a radially outwardly directed mounting flange 95 for securing it with respect to the base 12 and, at a second end 96 , radially inwardly directed flange means 97 which provides the abutment surface 92 .
[0027] The nature of the rotor restraining means is that the abutment, by its abutment surface, prevents removal of the rotor from the base without first removing the abutment. To this end, and having regard to the annular nature of the space available between rotor and housing, the abutment is arranged to engage with the base by approach thereto in an axial direction and be secured thereto by rotating the abutment about its axis so that it interlocks in the manner of a bayonet or similar type fitting. As shown, the mounting flange 95 comprises at least one mounting aperture 98 therethrough having a varying radial width circumferentially. Additionally, the base 12 carries a corresponding number of headed fasteners 99 each arranged to pass through a said mounting aperture at the point of greatest radial width but prevented from so doing at the point of least radial width.
[0028] It will be appreciated that the precise structure of the abutment and the restraining surface may be open to variation, as desired and to accommodate different design features of the rotor housing. For example, if the rotor does not have a conveniently placed seam at some point on its peripheral wall, the abutment could be dimensioned to have its abutment surface overlying the upper end wall of the rotor (indicated at 30 1 ), or one or more flanges of arbitrary extent in the circumferential direction may be secured to the peripheral wall of the rotor or possibly, in the case of a rotating spindle, to the spindle means.
[0029] It will be appreciated that provided at least one of the restraining and abutment surfaces is circumferentially continuous, the other one need not be. Therefore, if the restraining surface is circumferentially complete the abutment surface, and indeed other parts of the surface, and indeed the abutment itself, may be circumferentially discontinuous.
[0030] Referring now to FIG. 2 a second form of rotor restraining means ( 190 ) comprises the aforementioned rotor restraining surface 36 1 and abutment 191 . The abutment 191 differs from abutment 90 described above in that the abutment surface and axially extending body is discontinuous circumferentially and comprises one or more discrete axially extending fingers 193 1 . 193 2 . 193 3 each topped by respective flanges 197 1 . 197 2 . . . that define circumferentially limited components 192 1 . 192 2 . . . of abutment surface 193 . Mounting flange means 195 maybe discontinuous as a flange 195 1 , 195 2 . . . associated with each finger or may be circumferentially continuous, as shown in broken lines, in the manner of flange 95 for easier manipulation.
[0031] It will be appreciated that when the rotor restraining surface 36 1 is tapered, any force it exerts on the abutment surface components has a radial component and the fingers 192 1 , 192 2 . . . should be capable of resisting deflection thereby. However, if the rotor restraining surface does not exert a component of force radially on the abutment, then the fingers may be manually deflectable to permit engaging the rotor with, and removing it from, the base 12 . Notwithstanding the form taken by the abutment, it may be secured with respect to the base by other forms of attachment.
[0032] It will be appreciated that there is a possibility of the abutment being inadvertently omitted when the cover is secured to the base and for the operator to be unaware that the safety factor of the restraining means is not present and about which, at the very least, the operator should not be complacent. This is particularly so if the optional valve 80 is omitted.
[0033] Simple warning means may be included, such as a window in the cover which makes the present or absence of the abutment apparent or a resilient tongue which extends radially inwardly from the peripheral wall of the cover or base to scrape audibly against the rotor unless deflected away therefrom by the abutment, that is, remain silent when the abutment means is in place.
[0034] Alternatively, more complex interlock may by provided that inhibits operation of the centrifugal separator without the abutment. Such an interlock may take the form of a valve (not shown) which is linked to the presence of the abutment adjacent the body to permit liquid to be supplied to the spindle passage, or if the valve 80 is included, such interlock may require the presence of the abutment adjacent the body to permit the valve to be moved from diversion to through-flow status. The interlock may alternatively or additionally take a form that inhibits attachment of the cover to the base in the absence of the abutment. For example, the base may carry a resilient member extending at least in part radially outwardly so that it prevents the cover from moving into engagement with the base, which member has a radially inwardly directed component upon which force is exerted by installation of the abutment to deflect member out of the path of the cover. These should be considered as exemplary only and may be used alone or in conjunction with each other or other methods within the knowledge of the skilled practitioner.
[0035] It will be appreciated that the centrifugal separator of the invention is not confined to having the rotor mounting means or rotor drive arrangements described above. The rotor may be driven by more conventional reaction nozzles at container outlet 72 and/or be driven by fluid other than the liquid being cleaned within the rotor container. The rotor mounting means may comprise a stationary spindle fixed with respect to the base, or stationary stub axles fixed with respect to the base and cover.
[0036] Although a centrifugal separator in accordance with the invention may benefit particularly from having rotor restraining means when the supply liquid pressure exerts an axial force on the rotor tending to separate it from the base, the provision of such restraining means is beneficial even when the rotor is not susceptible to such forces, in avoiding the liquid spillage consequences of inadvertent normal removal of the rotor.
[0037] The foregoing description and examples have been set forth merely to illustrate the invention and are not intended to be limiting. Since modifications of the described embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed broadly to include all variations falling within the scope of the appended claims and equivalents thereof. | A centrifugal separator ( 10 ) for an engine includes a rotor ( 30 ) mounted within a housing ( 12, 14 ) for rotation on hollow spindle ( 42 ) to the end of which oil is supplied at high pressure to enter the rotor. To prevent the rotor from flying from the base and oil spraying if the cover ( 14 ) is removed without shutting off the oil supply via optional valve ( 80 ), a rotor restraint ( 90 ) is provided in the form of a ring ( 91 ) which surrounds and overlies a flange of the rotor. The ring may be complete or discontinuous and may also include an interlock to prevent attachment of the cover and/or supply of oil if the ring is not in place. | 1 |
FIELD OF THE INVENTION
The present invention relates to a method for the production of sealing means in microfluidic type assemblies, and to a microfluidic assembly or a member thereof having such sealing means.
BACKGROUND OF THE INVENTION
In one type of microfluidic system the conduit system is defined by micro-sized grooves or channels made in a first plate member and covered by a second flat plate member applied against the first plate member. A conventional material for the plate members is silicon. For the provision of adequate sealing between such silicon members in order to prevent fluid leakage between adjacent conduits or conduit portions, the plate members are bonded to each other, e.g. by glueing, anodic bonding or heating, to make the contact surfaces fuse together. Such a microfluidic silicon structure permits extremely small conduit dimensions, e.g. as low channel heights as 1 micrometer or even less.
For certain applications, however, it is required that the two plate members defining the microfluidic system are not permanently bonded together but may be repeatedly brought apart and put together, respectively. One such application is disclosed in, for example, WO 90/05295 relating to an optical biosensor system based upon surface plasmon resonance (SPR) and comprising a set of microfluidic flow cells for contacting the sample fluid with a sensing surface. Upwardly open flow-through cell channels are recessed into the surface of one plate member and closed by a second plate member supporting the sensing surface on the side thereof facing the first plate member. To provide for the necessary mutual sealing of the flow cells defined between the two plates when pressed together (conventional sealing means of the o-ring type or the like not being feasible in microscale connections) the upwardly open flow cell channels are formed as precision-cast cuts or slits extending through a top layer of an elastomeric material integral with the first plate member. Thereby efficient sealing is obtained when the sensing surface member is pressed against the elastomeric layer and a relatively large number of such dockings may be performed with retained sealing effect. With such an elastomeric layer channel heights as small as 50 micrometers may be provided, a practical lower limit being about 20 micrometers. Channels of still smaller heights may, however, not be made with adequate accuracy.
It has now been found that for obtaining optimum mass transfer conditions in, for example, the above mentioned biosensor application in order to obtain faster analyses and/or a higher sensitivity and/or a more reagent-saving system and/or more accurate kinetic measurements, it would be desired to use a maximum flow cell height of about 10 micrometers. While the desired low height channels, as mentioned above, can be performed in hard materials like silicon, there has so far been no satisfactory solution to the sealing problem associated with non-resilient materials.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a solution to this sealing problem in order to permit inter alia a two-part microfluidic system device of the above mentioned type to be produced in a hard or non-resilient material such as silicon.
In accordance with the present inventive concept an efficient sealing strip may be accomplished by moulding into a channel structure recessed into one of the two plate members to be combined, a resilient sealing material such that the top part of the sealing strip formed projects above the groove structure edges, and has such a configuration in the upper part of the groove structure that, when the sealing strip is compressed by pressing of the two plate members against each other, the deformed material is capable of being completely accommodated in the upper part of the groove structure. Such a sealing strip may be produced in the necessary small size and will permit complete contact between the non-recessed areas of the plate members while simultaneously providing efficient leakage-proof sealing between areas on either sides of the sealing strip. A sealing strip produced in the described manner will be excellently useful for microfluidic purposes, and particularly when very small channel heights are involved.
Thus, in one aspect the present invention provides a method for producing a leakage-proof sealing means in a microfluidic channel assembly comprising first and second flat surface members which when pressed against each other define at least part of a microfluidic channel system between them, which method comprises the steps of
(i) recessing at least one groove structure into the flat surface of the first member;
(ii) providing a counter mould, the mould surface of which has at least one groove structure or at least one ridge structure, optionally in combination, said structure or structures having a corresponding extension as, but a smaller width than the groove structure or structures of the first member;
(iii) applying the counter mould against the first member such that a mould cavity or cavities are defined by the groove structure or structures of the first member with the counter mould surface portions comprising said groove or ridge structure or structures;
(iv) introducing, e.g. injecting, a fluid sealing material capable of hardening to form a resilient sealing structure into the mould cavity or cavities; and
(v) after hardening of the fluid sealing material removing the mould from the first member;
the top part of the mould cavity or cavities being configured in dependence of the shrinkage or expansion properties of the fluid sealing material such that the resulting moulded resilient sealing structure projects above the groove edges of the first member while leaving sufficient space in the upper part of the groove to permit complete accommodation therein of the deformed top part of the resilient sealing structure when compressed by the second member.
The term "channel" or "channel system" as used herein is to be interpreted in a broad sense. It is thus not restricted to elongate configurations but is meant to comprise fluid cavities of any desired shape. Such a fluid cavity may, for example, be a flow-through cell which is to be continuously passed by a fluid, but it may also be a chamber for holding a desired fluid volume for a certain time. A fluid channel system may comprise several such channels or cavities which may be separate or interconnected.
By the term "microfluidic" as used herein is usually to be understood, without any restriction thereto, however, fluid structure widths or depths of below about 500 micrometers.
The sealing means may have any desired configuration as long as they will serve the purpose of sealing off one area of the contact surface of the microfluidic assembly members from another. Preferably, the sealing means will completely enclose a fluid channel to prevent fluid leakage in any direction from the channel. Generally the microfluidic assembly will comprise several separate channels and the sealing means will then form one or more sealing structures isolating each channel from another. Optionally, for example, two adjacent sealing means may be provided for increased security.
While the two members of the fluid assembly which together define the fluid system in question between them generally are plate-shaped, they may have any other configuration as long as they exhibit a flat contact surface for defining the channel system with the other assembly member.
The channel system to be isolated by the sealing means may be provided as a groove structure in one of the two assembly members, which groove structure together with the flat surface of the other member will define the channel system. Alternatively, but perhaps not so attractive from the viewpoint of manufacture and assembly, complementary groove structures may be provided in the two members, these groove structures together defining the channel system.
The sealing means may be provided in either of the two members forming the microfluidic assembly. Preferably, however, the sealing means are provided in the same assembly member as that carrying the channel system to be sealed off by the sealing means.
As mentioned above, the sealing means provided by the method of the invention will be provided as a basal part situated in a groove structure, said basal part having projecting therefrom a top portion which upon deformation when the two assembly members are combined will be accommodated in the groove structure. Generally this projecting portion will have the form of a ridge or the like provided substantially centrally in the basal part. It is, however, within the scope of the invention to provide two or more adjacent ridge structures extending from the same basal part.
Generally, the fluid sealing material injected into the mould cavity will exhibit a slight contraction or shrink upon hardening. Such shrink will normally be sufficient for providing the necessary space in the upper part of the sealing material groove for permitting the projecting part of the hardened sealing means to be completely received therein when deformed. The extent of the shrinkage may inter alia be controlled by selecting the depth or height of the groove properly, i.e. a greater depth will give a greater vertical shrinkage and thereby a larger resulting space or spaces in the upper part of the sealing material groove.
In the case, however, that the sealing material will not by itself provide for the desired shrinkage or even expand during the curing, the required space or spaces in the groove top may be effected by configuring the counter mould surface accordingly to provide such space, for example, by forming an elevated strip or ridge portion on either side of the mould groove to occupy the upper side portions of the corresponding sealing material groove structure; in the case of an expanding material no groove structure in the counter mould will, of course, be necessary but only such strips or ridges.
The fluid material for forming the resilient sealing means may, for example, be an elastomer-forming material, such as a silicone rubber, an elastic epoxy resin or fluorocarbon polymer. At present a silicone rubber is considered to be a particularly suitable material for the purposes of the invention.
The material member carrying the channel system may be any hard or rigid material permitting the channel system to be produced therein by per se conventional techniques, such as chemical or electrochemical etching, laser processing, etc. Exemplary of such materials are silicon, ceramics, metals and plastics. Suitably such a hard member is of silicon, the different channel structures being produced by chemical etching.
Advantageously, the groove structure for the sealing means is produced in connection with that of the channel system, e.g. simultaneously, as will be illustrated below in the detailed description of the invention.
In another aspect the present invention provides a microfluidic device comprising one or more sealing means of the type described above. Such a microfluidic device therefore comprises a first member having a substantially flat surface designed to be applied to a second member having a substantially flat surface, which surfaces when pressed against each other define at least part of a microfluidic channel system between them. One of the first and second members additionally comprises a groove structure supporting a resilient sealing material structure, part of which projects above the surface of that member. In accordance with the above this resilient structure is configured such that, when the two members are applied against each other, the resilient material is compressed to permit the flat surfaces of the first and second members to contact each other while providing adequate sealing between areas on either side of each resilient material structure.
As already mentioned previously a suitable material for the sealing material is liquid silicone rubber which may be cross-linked by appropriate cross-linking means, e.g. by incorporating an initiator, or by other means such as UV-light, electron beam curing, etc.
In one embodiment the microfluidic device provided by the present invention comprises both the assembly members which together define the channel system between them. One of the members may then contain the channel system, which at least partially may be in the form of a groove structure or structures arranged to be closed by the flat surface of the second member to complete the channel system. Depending on the contemplated use of the microfluidic device it may further comprise additional channels or conduits, valve means etc. As mentioned above the sealing means may be provided in either of the two members, but preferably in the one carrying the channel system.
In another embodiment the microfluidic device of the invention comprises only the assembly member carrying the channel system and the sealing means, whereas the flat surface necessary to complete the channel system and compress the sealing means is provided as a separate member. One of the members may then form part of, for example, an instrument or apparatus in which the microfluidic device is to be used. An example of the latter case is the use for the previously mentioned optical biosensor application, for example as disclosed in the aforementioned WO 90/05295 where the member containing the channel system and, in accordance with the present invention, also the sealing means, is stationarily provided in the biosensor instrument while the above mentioned flat surface member supports the sensing surface and is in the form of an exchangeable sensor chip insertable into the instrument to dock with the first member.
In the WO 90/05295 publication there is also described a method of monitoring the temperature at the sensing layer. According to this method one or more of the sealing areas between the flow channels are coated with or consist of a dielectric having a known temperature dependence of its refractive index, the latter being within the detection range of the instrument. The signal representing the resonance angle as measured at the sealing areas between the flow channels will then represent an actual temperature value at the dielectric layer. By applying the present invention and selecting the sealing material properly with regard thereto the resilient sealing material areas in the present microfluidic system device may well serve such purpose as a temperature reference. Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described in more detail by way of a specific embodiment, reference being made to the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a schematic transparent top plan view of an embodiment of a microfluidic flow cell block according to the present invention;
FIG. 2 is a sectional view of the flow cell block along 2--2 in FIG. 1;
FIG. 3 is a sectional partial view of the bottom part of the flow cell block in FIGS. 1 and 2;
FIG. 4 is a corresponding view as in FIG. 3 with the complete flow cell block in FIGS. 1 and 2;
FIG. 5 is a schematic sectional view of a flow cell block member having recesses for sealing material, and separated therefrom a counter mould for forming mould cavities with the flow cell block member;
FIG. 6 is a corresponding view as in FIG. 5 with the flow cell block member and counter mould brought together;
FIG. 7 is a corresponding view as in FIG. 6 with sealing material injected into the mould cavities;
FIG. 8 is a sectional view of the flow cell block in FIG. 7 with the counter mould removed and a top plate member to be applied against it;
FIG. 9 is a corresponding view as in FIG. 8 with the top plate applied to the flow cell block member;
FIG. 10 is a schematic transparent view from above of a sheet of a set of flow cell block/counter mould units permitting the resilient sealings to be moulded simultaneously for the whole set;
FIG. 11 is a sectional view of a modified counter mould applied to a mould plate for forming an elastic layer on the counter mould surface;
FIG. 12 is a sectional view of the elastic layer coated counter mould formed in FIG. 11; and
FIG. 13 is a corresponding view as in FIG. 6 but including the modified elastic layer coated counter mould of FIG. 12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 are schematic illustrations of a microfluidic flow cell block, e.g. to be used in an optical biosensor instrument of the type described in the aforementioned WO 90/05295. It consists of a bottom plate 1 of a suitable hard material, for example silicon, into the upper surface of which there are recessed four upwardly open flow cell channels 2. The bottom of each flow cell channel 2 is provided at each end thereof with orifices 3 and 4 serving as fluid inlets and outlets, respectively. The orifices 3, 4 are connected to conduits not further illustrated in the figures, such as vertically extending riser ducts. Adjacent flow cell channels are separated by resilient sealing strips 5, e.g. of silicon rubber, moulded into respective grooves or recesses 6 in the bottom plate 1. As appears from FIG. 1 the sealing strips 5 also extend along the short ends of the flow cell channels such that each flow cell channel 2 is surrounded by a sealing strip. To complete the flow cells a top plate 7 is placed against the bottom plate 1. For purposes of illustration only the top plate 7 is shown in FIG. 2 as resting upon the resilient sealing strips 5, but in the actual practice the bottom and top plates 1, 7 are pressed against each other to compress the sealing strips 5 and bring the opposed plate surfaces in mutual contact to complete the respective flow cells as will be described below.
Although not shown in FIG. 2, to permit the necessary compression of each sealing strip 5, the top part thereof is configured not to fill up the groove 6 completely in order to leave sufficient space for accommodating the deformed sealing material. Thus, with reference to FIG. 3 the top part 5a of the sealing strip 5 is formed as a ridge or the like which is thinner than the base part of the member 5 and extends from a distance d below the upper edge of the groove 6. Thereby an interspace 6a with respect to the groove wall is defined on either side of the top part 5a. When the sealing member 5 is deformed by pressing the plate 7 against the flow cell block 1, on one hand, the part 5a broadens, and, on the other hand, the surrounding material is pressed upwards. The deformed material portions are, however, completely accommodated in the above mentioned interspaces 6a as is illustrated in FIG. 4, thereby ensuring that the compressed sealing strip will not be forced in between the contacting surfaces of the bottom plate 1 and the top plate 7 but provide for efficient sealing between the flow cells simultaneously as allowing maximum contact of the respective contact surfaces. As is indicated in FIG. 4 a small gap 6a' will consequently remain between the sealing strip parts on either side of the ridge 5a and the top plate 7. In this manner efficient sealing will be obtained even in the case of very minute channel sizes, such as channel heights in the range of about 0.1 to about 10 micrometers.
For the above mentioned biosensor application the top plate 1 will comprise a sensing surface (not specifically shown) as the contact surface, the latter thereby forming the top wall of each complete flow cell.
As an example of the channel sizes contemplated herein, the flow cells illustrated in FIGS. 1 and 2 may have a width of about 300 micrometers, a length of about 2 millimeters and a height typically in the range of about 5 to 50 micrometers.
The channels 2 and 5 in the bottom plate 1 illustrated in FIGS. 1 and 2 may be produced by per se conventional techniques. Thus, in case the plate is of silicon, the grooves or channels may be produced by chemical etching. Since the flow cells and the sealing material grooves have different depths two sequential etching operations will be required. This may be performed as follows.
The plate surface is first oxidized whereupon a photoresist is applied to the oxide layer, e.g. by spinning technique. A suitable oxide layer thickness for the present purposes may be about 8000 Å. A mask having the desired opening pattern for the sealing material grooves is then placed upon the surface and the bare photoresist portions are subjected to light exposure. After development causing the exposed portions of the photoresist to be removed and thereby bare the oxide layer, the bared oxide areas are etched and the remaining photoresist is dissolved and removed. By a first silicon etching procedure a first part of each sealing material groove 6 is then recessed. Following a second photoresist application the areas defining the flow cells are exposed through a corresponding mask. Development of the exposed photoresist, oxide etching, photoresist removal, and a second silicon etching will produce the flow cell channels 2 as well as the remaining depth of the sealing material grooves. In case three or more different channel depths are desired rather than two as described above, one may proceed in the same way as above, i.e. successively open region after region for etching without intermediate oxidation, the channel or groove which is desired to have the smallest depth being opened last for etching, the etching depth of the first opened area being the sum of all the etchings that the silicon plate has been subjected to. By appropriate selection of the etching times the resulting etching depths of the different etching steps may be varied. The above (in connection with FIGS. 1 and 2) mentioned riser ducts ending in the bottom openings 3 of the flow cell channels 2 are, for example, produced by laser drilling.
In an alternative procedure the flow cell channels 4 are first etched as above by the described process steps. The plate surface is then subjected to a renewed oxidation and all the steps are repeated for etching the sealing material grooves. In this way as low channel depths as will be desired may be produced. Thus, while the first mentioned method with a single oxidation conveniently permits channel depths down to about 5 μm to be produced, as small channel depths as, say, 0.1 μm may be obtained by the last-mentioned method.
FIG. 5 illustrates a flow cell bottom plate 1 corresponding to that in FIGS. 1 and 2 but which for ease of illustration, however, has only three flow cell channels 2 and two sealing material grooves 6 which may have been obtained by one of the etching procedures just described. Also illustrated in the figure is a counter mould plate 8, having two grooves 9 of a smaller size as compared with grooves 2 and 6 of the plate 1 and designed to be aligned with the sealing material grooves 6 when the counter mould 8 is correctly applied to the flow block 1. The counter mould 8 may, for example, also be of silicon with the grooves 9 produced by etching as above. It may, however, alternatively at least partially be made of an elastomeric material as will be described below.
FIG. 6 shows the counter mould 8 applied to the flow cell bottom plate 1, the sealing material grooves 6 of the latter and the grooves 9 of the counter mould 8 together defining mould cavities for sealing material to be injected into them.
In FIG. 7 a fluid sealing material 5 has been injected into the mould cavities 6, 9. The sealing material may, for example, be a fluid cross-linkable silicone rubber. A commercially available silicone rubber containing an initiator and useful for the purposes of the present invention is supplied by General Electric Company under the designation RTV 670. Prior to injecting the fluid silicone rubber the counter mould surface is treated with a release agent. After the silicone liquid has been injected it is hardened or cured, either by itself at ambient temperature when it contains an initiator, or by external means, such as UV light or electron beam curing, whereupon the counter mould is removed.
The resulting flow cell block is shown in FIG. 8. It thus consists of a rigid plate 1 having three parallel flow cell channels 2 separated by two resilient sealing strips 5, the top portions 5a of the latter projecting above the plate surface. Due to a certain shrinkage in connection with the hardening or curing of the sealing material the sealing strip 5 will, however, have the slightly vertically contracted configuration in the top part thereof as is illustrated in FIG. 3 and which is necessary for the desired function of the sealing. The extent of this shrinkage is inter alia determined by the height of groove 6. The latter height will also determine the resistance to compression. By proper selection of the heights of sealing material groove 6 and counter mould groove 9 it is thus possible to obtain a suitable protrusion 5a as well as a suitable deformation space (distance d in FIG. 3) for the desired sealing properties to be obtained. In the microsize contexts contemplated herein, i.e. flow cell channel depths of about 0.1 to about 500 μm, while the extension of the projecting part 5a of the sealing strip depends on the flatness of the plate to be applied against it, an exemplary extension in the case of the latter plate being for instance of a standard float glass is about 2.5 μm. Upon the application of a rigid top plate member 7, e.g. a plate supporting a sensing surface in case of use in connection with a biosensor as mentioned previously, the sealing strip protrusions are compressed such that the opposed surfaces contact each other, as is illustrated in FIG. 9. Thereby three flow cells 10 are defined by the channels 2 and the plate member 7, which flow cells are efficiently sealed off from each other in respect of fluid leakage by the two sealing strips 5 as has been explained above.
FIG. 10 illustrates schematically an embodiment of a channel system for the counter mould 8 for the injection of fluid sealing material into the sealing material grooves 6. In the illustrated case five parallel grooves 9, corresponding to the top parts of the sealing strips 5 to be moulded, each extend between a common inlet channel 11 and a common outlet channel 12. With the counter mould properly applied to the flow cell bottom plate 1 (e.g. by means of guide pins or the like) the grooves 9 will extend centrally above the aforementioned grooves 6 and between the flow cell channels 2, indicated by thin lines. It is realized that when fluid sealing material is injected into inlet channel 11, it will successively fill the sealing strip cavities and then exit through the outlet channel 12. It will readily be appreciated that a plurality of counter mould units such as shown may be connected in series and/or in parallel in one single sheet to be applied to a corresponding flow cell bottom sheet having a plurality of sets of flow cell channels and sealing material grooves. After injection and curing of the fluid sealing material, the counter mould plate is removed and the individual flow cell blocks are cut out.
When the above described microfluidic system is used in connection with an optical biosensor of the aforementioned type, plate 7 in FIG. 2 is of glass and is covered by a thin film of, for example, gold. P-polarized incident light coupled to the lower surface of the sensor plate 7 through a prism (not shown) is totally internally reflected at the glass-metal interface, an intensity dip appearing in the reflected light at a specific angle of reflectance due to surface plasmon resonance (SPR). The angle will vary with the refractive index of the solution close to the metal film, and by measuring the displacement of the reflectance minimum, the extent of changes in surface concentration of biomolecules may be determined. In this manner e.g. an immunoassay for an analyte in a solution may be performed by immobilizing an antibody to the metal surface, passing the sample over the surface and measure the change in resonance angle caused by the binding of analyte to the immobilized antibody.
If the sealing strips 5 in FIGS. 1 and 2 are of a material having a refractive index within the measuring range of the biosensor instrument, the reflected light from the metal surface opposite to the sealing strip may be used as a temperature reference, since the refractive index of the material will vary with the temperature and thereby be representative thereof. This may, for example, be used for controlling the necessary thermostating means.
The use in the method of the present invention of a modified counter mould having an elastic surface coating layer is illustrated in FIGS. 11 to 13. FIG. 11 schematically illustrates the manufacture of such a modified counter mould and shows a counter mould member 13 having two parallel grooves 14 which is applied to a mould plate 15 having protrusions or ridges 16 of a corresponding extension as the grooves 14. The ridges 16 are designed to define grooves in the elastic counter mould surface to be produced corresponding to grooves 9 in FIG. 6. Spacing means 17 extend from the surface of the mould plate 15 to keep the two mould members 13, 15 spaced from each other to define a mould gap therebetween. This mould gap has in FIG. 11 been filled with a fluid sealing material 18, such as a cross-linkable silicone rubber. When the sealing material 18 has hardened the counter mould 13 is removed from mould plate 15. FIG. 12 shows the resulting counter mould exhibiting an elastomeric mould surface with grooves 19 therein.
FIG. 13 illustrates the modified counter mould 13 applied to the flow cell bottom plate 1 of FIG. 6, for example. In comparison with the FIG. 6 embodiment the counter mould 13 has an elastic surface with grooves 19 corresponding to grooves 9 in FIG. 6. Reference numeral 20 designates cavities resulting from the spacing means 17 in FIG. 11.
Such a counter mould having an elastic mould surface is advantageous especially in that the surface smoothness requirements on the flow cell bottom plate 1, e.g. of silicon, may be reduced, and that the channels 6 may be arranged more closely, i.e. with smaller interspaces.
The invention is, of course, not restricted to the embodiments specifically described above and illustrated in the drawings, but many modifications and changes are possible within the scope of the present inventive concept as defined in the following claims. | A leakage-proof sealing means is provided in a microfluidic channel assembly of the type having first and second flat surface members which when pressed against each other define a microfluidic channel system between them, by recessing a sealing groove structure into the flat surface of the first member, and applying against the first member a counter mould surface having an aligned groove and/or ridge structure of smaller width than the sealing groove structure to define a mould cavity therewith, into which a fluid sealing material is introduced and hardened to form a resilient seal, the top part of which projects above the edges of the sealing groove structure while leaving sufficient space in the upper part thereof to permit complete accommodation of the top part of the resilient seal when compressed by the second assembly member. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a baler particularly suitable for forming bales of hay or other similar products.
Conventional balers generally comprise a front spring-mounted pick-up roller, which raises the hay from the ground and conveys it along a tubular member, hereinafter indicated by the term "rear tube", inside which the hay or straw is first compressed against a mobile obstacle, and then bound by one or more binding assemblies to form bales, which are discharged in succession through a rear open end of said rear tube.
The aforesaid known balers have certain drawbacks, due mainly to the fact that said binding assemblies are mounted directly on brackets and supports rigid with said rear tube.
A first consequence of this construction is that since the binding assemblies are assembled during their mounting on to said rear tube, the binding assemblies can be tested only when the baler is substantially finished. Moreover, with regard to the rear tube, a relatively high constructional precision is normally required, due to the fact that the support and connection points for a number of mutually cooperating mechanical members constituting the binding assemblies are disposed thereon. Such precision assembly is impossible in the case of a member constituted of welded plate, as in the case of said rear tube, the binding assemblies can be mounted only as the result of long and costly adjustments, which have to be carried out individually on each rear tube, which considerably influences the production cost of the entire baler.
Finally, the structural unity between the binding assemblies and said rear tube considerably complicates any repairs on the binding assemblies, and any necessary replacement of component parts thereof, as these operations automatically mean the baler cannot be used for relatively long periods, and it becomes substantially impossible to fit the same baler with a number of interchangeable binding assemblies using different binding materials, such as twine made from natural or synthetic fibres, and metal wire.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a baler which is free from the aforesaid drawbacks.
The said object is attained according to the present invention by a baler comprising a rear tubular member of substantially parallelepiped section and arranged to be traversed by material to be baled, and a binding unit comprising at least one binding assembly disposed on said tubular member and arranged to cooperate with said material in order to bind it into bales as it moves along said tubular member, characterised in that the top of said tubular member comprises an aperture, and said binding unit comprises a modular frame connected to the tubular member by connection means; said frame supporting said binding assembly and at least partly closing said aperture.
In the aforesaid baler according to the present invention, the presence of said modular frame makes it possible to assemble the binding assemblies on the work bench and to test the entire binding unit before mounting it on said tubular member by means of said connection means.
In this manner, all the aforesaid adjustment operations are substantially dispensed with because of the fact that as said modular frame is of relatively small dimensions, it can be constructed with relatively narrow tolerances without this involving costs which would nullify the considerable economical advantages deriving from the fact that the binding units are series-assembled and are tested on the work bench.
The presence of said frame also enables the entire binding unit to be immediately replaced without having to stop the baler, with obvious advantages for the user both in the case of defects and in the case of the user himself wishing to change the type of binding by replacing the actual binding unit with another binding unit using a different binding material. For this purpose, the user has only to detach the connection means in order to remove the frame from the tubular member, on which a new binding unit can then be mounted.
BRIEF DESCRIPTION OF THE DRAWINGS
Further characteristics and advantages of the present invention will be apparent from the description given hereinafter with reference to the accompanying drawings, in which:
FIG. 1 is a partly exploded perspective view, with parts removed for clarity, of the rear end of a baler according to the present invention;
FIG. 2 is a perspective enlarged view of a detail of FIG. 1;
and
FIG. 3 is a perspective view of the detail of FIG. 2, completed by means of two binding assemblies of known type.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a baler indicated overall by 1, in which a front roller (not shown) provided with radial springs and driven by a tractor by way of a Gardan shaft is arranged to collect from the ground in known manner the hay or straw to be baled, and to feed it through an aperture 2 to a tubular member 3, known as the rear tube, which extends towards the rear of the machine 1 and has a substantially parallelepiped section.
As shown in FIG. 1, the tube 3 is constituted by two U-shaped metal longitudinal members 4 and 5 mounted with their concavity opposing each other. The longitudinal members 4 and 5 each comprise a web 6, an upper flange 7 and a lower flange 8, which joined together at their front end by an upper plate 9 welded to the flanges 7 and a lower plate 10 welded to the flanges 8. The upper flanges 7 are also joined together by two cross members 11 and 12 constituted by strips disposed on their edge and defining between themselves and together with the edges of the two flanges 7 an upper aperture 13 of substantially rectangular shape. The two flanges 7 are also connected together by a U-shaped piece 14 disposed to the rear of the cross member 11 and in contact with it.
As shown in FIG. 1, the aperture 2 is provided through the web 6 of the longitudinal member 5 immediately upstream of the aperture 13 in the direction of movement of the material to be baled along the tube 3, said direction of movement being indicated by an arrow 15 in FIG. 1.
Pairs of bores 16 are provided through each web 7 in the space between the cross members 11 and 12, and a bore 16 is also formed in each flange 6, each of the bores being arranged to be engaged by a related bolt 17 for connecting a binding unit indicated overall by 18 and mounted on the tube 3 between the cross members 11 and 12 in such a manner as to at least partly close the aperture 2.
As shown in particular in FIG. 3, the binding unit 18 comprises a modular frame 19, in which are mounted two identical binding assemblies 20 arranged to bind the material moving along the tube 3 into bales.
The frame 19 comprises two parallel side plaes 21 and 22 disposed in a substantially vertical position, each substantially in the form of a rectangular trapezium disposed with its major base 23 at the bottom, its minor base 24 at the top and a vertical edge 25 facing the front end of the machine 1.
The base 23 is inclined downwards towards the rear end of the machine 1 starting from the lower end of the edge 25, and converges towards the rear end of a respective upper edge 26 which is inclined downwards starting from the rear end of the base 24. Stiffening ribs indicated by 27, 28 and 29 extend outwards from the base 23 and from the edges 25 and 26, respectively.
The side plates 21 and 22 are joined together by means of an upper tie bar 30 which connects together the upper ends of the ribs 28, and by a base 31 which rests on the flanges 7 of the tube 3 in the space between the strips 11 and 12 in order to at least partly close the aperture 13.
Each plate 21, 22 is provided with a bore 22a aligned with the bores 16 of the corresponding webs 6, and engaged by the related bolts 17.
In FIG. 2, the base 31 is defined at its front by an angle section 32 comprising a substantially vertical flange 33 welded to the lower ends of the ribs 28, and a substantially horizontal flange 34 extending rearwards between the plates 21 and 22, and defined at its rear by a substantially vertical plate 35 extending between two intermediate points of the plates 21 and 22 and rigid therewith. The base 31 also comprises two angle sections 36 (FIG. 1) and 37, one flange of which is welded into contact with the respective plates 21, 22, whereas the other flange, indicated by 38, is disposed in contact with the adjoining flange 7 and comprises two through slots 39 engaged by the related bolts 17 (FIG. 1). The flanges 38 are disposed on opposite sides of two further angle sections 40 and 41, each of which has a flange 42 rigidly connected to the flanges 34 and 35, respectively and a flange 43 which extends vertically downwards from the inner edge of the corresponding flange 42. The flange 42 of the section 40 comprises a recess along an edge thereof facing the corresponding flange 38, to define an elongated through aperture 44.
A central U-shaped section 45 is disposed between the sections 40 and 41, and has its web 46 rigidly connected to the flange 34 and plate 35, and its flanges 47 extending downwards parallel to the flanges 43, with which they define two slots 48 disposed on opposite sides of the section 45 and extending perpendicular to the flanges 34 and 35 throughout; the entire base 31. The base is further provided with an aperture 49 similar to the aperture 44 and provided centrally through the web 46.
From the flange 34 there extend upwards two pairs of appendices defining two forks 50 rotatably supporting two straw retention arms (not shown) arranged to penetrate into the tube 3 through the apertures 44 and 49 in order, in known manner, to halt the flow of straw to the tube 3 during a binding operation carried out by the binding unit 18. As shown in FIG. 3, the binding unit comprises two binding assemblies 51 of known type, each of which is supported at its rear end by a separate bracket 52 extending forwards and upwards from the plate 35 and rigid therewith.
Each binding unit 51 is controlled by a separate cam 53 keyed on to a shaft 54 supported by bearings 55 housed in the recesses 56 provided in the minor base 54 of each of the plates 21 and 22. The shaft 54 is connected by a clutch 57 to a gear wheel 58 for driving the unit, and the angular connection between the wheel 58 and shaft 54 is controlled by the position of a lever 59 rotatable about a pivot 60 as the result of its connection by a rack-pinion coupling 61 to a shaft 62 supported by two struts 63 extending upwards from the edges 26 in a direction substantially perpendicular to the edges 26. A star wheel 64 is keyed on to the shaft 62, and is rotated by the straw advancing along the tube 3.
On one end of the shaft 54 there is keyed a crank 65 which, by way of a connecting rod 66, operates a lever 67 supporting two needles 68 arranged to move with pendular motion through the tube 3 and to extend through the two slots 48 in order to bring two wires (not shown) into cooperation with the binding units 51. The lever 67 is substantially of U-shaped configuration, and comprises two lateral arms 69 pivoted at 70 to the plates 21 and 22, and a central rod 71 supporting the needles 68.
One of the struts 63 is provided with a welded side bracket 72 which supports an adjustable stop 73 arranged to control the width of the angular movement of the lever 59.
Finally, the frame 19 comprises two wire guide brackets 74 of substantially triangular shape, welded respectively on to the plates 42 and 43 above the slots 48 and supporting wire tensioning sectors, not shown.
As the binding assemblies 20 are of known type, a detailed description of their operation is superfluous herein. What however is important to note is the fact that all the connectors and supports for the binding assemblies 20 are carried by the frame 19 and not by the tube 3, as in the case of known balers.
Within the principle of the invention, numerous modifications can be made to the baler 1 described by way of non-limiting example, without this leaving the scope of the present invention. | A baler having a tubular member arranged to be traversed by the material to be pressed and collected into bales, the tubular member having an upwardly opening aperture therein, a modular binding unit comprising at least one binding assembly and a modular frame for supporting the binding assembly, the modular frame being detachably connected to the tubular member and positioned to at least partially close the aperture therein, the modular frame serving to mount the binding assembly in operative relation with respect to the tubular member. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority under 35 U.S.C. § 119(e) to U.S. provisional patent application Ser. No. 60/650,185, filed Feb. 7, 2005, which is incorporated herein by reference in its entirety
BACKGROUND OF THE INVENTION
This invention is directed toward the measure of temperature, and more particularly toward a sensor for measuring temperature of well borehole environs in the vicinity of a borehole instrument that is conveyed along the borehole. The temperature sensor is removably disposed preferably within the wall of the borehole instrument. The sensor can be embodied in a wide variety of borehole exploration and testing equipment including measurement-while-drilling, logging-while-drilling, and wireline systems.
FIELD OF THE INVENTION
Borehole geophysics encompasses a wide variety of measurements made with an equally wide variety of apparatus and methods. Measurements can be made during the drilling operation to optimize the drilling process, where borehole instrumentation is conveyed by a drill string. These measurements are made with systems commonly referred to as measurement-while-drilling or “MWD” systems. It is also of interest to measure, while drilling, properties of formation materials penetrated by the drill bit. These measurements are made with systems commonly referred to as logging-while-drilling or “LWD” systems, and borehole instrumentation is again conveyed by a drill string. Subsequent to the drilling operation, borehole and formation properties can be made with systems commonly referred to as “wireline” systems, with borehole instrument being conveyed typically by a multiconductor cable. Various types of formation testing is also performed both during the drilling of the borehole, and after the borehole has been drilled or “completed”, using drill string conveyed and wireline conveyed instrumentation.
The temperature of fluid within the borehole is a parameter of interest in virtually all types of geophysical exploration. A measure of temperature of liquid or gas within the annulus formed by the borehole wall and the borehole instrument is of particular interest. A variation in annulus temperature at a particular depth within the borehole can indicate formation liquid or gas entering or leaving the borehole at that depth. Such information can, in turn, be related to formation fracturing, formation damage, wellbore tubular problems, and the like. A measure of annulus temperature as a function of depth can define thermal gradients which, in turn, can be related to a variety of geophysical parameters and conditions of interest. Certain electromagnetic, acoustic and nuclear formation evaluation logging systems, both drill string and wireline conveyed, require corrections for annulus temperature in order to maximize measurement accuracy and precision.
From the brief discussion above, it is apparent that methods and apparatus for measuring annulus temperature are critical to a wide variety of geophysical operations. It is desirable that an annulus temperature measurement system be accurate and precise. It is further desirable for the measurement system to respond rapidly to any changes in temperature. Ruggosity is required for the harsh conditions typically encountered a borehole environment. Operationally, it is desirable to dispose an annulus temperature sensor in the wall of the borehole instrument defining the annulus. Furthermore, it is operationally advantageous if the sensor can be easily removed and replaced from the outside of the borehole instrument therefore removing the need to dismantle the instrument. As an example, sensors may be designed for maximum response in a given temperature range. If the range is exceeded, it is advantageous to replace the sensor optimized for another range. Ease of replacement is also operationally advantageous in the event of sensor failure.
BRIEF SUMMARY OF THE INVENTION
The present invention comprises a sensor assembly that responds to temperature of fluids within an annulus formed by an outer surface of a borehole instrument and the wall of a borehole. The sensor assembly is removably installed preferably in the wall of the borehole instrument. Installation and removal are from outside of the borehole instrument thus eliminating the need to disassemble the instrument. The sensor assembly comprises a temperature transducer that is hermetically sealed within a housing. The housing is designed to obtain maximum thermal exposure of the transducer. This yields optimum thermal response of the transducer to temperature variations in the surrounding annulus environment. The sensor is designed to operate at high temperature, high pressure, and high vibration/shock typically encountered in the borehole environment. The sensor assembly housing has a locking feature to ensure that it remains in the borehole instrument during operation. Power to the temperature transducer is supplied from a separate electronics package in the borehole instrument through a rotary connector within the sensor housing. Response of the temperature transducer is received, through the same rotary connector, by the electronics package for processing and transmission via a suitable telemetry system to the surface of the earth.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features, advantages and objects the present invention are obtained and can be understood in detail, more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings.
FIG. 1 is a cross sectional view of the temperature sensor assembly;
FIG. 2 is an exploded view of major elements of the temperature sensor assembly;
FIG. 3 is a sectional view of the temperature sensor assembly mounted in a cylindrical receptacle in the wall of a borehole instrument;
FIG. 3A is a sectional view of the temperature sensor assembly mounted in a thermal isolator insert and within a cylindrical receptacle in the wall of a borehole instrument and
FIG. 4 illustrates conceptually the temperature sensor assembly disposed in a well borehole for measuring temperature of borehole fluids.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a cross sectional view of the temperature sensor assembly 10 . Internal elements of the assembly 10 are hermetically sealed within a cylindrical housing 12 . The housing material is preferably beryllium-copper, although other metals or alloys such as Inconel can be used. The top or “outer” end of the housing 12 , as will be shown in subsequent illustrations, is exposed to borehole fluid. This outer end comprises a protrusion 13 . A temperature transducer 14 is disposed inside of the housing and positioned within the protrusion 13 . The transducer 14 is in thermal contact with the housing 12 , and is preferably soldered to the housing to insure good thermal contact. This arrangement surrounds, as much as practical, the temperature transducer 14 with borehole fluid thereby maximizing the response of the temperature transducer to borehole fluid temperature. Electrical leads 16 a and 16 b from the temperature transducer 14 extend through an “upper” connector assembly. The upper connector comprises an upper insulating base member 24 , and outer electrical contact 22 , and an inner electrical contact 18 . The electrical leads 16 a and 16 b terminate at the electrical contacts 18 and 22 , respectfully.
Still referring to FIG. 1 , a large spring 28 and a small spring 26 are positioned coaxially within the housing 12 . The upper end of the large spring 28 is in electrical contact with the outer electrical contact 22 , and the upper end of the small spring 26 is in electrical contact with the inner electrical contact 18 . Opposing or lower ends of the large spring 28 and small spring 26 contact a rotary connector assembly. The rotary connector assembly or “rotary connector” is illustrates as a whole in FIG. 2 , and designated by the numeral 41 . The assembly 41 comprises an outer sensor contact 30 which is in electrical contact with the large spring 28 , and an inner sensor contact 34 which is in electrical contact with the small spring 26 . An insulator ring 31 separates the two sensor contacts 30 and 34 . The large and small springs 28 and 26 , respectively, serve as electrical conductors between the temperature transducer 14 and the rotary connector assembly 41 . Both springs also provide a mechanical load to the rotary connector assembly 41 . The rotary connector assembly 41 , large spring 28 and small spring 26 are retained in the housing 12 by a retaining ring 40 . The rotary connector assembly 41 also comprises an electrical insulating base member 36 forming an insulating ring 31 containing alignment indentions 33 . The insulating base member 36 defines the lower or “inner” end of the sensor 10 , and is penetrated by extensions of the sensor contacts 30 and 34 in the form of protrusions, as shown in FIG. 1 . These protrusions are hermetically sealed with O-rings rings 44 . The insulating base 36 is hermetically sealed to the interior of the housing 12 by an O-ring 46 . The insulating base 36 also has an alignment tab 54 which properly aligns the rotary connector assembly 41 within the borehole instrument wall in which it is received. Alignment will be discussed in a subsequent section of this disclosure.
The temperature sensor assembly 10 is threaded into a cylindrical receptacle in the wall of the borehole instrument via the threads 42 . Hermetic sealing between the housing 12 and the borehole instrument receptacle is provided by O-rings 50 and cooperating back-up rings 52 .
FIG. 2 is an exploded view of major elements of the temperature sensor assembly 10 , and best illustrates the functionality of the rotary connector assembly which allows the temperature sensor to be inserted and removed from the wall of a borehole instrument. The housing 12 , transducer 14 , upper base member and connector assembly 24 , large spring 28 , and small spring 26 all rotate with respect to the rotary connector assembly 41 . As the housing 12 is threading into or out of the borehole instrument wall, the O-ring 46 maintains a hermetic seal within the housing 12 as it is rotated with respect to the rotary connector assembly 41 . The rotary connector assembly 41 is held fixed with respect to the wall of the borehole instrument by the alignment tab 54 which is received in a slot within the wall of the borehole instrument. Hermetic seal between the outer surface of the sensor housing 12 and the cylindrical borehole instrument receptacle is maintained by the O-rings and back-up rings 50 and 52 , respectfully, as the sensor assembly 10 is threaded into or out of the wall of the borehole instrument. The outer end of the housing 12 is fabricated to receive an appropriate means for turning, such as an Allen wrench or the like.
FIG. 3 is a sectional view of the temperature sensor assembly 10 mounted in a cylindrical receptacle 62 in the wall 60 of a borehole instrument. O-rings 50 and back-up rings 52 are shown hermetically sealing the housing 12 within the wall 60 of the borehole instrument. The lower portion of the temperature sensor assembly 10 is cut away to show the cooperation of the elements of the rotary connector assembly 41 with elements of the borehole instrument wall. The male threads 42 on the housing 12 are received by corresponding female threads 42 a cut at the base of the receptacle 62 . The alignment tab 54 is received by a slot in the borehole instrument wall 60 so that the rotary connector assembly is held fixed with respect to the instrument wall. The alignment tab 54 is also positioned so that the sensor contacts 30 and 34 are aligned and make electrical contact with corresponding borehole instrument or “tool” contacts 72 and 70 , respectfully. Power for the temperature transducer 14 (see FIGS. 1 and 2 ) is supplied by an appropriate power supply in an electronics package 78 via electrical leads 74 and 76 which terminate at the tool contacts 72 and 70 , respectively. The electronics package 78 and leads 74 and 76 are hermetically sealed within the borehole instrument wall. The sensor and tool contact arrangement allows the temperature sensor 10 to be inserted into and removed from the instrument wall 60 without disturbing the “tool” hermetic seal of elements within the instrument wall 60 . Response of the temperature transducer 12 is conveyed from the sensor assembly 10 via the sensor contacts 30 and 34 through the tool contacts 72 and 70 and to the electronics package 78 via the leads 74 and 76 . Temperature sensor response is typically telemetered from the electronics package 78 to the surface of the earth for processing and use, as illustrated conceptually with the arrow 79 . Optionally, the sensor response can be processed within the electronics package 78 . These processed results can be recorded in the electronics package, or used to control or correct functions of other sensors or equipment disposed within the borehole instrument.
As shown in FIG. 3 , the housing 12 is disposed entirely within a radius defined by the outer surface of the borehole instrument wall 60 . Alternately, the housing 12 can protrude outside of the radius defined by the outer surface of the borehole instrument wall 60 .
It is advantageous for the temperature sensor assembly 10 to respond to changes in drilling fluid temperature as quickly as possible. The wall 60 of the borehole instrument is typically massive and does not, therefore, rapidly reach thermal equilibrium with the drilling fluid temperature. Response of the temperature sensor assembly 10 to changes in drilling fluid temperature can, therefore, be maximized by thermally isolating the temperature sensor assembly 10 , and the transducer 14 therein, from the wall 60 of the borehole instrument. One method for thermal sensor assembly isolation is shown in FIG. 3A . The cylindrical receptacle 62 in the wall 60 of the borehole instrument is lined with a thermal isolator insert 51 . The thermal isolator insert 51 is fabricated from any suitable temperature insulating material, such as composite graphite or thermal plastic, that can function within the typically harsh borehole environment. The male threads 42 on the housing 12 are received by corresponding female threads 42 b cut at the base of the thermal isolator insert 51 . The alignment tab 54 is received by a slot in the thermal isolator insert 51 so that the rotary connector assembly is held fixed with respect to the instrument wall, as is the case in the embodiment shown in FIG. 3 . Once again, the alignment tab 54 is positioned so that the sensor contacts 30 and 34 are aligned and make electrical contact with corresponding contacts 72 and 70 , respectfully. Power for the temperature transducer 14 is again supplied by an appropriate power supply in an electronics package 78 via electrical leads 74 and 76 . The leads 74 and 76 are disposed within the borehole instrument wall 60 and within the thermal isolator insert 51 , and terminate at the tool contacts 72 and 70 , respectively. FIG. 3A illustrates one means for thermally isolating the temperature transducer 14 from the wall 60 of the borehole instrument. It should be understood that the desired thermal isolation of the temperature transducer 14 can be obtained using other embodiments, such as fabricating the housing 12 with a thermally insulating material.
FIG. 4 illustrates conceptually the temperature sensor assembly 10 disposed in a well borehole for measuring temperature of borehole fluids. A borehole instrument 84 is suspended in a well borehole 92 that penetrates earth formation 90 . The borehole instrument is operationally connected to a lower end of a data conduit 82 by a suitable connector 83 . The upper end of the data conduit 82 is operationally connected to a conveyance means 80 at the surface 96 of the earth. The conveyance means 80 is operationally connected to surface equipment 89 which can power and transmit down-link data to the borehole instrument 10 , and receive and process up-link data transmitted from the temperature sensor assembly 10 and other instrumentation within the borehole instrument 84 . The temperature sensor 10 responds primarily to temperature of borehole fluid in the annulus defined by the outer surface of the borehole instrument 84 and the wall 94 of the borehole 92 .
As mentioned previously, the temperature sensor assembly 10 can be embodied in LWD, MWD, wireline and other types of borehole systems. If embodied in an LWD or MWD system, the borehole instrument 84 is typically a drill collar, the data conduit 82 is a drill string, and the conveyance means 80 is a rotary drilling rig which incorporates an appropriate telemetry system, such as a mud pulse system. If embodied in a wireline system, the borehole instrument 84 is typically a cylindrical pressure housing, the data conduit 82 is a logging cable cooperating with a suitable up-hole and down-hole telemetry system, and the conveyance means 80 is a wireline draw works assembly.
While the foregoing disclosure is directed toward the preferred embodiments of the invention, the scope of the invention is defined by the claims, which follow. | A sensor assembly that responds to temperature of fluids within an annulus formed by an outer surface of a borehole instrument and the wall of a borehole. The sensor assembly is removably installed preferably in the wall of the borehole instrument. Installation and removal are from outside of the borehole instrument thus eliminating the need to disassemble the borehole instrument. The sensor assembly comprises a temperature transducer that is hermetically sealed within a housing designed to obtain maximum thermal exposure of the transducer. Power to the temperature transducer is supplied from a separate electronics package in the borehole instrument through a rotary connector within the sensor housing. | 4 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims benefit of prior filed copending provisional application Appl. No. 60/006,929, filed Nov. 17, 1995.
BACKGROUND OF THE INVENTION
The present invention refers to a tensioning device for traction means such as belts and chains, and in particular to a tensioner of a type including a tensioner arm which carries a tensioning member, preferably a tension roller, and is spring-loaded in direction toward the traction means, with the tensioner arm being rotatably supported relative to a fixed structure by means of a conical sliding bearing which exhibits sliding bearing surfaces in parallel relationship to one another and positioned concentrically to the tensioner arm shaft, and a helical torsion spring wound about the tensioner arm shaft and extending between a support secured on the tensioner arm and a fixed support.
A tensioning device of this type is known e.g. from U.S. Pat. No. 4,698,049. The tensioner arm shaft and the fixed structure exhibit each a conical surface, with a conical sliding bearing bush being disposed between these two conical surfaces. A radial play in the sliding bearing caused by abrasive wear on the sliding bearing surfaces requires that the conical surfaces of the sliding bearing be pushed manually toward each other in axial direction and so positioned that the radial play in the sliding bearing again lies within an admissible tolerance range.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved tensioning device of this type, obviating the afore-stated drawbacks.
In particular, it is an object of the present invention to provide an improved tensioning device which allows an automatic adjustment of the sliding bearing surfaces in a simple and yet reliable manner.
These objects and others which will become apparent hereinafter are attained in accordance with the present invention by incorporating a helical torsion spring which is so clamped between a support secured to the tensioner arm and a fixed support as to exert an axial force which is introduced into the sliding bearing in the form of a reaction force that acts perpendicular to the sliding bearing surfaces.
The provision of such a tensioning device results in numerous advantages. Firstly, it is ensured that upon abrasive wear of the sliding bearing surfaces the axial force and the reaction force acting perpendicular to the sliding bearing surfaces pushes the sliding bearing surfaces together so as to effect a clearance-free sliding bearing. At constant angle of inclination of the sliding bearing surfaces relative to their axis, the reaction force can be varied commensurate with the axial attachment and the axial force of the helical torsion spring.
Typically, the sliding bearing includes a conical sliding bearing bush of plastic material which is in frictional contact and thus subject to increased wear by sliding friction as a consequence of the perpendicular reaction force. This wear by sliding friction is compensated without any problems by a self-adjusting motion of the tensioner arm and the fixed structure. When the tensioner arm shaft and the fixed structure are each formed with a conical surface, it is possible to loosely dispose the conical sliding bearing bush between these conical surfaces. At operation, a sliding friction is normally encountered between the outer conical surface of the sliding bearing bush and the adjoining stationary or tensioner arm fixed conical surface at same friction conditions on the sliding bearing surfaces. The helical torsion spring of the tensioning device according to the present invention is subject to a torsional load in a same manner as described in the prior art and spring-loads the tensioner arm against the traction means.
U.S. Pat. No. 4,698,049 further discloses a damping unit for damping swinging motions of the tensioner arm relative to the fixed structure. This damping unit is formed by providing the fixed structure and the tensioner arm shaft with terminal end faces that oppose each other, with a friction disk being disposed between theses end faces. The end face associated to the fixed structure is formed on a separate disk. Compared to conventional tensioners, a tensioning device according to the present invention realizes a damping unit, without necessitating additional measures. The sliding friction between the sliding bearing surfaces is increased as a result of the reaction force and the resulting surface pressure, respectively, so that the desired damping effect is accomplished in both rotational directions of the tensioner arm.
In a helical torsion spring which is e.g. axially compressed to exert an axial force, a particularly advantageous disposition of the spring supports and the sliding bearing surfaces is attained when the sliding bearing surface associated to the tensioner arm is disposed radially outwards, and the sliding bearing surface associated to the fixed element is disposed radially inwards, whereby in direction from the converging ends of the sliding bearing surfaces toward the diverging ends of the sliding bearing surfaces, the fixed support is positioned ahead of the tensioner arm based support. It is however also conceivable to form, in the event the helical torsion spring is axially compressed to exert an axial pressure force, the sliding bearing surface associated to the tensioner arm radially inwards and the sliding bearing surface associated to the fixed structure radially outwards, whereby in direction from the converging ends of the sliding bearing surfaces toward the diverging ends of the sliding bearing surfaces, the tensioner arm based support is now positioned ahead of the stationary support. Both dispositions result in the generation of a reaction force that acts perpendicular to the sliding bearing surfaces, without necessitating any additional components or measures.
A tensioning device in accordance with the present invention is typically employed for aggregate drives of engines of motor vehicles. Upon construction of such a tensioning device, consideration should be taken also with regard to i.a. existing spatial needs.
In accordance with an especially space-saving embodiment of the tensioning device, the tensioner arm shaft fixed on the tensioner arm is formed radially within the sliding bearing with an axially open recess for receiving the helical torsion spring, whereby the recess is radially overlapped by the fixed support. This variation is particularly advantageous because the radially outer sliding bearing exhibits a reduced surface pressure as a consequence of the circumferentially increased sliding bearing surfaces, and therefore is subject to a reduced abrasive wear.
According to another embodiment of the present invention, which is particularly advantageous with respect to installation, the tensioning device includes a fixed structure of pot-shaped configuration with a bottom, a cover and a jacket between the bottom and the cover, for accommodating the tensioner arm fixed tensioner arm shaft, with the cover defining the fixed support for the helical torsion spring and being secured to the jacket e.g. by means of bayonet fastener. Suitably, the fixed structure is formed with a circumferential slot through which the tensioner arm is radially guided.
According to a further variation, the stationary tensioner arm shaft is formed with a cylindrical section, with a conical bush being secured, preferably detachably, to this section and exhibiting an outer conical surface and an inner cylindrical surface. The tapered end of the conical bush faces the tensioner arm shaft at an end that is distant to the tensioner arm, with the tensioner arm shaft being formed with a coaxial throughbore. This ensures that the tensioner arm, which is formed with a conical bore coaxial to the tensioner arm shaft, and the tensioner arm shaft, which is formed in one piece with the tensioner arm, can be placed together with the conical bush and the helical torsion spring on the tensioner arm shaft. As a result of the axial force exerted by the torsion spring, the tensioner arm and the conical bush are suitably secured against sliding off axially from the tensioner arm shaft. Suitably, a screw positioned in coaxial disposition to the tensioner arm shaft can be screwed into the end face of the tensioner arm end at the free end of the tensioner arm shaft, with one end of the conical bush being axially supported on the screw head. It may be suitable to guide this screw through the coaxial throughbore of the tensioner arm shaft and to screw it into the engine block. In this manner, the screw accomplishes two functions, that is, firstly, the securement of the tensioner arm shaft to the engine block, and, secondly, the axial securement of the tensioner arm and the conical bush.
In accordance with a further feature of the present invention, the support is formed by a support disk which is secured to the tensioner arm shaft at an end facing away from the tensioner arm, with the converging ends of the sliding bearing surfaces facing the support disk. In such a tensioning device, the fixed support is preferably formed with a conical bore which exhibits a diverging end adjacent the tensioner arm. The tensioner arm shaft, formed preferably in one piece with the tensioner arm, is inserted in the conical bore and has a free end axially extending beyond this conical bore, with the support disk being preferably press-fitted on this end. In this case, there is no need to specially secure the support disk against axial displacement upon the tensioner arm shaft. The conical bore wall of the conical bore forms in this case the one sliding bearing surface.
There is no need to design the conical bush as a separate component. It may also be suitable to provide the conical outer jacket of the tensioner arm shaft with circumferentially spaced holes and to form a sliding bearing bush through spraying sliding bearing material onto the jacket to penetrate the holes and engage therebehind. In this manner, an intimate connection e.g. between the tensioner arm and the sliding bearing bush is effected.
Particularly favorable force relationships in the sliding bearing are accomplished when the angle of inclination of the sliding bearing surfaces relative to the tensioner arm shaft ranges between 8° and 30°.
In some circumstances, it may be advantageous to provide at least one sliding bearing surface with circumferentially spaced pockets containing lubricant to ensure optimum damping and sliding properties over an extended period. The lubricant pockets may certainly also be provided on a sliding bearing bush.
Taking into account the load upon the sliding bearing, it is suitable to securely clamp both ends of the helical torsion spring. This ensures that the torsion of the spring does not result in any radial forces which are directed into the sliding bearing and cause undesired edges stress. A secure attachment of the spring ends can also be attained when subjecting each of both ends of the helical torsion spring under torsion by a pair of forces which acts transversely to the longitudinal axis of the helical torsion spring. This is for example the case when the spring as a result of its torsion is supported with its angled end by a tensioner arm fixed first point of support, with one supporting force of one pair of forces acting thereon. The helical torsion spring has a winding connected to this end and bearing upon a second point of support, with the second supporting force of the one pair of forces acting thereon. The other pair of forces is formed in like manner on stationary support points. This also ensures that as a result of the clamped helical torsion spring, no further radial forces act on the sliding bearing.
In a tensioning device according to the present invention, the diverging ends of the sliding bearing preferably face the tensioner arm. Certainly, a reversal of this configuration also results in the advantages as attained by the present invention; However, an increased surface pressure and a resulting increased abrasive wear can be encountered at the converging end of the sliding bearing.
BRIEF DESCRIPTION OF THE DRAWING
The above and other objects, features and advantages of the present invention will now be described in more detail with reference to the accompanying drawing in which:
FIG. 1 is a longitudinal section of one embodiment of a tensioning device according to the present invention,
FIG. 2 is a schematic illustration of a sliding bearing bush for use in a tensioning device according to the present invention;
FIG. 3 is a fragmentary cross sectional view of the sliding bearing bush of FIG. 2, taken along the line III--III in FIG. 2;
FIG. 4 is a schematic, sectional illustration of a modified tensioner arm shaft;
FIG. 5 is a schematic, sectional illustration of still another variation of a tensioner arm shaft;
FIG. 6 is a schematic, sectional illustration of a modified fixed structure;
FIG. 7 is a longitudinal section of another embodiment of a tensioning device according to the present invention, similar to the tensioning device of FIG. 1, however with modified tensioner arm fixed support;
FIG. 8 is a longitudinal section of still another embodiment of a tensioning device according to the present invention;
FIG. 9 is a longitudinal section of still another embodiment of a tensioning device according to the present invention; and
FIG. 10 is a fragmented, sectional view of the tensioning device, taken along the line X--X in FIG. 9 and showing in detail the securement of the ends of the helical torsion spring.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Turning now to the drawing, and in particular to FIG. 1, there is shown a longitudinal section of one embodiment of a tensioning device according to the present invention, including a tensioner arm 1 on which a tensioning roller 2 is secured for engagement on a not shown traction element, e.g. a belt or a chain. The tensioner arm 1 is rotatably supported relative to a housing 4 by a sliding bearing, generally designated by reference numeral 3. The housing 4 is provided with a conical bore 8 defined by a conical wall 7. Formed in one piece with the tensioner arm 1 is a tensioner arm shaft 5 which exhibits an outer conical surface area 6. The tensioner arm shaft 5 is received in the housing 4 within the conical bore 8. The sliding bearing 3 includes a sliding bearing bush 9 which is placed between the outer conical surface area 6 of the tensioner arm shaft 5 and the parallel conical wall 7 of the housing 4, and exhibits an inner conical surface 7 and an outer conical surface 12. In order to effect an interlocking or form-fitting connection between the sliding bearing bush 9 and the tensioner arm shaft 5, the sliding bearing bush 9 is formed with a projection 10 which engages a recess 11 of the tensioner arm shaft 5, as best illustrated in particular in FIGS. 2 and 3. The conical wall 7 and the outer conical surface 12 of the sliding bearing bush 9 form sliding bearing surfaces for rotatable support of the tensioner arm 1 relative to the housing 4. The tensioner arm shaft 5 has a tensioner arm distant end which extends beyond the conical bore 8 of the housing 4 for carrying a support disk 13 which is press-fitted onto this tensioner arm end. Persons skilled in the art will appreciate that the support disk 13 may certainly also be connected in form-fitting or material locking connection with the tensioner arm shaft 5.
Arranged coaxial to the tensioner arm shaft 5 is a helical torsion spring 14 which has one end secured to a support 15 formed by the support disk 13 and another end secured to a fixed support 16 formed by the housing 4. The helical torsion spring 14 is thus axially compressed between the supports 15, 16 to exert an axial pressure force F D and a torsion force F R acting perpendicular to the sliding bearing surfaces 7, 12. The diverging ends of the sliding bearing surfaces 7, 12 face the tensioner arm 1, whereby in direction from the converging ends of the sliding bearing surfaces 7, 12 towards the diverging ends of the sliding bearing surfaces 7, 12, the tensioner arm fixed support 15 is arranged ahead of the housing fixed support 16.
The tensioner arm 1 and the tensioner arm shaft 5 are made in one piece, preferably through a die casting process, with aluminum alloy being used as suitable material.
FIGS. 2 and 3 show details of the sliding bearing bush 9 and the formed projection 10, and it can be seen that the outer conical surface 12 has formed therein pockets 16a for receiving lubricant to ensure optimum damping and sliding properties over an extended period.
FIG. 4 shows another embodiment of a tensioning device according to the present invention, with a modified tensioner arm 1 in single piece construction with the tensioner arm shaft 5 which is formed by a cylindrical tube 17, with the sliding bearing bush 9 being applied by injection molding onto the cylindrical tube 17. Also in this case, the outer conical surface 12 is selected as sliding bearing surface. As a constant wall thickness should be maintained during injection molding, recesses 19 are formed within the sliding bearing bush 9 in direction towards the diverging ends of the sliding bearing surface 12.
In the event, the configuration of the tensioner arm shaft 5 of FIG. 1 is preferred, it is certainly possible to apply the sliding bearing bush 9 by injection molding onto the outer conical surface area 6 of the tensioner arm shaft 5, as shown in FIG. 5. To effect an intimate connection between the sliding bearing bush 9 and the tensioner arm shaft 5, the tensioner arm shaft 5 has a jacket 20 which is formed with holes 21, with sliding bearing material being sprayed onto the outer conical surface area 6 to penetrate the holes 21 and to engage therebehind.
The procedure described in FIG. 5 for forming the sliding bearing bush 9 can be applied in analogous manner also to the housing 4, as shown in FIG. 6. In this case, holes 22 are provided in a jacket 23 of the housing 4.
FIG. 7 shows a longitudinal section of another embodiment of a tensioning device according to the present invention, which differs from the tensioning device of FIG. 1 in the configuration of the tensioner arm fixed support 15. As shown in FIG. 7, the helical torsion spring 14 is secured with its end facing the support disk 13 in a groove 24 which is formed in the tensioner arm shaft 5, with the support disk 13 engaging in this groove 24 and axially supporting the helical torsion spring 14. A further difference to the tensioning device of FIG. 1 resides in the loose fit of the sliding bearing bush 9 between the tensioner arm shaft 5 and the housing 4. The sliding bearing bush 9 can thus freely rotate relative to the conical wall 7 as well as relative to the conical outer surface area 6 of the tensioner arm shaft 5.
The embodiment of a tensioning device according to the invention, as shown in FIG. 8, differs from the previous embodiments essentially in the configuration of the tensioner arm shaft 5 which is provided with an axially open recess 25 formed coaxial to the tensioner arm 1 for receiving the helical torsion spring 14. The housing 4 is of pot-shaped configuration and exhibits a bottom 26, an outer jacket 27 and a cover 28 which axially overlaps the jacket 27 and is secured thereto, with the fixed support 16 being formed by the cover 28 for supporting one end of the helical torsion spring 14. The other end of the helical torsion spring 14 rests against a bottom 31 formed by the tensioner arm shaft 5. The jacket 27 and the cover 28 define a circumferential slot 30 for receiving and radially guiding the tensioner arm 1 therethrough.
While in the preceding embodiments of the tensioning device, the tensioner arm shaft 5 is fixedly secured to the tensioner arm 1, FIG. 9 shows a tensioning device with a stationary tensioner arm shaft 32 which is formed with a support flange 33 for attachment to a not shown engine block. The tensioner arm shaft 32 includes a cylindrical section 34 for rotatably supporting a tensioner arm 35 via a sliding bearing, generally designated by reference numeral 36. The tensioner arm 35 includes a tensioner arm jacket 37 which extends coaxial to the tensioner arm shaft 32 and is formed with a conical bore 38, with the tapered end of the conical bore 38 facing away from the tensioner arm 35. Placed between the tensioner arm jacket 37 and the tensioner arm shaft 32 is a conical bush 39 which exhibits an outer conical surface area 40 and an inner cylindrical surface 41, with a conical sliding bearing bush 42 being disposed between the outer surface 40 of the conical bush 39 and the tensioner arm jacket 37. The conical sliding bearing bush 42 and the conical bush 39 may certainly be made in one piece of plastic material, e.g. by injection molding.
Sliding motions are effected in this case between the conical wall 43 of the conical bore 38 and an outer conical surface 44 of the conical sliding bearing bush 42. Clamped between the support flange 33 and a tensioner arm fixed support 46 is a coaxial helical torsion spring 45 to exert an axial pressure force F D and a torsion force F R which acts perpendicular to the sliding bearing surfaces 43, 44 of the sliding bearing 36. The tensioner arm shaft 32 is provided with a coaxial throughbore 47, with a screw 48 being directed through the throughbore 47 and screwed onto the not shown engine block. It is certainly possible to provide a washer between the screw head 49 and the sliding bearing bush 42 at the end face proximal to the screw head 49. This ensures that the sliding bearing bush 42 cannot slide off axially from the tensioner arm shaft 32.
FIG. 10 shows a cross section of the tensioning device of FIG. 9, however without the screw 48, for illustration of the tensioner arm fixed support 46. The angled end of the helical torsion spring 45 engages in an opening 50 of the support flange 33 and is supported circumferentially therein. The helical torsion spring 45 has a winding 51 secured to this end and bearing spotwise on the tensioner arm shaft 32 at two points of contacts which are acted upon by support forces F S to form a pair of forces. When configuring the stationary support for the helical torsion spring 14 in analogous manner, it is evident that the torsion of the helical torsion spring 45 does not generate a radial force that acts on the sliding bearing. The attachment of the helical torsion spring 45 on the supports, as illustrated with reference to the embodiments according to FIGS. 9 and 10, is certainly applicable in the same advantageous manner for the other embodiments.
Subsequently, the mode of operation of the tensioning device according to the invention is described. The disposition of the helical torsion spring 14, 45 in accordance with the present invention effects that the axial pressure force F D is introduced into the sliding bearing 3, 36 as a reaction force F R which acts perpendicular to the sliding surfaces 7, 12, 43, 44. The resulting increased friction dampens in advantageous manner swinging motions of the tensioner arm 1, 35. The tensioning device according to the invention ensures that the tensioner arm 1, is permanently swingably supported without significant clearance relative to the housing 4 and the stationary tensioner arm shaft 32, respectively. As soon as abrasive wear on the sliding bearing surfaces 7, 12, 43, 44 causes a play, an axial displacement of the tensioner arm shaft 5, 32 is effected relative to the tensioner arm 1, 35 to press the sliding bearing surfaces 7, 12, 43, 44 towards each other.
While the invention has been illustrated and described as embodied in a tensioning device for traction means with cone-type sliding bearing, it is not intended to be limited to the details shown since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
What is claimed as new and desired to be protected by letters patent is set forth in the appended claims: | A tensioning device for a traction element includes a tensioner arm having a tension roller which is spring-loaded against the traction element. The tensioner arm is rotatably supported relative to a housing by means of a conical sliding bearing exhibiting parallel sliding bearing surfaces which extend concentric to the tensioner arm shaft. A helical torsion spring wound along the tensioner arm shaft and clamped between a support secured on the tensioner arm and a fixed support area exerts an axial force which is introduced into the sliding bearing as a reaction force perpendicular to the sliding bearing surfaces. | 5 |
BACKGROUND OF THE INVENTION
This invention relates to a method for producing 100% mesophase pitch, as a raw material for high strength, high modulus carbon fibers. More particularly it relates to a method for producing 100% mesophase pitch which enables us to produce with a high efficiency and at a low price, high strength, high modulus carbon fibers which are preferable as a raw material for composite articles.
DESCRIPTION OF PRIOR ART
As the result of recent rapid growth of industries for manufacturing aircrafts, motor vehicles and other transport a demand for materials capable of exhibiting remarkable characteristics because of the superiority of some of their physical properties is ever increasing. Particularly, the demand for the advent of inexpensive materials provided with high strength and high modulus together with lightness of weight is great. However, since the material which satisfies the above-mentioned demand cannot be supplied in a stabilized manner according to the present status of art, research works relative to composite articles (reinforced resins) which meet the above-mentioned requirement are prevailing.
As one of the most promising material to be used as reinforced resin, there can be mentioned high strength high modulus carbon fibers. These materials have appeared from about the time when the rapid growth of the above-mentioned industry just started. When the carbon fibers are combined with a resin, it is possible to produce reinforced resins capable of exhibiting characteristic feature unparalleled in the past. To be regretful enough, however, in spite of the high strength and high modulus of the carbon fibers for the above-mentioned reinforced resins capable of exhibiting extremely notable characteristic feature, the application fields of these fibers have not expanded. The cause of this fact, as explained later, lies in the higher production cost.
It is well known that the material for high strength, high modulus carbon fibers which are commercially available are mostly polyacrylonitrile fibers produced by a special production process and a special spinning process but these acrylonitrile fibers are not only expensive as a precursor of carbon fibers but also the production yield thereof from the precursor is as low as less than 45%. These facts complicate the treatment steps for producing superior carbon fibers, resulting in the increasing production cost of the ultimate products of carbon fibers.
As for the methods for producing inexpensive raw materials for carbon fibers, there are many reports in such as U.S. Pat. No. 3,974,264 and U.S. Pat. No. 4,026,788 issued to E. R. McHenry and assigned to Union Carbide Corporation etc. Beside these, there are many reports in the official gazettes of patent publications. According to these methods, petroleum origin pitch or tar-origin pitch is subjected to heat treatment at a temperature of 380° C. to 440° C. to produce a pitch containing 40% to 90% preferably 50% to 65% mesophase and resulting products are used, as they are, for raw materials for carbon fibers. Accordingly, these products contain a large amount of non-mesophase pitch and cannot be called as 100% mesophase pitch which is required as a raw material for high strength, high modulus carbon fibers and is not provided with the characteristic properties of 100% mesophase pitch.
Further, there is a method which is directed to the production of a mesophase claiming to be essentially 100% mesophase, in the official gazette of Japanese laid open patent No. 55625 of 1979. According to this method, inert gas such as nitrogen, argon, xenon, helium, steam, etc. in a very large amount e.g. at least 8 l per kg raw material per minutes is introduced under pressure into isotropic pitch which is then subjected to heat treatment at a temperature of 380° C. to 430° C., with vigorous stirring even for 5 to 44 hours, until it is converted into a single phase system. Thus an attempt is made to produce a so-called 100% mesophase pitch. However, the isotropic pitch of raw material is of so-called huge molecule, complicated and not a pure compound. It contains impurities and forms emulsion. No matter how long a time, inert gas is compressed into and no matter how vigorously stirring treatment is applied to the pitch, it is impossible to simplify the emulsion completely. In any way, it is impossible to avoid the mixing of non-reacted isotropic pitch, completely and resulting product cannot be said to be a 100% mesophase.
It is an object of the present invention to provide a method for producing a 100% mesophase pitch, as a raw material for high strength and high modulus carbon fibers, preferable as a raw material for fabricating composite articles efficiently and at an inexpensive cost.
SUMMARY OF THE INVENTION
The above-mentioned object can be attained by the method of the present invention in which a residuum carbonaceous material formed, as a by-product of a catalytic cracking of vacuum gas oil (F.C.C.) or a thermal cracking of naphtha is subjected, if necessary to a preliminary treatment to produce a precursor* and their resulting precursor is heat treated with stirring under a stream of hydrocarbon gas of small carbon atom numbers, lower melting point naphtha fractions or a dry gas formed as a by-product at the time of heat treatment of raw material under atmospheric or superatomospheric pressure at a temperature of 360°˜450° C. for 30 minutes to 30 hours so as to bring the mesophase content in the heat-formed pitch in the range of 10 to 50%, then holding the heat-formed pitch in aging melt-coalescing state under a stream of hydrocarbon gas of small numbers of carbon atom, lower melting point naphtha fractions or a dry gas formed as a by product of the heat treatment of the raw material at a temperature of 290° C. to 350° C. for 5 to 30 hours (which is entirely different treatment condition from the heat-treatment condition) and separating a non-mesophase of the upper layer and a mesophase (easily observable by a polarization microscope) of the lower layer by the difference of physical properties (e.g. specific gravity or viscosity) at the same temperature as the aging melt-coalescing temperature to produce 100% mesophase pitch.
DETAILED DESCRIPTION OF THE INVENTION
Namely, residuum carbonaceous material formed, as a by-product in a catalytic cracking process (F.C.C.) of vacuum gas oil is made into a precursor* under atmospheric stream of a hydrocarbon gas of small numbers of carbon if necessary by subjecting to preliminary heat treatment and resulting precursor is treated at a temperature of 360°˜450° C. with stirring for 30 minutes to 30 hours so as to bring the mesophase content in the heat-formed pitch in the range of 10% to 50%.
It is possible to produce heat formed pitch containing 20% to 40% mesophase preferably by the heat-treatment carried out by selecting preferably the condition of heating temperature of 380° C. to 440° C. and reaction time of 1˜6 hours in order to rationalize the treatment condition with stirring and heating. It is possible to cause only mesophase to melt and coalesce (into huge one body) by holding heat-formed pitch in quiescent state at a temperature of 280° C. to 350° C. which is lower that the heat-treatment temperature, for 5 to 30 hours, under a stream of a hydrocarbon gas of small carbon atom numbers, lower boiling point naphtha fractions, or a dry gas obtained at the heat treatment of raw material of the present invention and further to divide clearly non-mesophase from mesophase at the temperature same as the melting-coalescing aging temperature. If a heating temperature in the melting-coalescing aging state is lower than 280° C., division and separation of heat-formed pitch into non-mesophase and mesophase cannot be carried out.
* The heating reaction for producing mesophase and the aging reaction for melting coalescing produced mesophase are entirely different and by treating these reactions separately, it is only possible to separate 100% mesophase and non-mesophase by the different physical properties (such as specific gravity viscosity, etc.) at the temperature same as the aging and melt coalescing temperature.
As for a carrier gas a stream used at the time of heat treatment as well as at the time of separation of heat formed pitch into non-mesophase and mesophase, a hydrocarbon of small carbon numbers such as methane, ethane, propane, butane or the like or naphtha fractions having lower boiling points which are not converted into heavier materials or pitch can be mentioned. However, economically most excellent gas is a dry gas which is formed as a by-product at the time of heat-treatment of raw material of the present invention (mostly a mixture of hydrocarbons of small carbon number).
Further mesophase can be easily confirmed to be 100% with a polarization microscope. It is preferable to separate non-mesophase and mesophase by selecting the condition of holding in quiescent state at a temperature of 300° C. to 340° C. and a residence time of for 5 to 25 hours in order to rationalize the condition for holding in quiescent state.
Further, it has been found by the inventor of the present invention that divided and separated mesophase is composed of Q.I. (quinoline insoluble portion measured by extraction with quinoline at 80° C.) and Q.S. (quinoline soluble portion) by setting condition for holding in quiescent state and that spinning property of mesophase can be greatly improved by composing the 100% mesophase of 75˜87% of Q.I. component and 13˜25% of Q.S. component.
The feature of the present invention lies in the point that the mesophase is composed only of Q.I. meso component and Q.S. meso component immediately upon the production of the 100% mesophase.
One example for producing carbon fibers by spinning 100% mesophase composed only of Q.I. and Q.S. component is set forth as follows.
The fibers obtained by spinning 100% mesophase composed only of Q.I. and Q.S. components at a spinning temperature of 320° C. and a viscosity of 50 poise (at the spinning temperature) and a spinning velocity of 100 m/min are subjected to thermosetting (crosslinking) with air at a temperature of 300° C. for 15 minutes and then subjected to carbonization at a temperature rising velocity of 10° C./min. and at an ultimate temperature of 1400° C. for 15 minutes to produce carbon filament yarns having high strength and high modulus.
The invention entitled "Method for producing mesophase-containing pitch by using carrier gas" filed by the inventor of the present application on the same day with the present application had been utilized in the present invention and the description of this application is incorporated herein by reference.
It is a very important point that the reason of separability of the non-mesophase of the upper layer from the 100% mesophase of the lower layer after the aging melt coalescing step has intimate relation with the preceding heat treatment condition.
Following examples are set forth for the purpose of illustration for those skilled in the art but not for the purpose of limiting the invention in any manner.
EXAMPLE 1
A residuum carbonaceous material which is formed as a by-product in a catalytic cracking process (F.C.C.) of vacuum gas oil was subjected to heat treatment of 400° C. for 2 hours under a stream of hydrocarbon gas of small carbon numbers, to produce a precursor pitch.
The yield of the precursor was 54% and the softening point of the precursor (corresponding to R & S) was 67° C.
Resulting precursor was treated under the following heat-treatment condition and then heat-formed pitch was held at a temperature of 300° C. for 24 hours in quiescent state and separation of, the divided non-mesophase layer and mesophase layer was carried out by using, as a carrier gas, a dry gas formed in the heat treatment reaction and recycled.
__________________________________________________________________________Result of atmospheric heat treatmentExperiment Number 1 2 3 4__________________________________________________________________________Amount of precursor (gr) 1500 1500 1500 1500 Temperature (°C.) 380 400 420 440Heatingcondition Time (hr) 20 6 2 45 minutes Formed amount (gr) 1,143 1,313 1,296 1,263Pitch Yield (%) 76.2 87.5 86.4 84.2 Formed amount (gr) 143 116 130 195Distilledoil Yield 9.5 7.7 8.6 6.2Yield gas (wt %) 14.3 4.8 5.0 6.2Property of pitch Non- Meso Non- Meso Non- Meso Non- Meso meso meso meso mesoYield of each phase (wt %) 66.4 33.6 78.9 21.1 79.3 20.7 68.1 31.9 Softening 229 246 226 225 point (°C.)Flow Softening 308 309 298 312test point (°C.) corresponding to R & BMeso- Q.I. component (%) 76.7 74.2 79.7 75.8phasefrac- Q.S. component (%) 23.3 25.8 20.3 24.2tion__________________________________________________________________________
The measurement of softening point corresponding to R & B was carried according to JISK-2531.
EXAMPLE 2
Heat-formed pitch prepared according to Experiment No. 2 of example 1 was subjected to mesophase separation test under the following condition for holding in quiescent state immediately after formation.
__________________________________________________________________________Result of meso-phase separation testExperiment Number 5 6 7 8 9 10__________________________________________________________________________Holding Temperature (°C.) 260 280 300 300 320 340inquiescent Time (hr) 16 16 16 24 16 16stateProperty of pitch non- meso upper non- meso non- meso non- meso non- meso non- meso meso meso meso meso meso meso mesoYield of each phase unseparable 7.2 83.6 9.2 84.4 15.6 78.9 21.1 84.8 15.2 84.4 15.6(wt %) Softening point 219 209 223 246 232 231Flow Softening point 282 112 287 116 294 118 309 120 299 129 302test corresponding to R & B Q.I. component 66.4 2.4 76.8 1.4 84.1 1.8 74.2 2.0 82.9 2.6 77.7Meso- (%) 23.2 15.9 25.8 17.1 22.3phase Q.S. componentfraction (%)__________________________________________________________________________
Under condition of holding in quiescent state of experiment number 6. Clear-cut separation into non-mesophase layer and mesophase layer could not be made and only division into 3 layers was effected. Thus the condition for holding in quiescent state was insufficient.
EXAMPLE 3
Residuum carbonaceous material having a boiling points of 200° C. or higher, which was formed as by-product in thermal cracking of naphtha was treated under the following heat-treatment condition, under a stream of methane gas.
______________________________________Result of atmospheric heat-treatmentExperiment number 11 12 13______________________________________ temperature (°C.) 380 380 380heatingcondition time (hr) 9 14 17Yield of pitch (wt %) 24 22 19.5 Softening point 162 166 190Flow Softening point 210 218 256test corresponding to R & BQ.I. component of pitch (%) 18.1 25.8 37.6______________________________________
The measurement of softening point corresponding to R & B was carried out according to JISK-2531.
The heat-formed pitch prepared according to experiment number 11 was subjected to mesophase separation test under stream of methane gas under the condition for holding in quiescent state immediately after preparation.
__________________________________________________________________________Result of mesophase separation testExperiment number 14 15 16__________________________________________________________________________holding temperature (°C.) 260 280 300inquiescent time (hr) 16 16 16stateproperty of pitch non- meso non- meso non- meso meso meso mesoYield of each phase unseparable 79.3 20.7 76.6 23.4 softening point (°C.) 152 212 158 224Flow softening point (°C.) 290 296test corresponding to R & Bmeso- Q.I. component (%) 1.4 76.1 1.6 77.3phasefrac- Q.S. component (%) 23.9 22.7tion__________________________________________________________________________ | A method for producing a 100% mesophase pitch composed only of Q.I. and Q.S. components is provided. This method comprises subjecting petroleum-origin pitch to heat treatment with stirring under a stream of a hydrocarbon gas of small carbon atom numbers at atmospheric or superatmospheric pressure, holding said heat-treated pitch in quiescent state to melt and coalesce only the mesophase therein and dividing and separating non-mesophase and mesophase layers. Resulting 100% mesophase enables us to produce high strength, high modulus carbon fibers. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an electro-photographic apparatus, and more particularly, to a method and apparatus for development using a dry two-component developer.
[0003] 2. Description of the Related Art
[0004] Conventionally, a magnetic brush development method using a two-component developer consisting of magnetic carriers and toners has been employed in an electro-photographic apparatus. A development apparatus using the method normally has a magnet roller having a magnetic body including a plurality of magnetic poles and a development sleeve which is a rotatably supported cylindrical developer supporter. The development apparatus develops by holding magnetic carriers having toners on a surface of the development sleeve and carrying them to a development area. On the other hand, a one-component development method in which development is performed by using only magnetic toners or non-magnetic toners without magnetic carriers has also been employed. The one-component development method is similar to the two-component development method in respect to development by holding toners on a surface of a development sleeve and carrying them to a development area, but different from it with respect to detailed structures and a means of charging toners, etc.
[0005] In such a development apparatus, it has been proposed to improve image quality by improving of toner carrying performance by increasing surface -roughness of a development sleeve using a one-component development method as described in Japanese Examined Application Publication No. 64-12386. A method to improve performance of carrying toners by increasing surface roughness of a development sleeve using a two-component development method has also been proposed as described in Japanese Laid-Open Patent Application No. 5-19632.
[0006] However, the methods described above presuppose non-contact development and that the quantity of developer on a developer supporter is controlled to be constant by using a developer quantity controller in the form of a bar. A non-contact development method using a developer quantity controller which is made from materials having rigidity or rigidity and magnetic properties have problems in providing enough developer on a developer supporter. Especially, size of carrier particles needs to be smaller to meet recent requirement for high image quality and downsizing. However, when size of carrier particles is made smaller, fluidity of the particles tends to be lower, so that the above mentioned method has problems in carrying developer to a development area uniformly when such a developer is used.
[0007] Furthermore, in most recent copying machines, a photo conductor and a development apparatus are combined and they can be easily exchanged, providing for labor savings related to maintenance by a service person. In such a system, since cost is higher if an exchanging cycle is short, a developer having a long service life and a latent image supporter having a service life comparable to the one of the developer, which is referred to below as a photo conductor, are required. However, when the two-component contact development method is employed, a photo conductor is always rubbed with developer, and, thus, it is easy for the photo conductor to become worn and difficult to have a long servicelife. Furthermore, density of a developer on a development area is required to be high to meet the demand for high image quality. However, if density of a developer on a development area is high, wear of the photo conductor is accelerated. In order to prevent wear of the photo conductor, prevention of wear by decreasing printing resistance has been attempted by adding a filler to the outermost layer of a photo conductor. Ozone generating from a charger and low resistance materials secondarily produced from nitrogen oxides fall on an outermost layer of a photo conductor and adhere to a surface of the layer. When a photo conductor in which a filler is not added to the outermost layer is used, abrasion of the outermost layer of a photo conductor is reduced and resistance of a surface of a photo conductor is reduced by adhesion of the low resistant materials, so that abnormal images having decrease in resolution or blur are not formed. The problem originates when wearing rate of the outermost layer is faster than the deposition rate of the low resistance materials. However, the abrasion loss of a photo conductor defines the service life of the photo conductor. On the other hand, when a layer having high wear resistance is laid on the outermost layer of a photo conductor as in the subject application, abrasion loss decreases and the service life of a photo conductor is not controlled by the wear resistance. However the deposition rate of the low resistance materials produced from ozone and nitrogen oxides, etc., described above overcomes the rate of wear resulting in deposition (adhesion) of the low resistance materials to the surface of the photo conductor. Consequently, side effects such as decrease in resolution and blur in an image resulting from decrease of resistance on a surface of a photo conductor are generated, therefore a new problem of the side effects controlling the service life of an image formation apparatus occurs.
[0008] When a layer including a filler is laid on the outermost layer of the above mentioned photo conductor, the wear resistance is improved, but side effects may occur. When a conductive filler is employed as a filler, resistance on a surface of a photo conductor is reduced, and decrease in resolution and blur in an image may occur due to a reason other than the above mentioned phenomenon. Especially, the phenomenon is significant when a photosensitive layer is made from an organic material. Therefore, it is necessary to employ a high resistance filler in an organic photo conductor. In this case, since the filler does not have charge transfer efficiency, when the photo conductor is repeatedly used in an electro-photographic apparatus, residual potential is elevated or electric potential of exposed areas is elevated in negative or positive development, so that there is produced a defect of decrease in image density.
[0009] Thus, as wear resistance of a photo conductor is improved and abrasion loss does not define the service life of a photo conductor, an electrostatic service life of the photo conductor defines the service life of the photo conductor. Specifically, point defects (stains and black points, etc.) on image background (white background), which are not in an original image, occur due to decreasing electrostatic property of a photo conductor (especially, local leak of electric potential). The defects may be taken for points in a drawing or period and comma, etc., in a draft in English so that the defects are crucial in an image.
SUMMARY OF THE INVENTION
[0010] The present invention is achieved in the situation as described above. It is a general object of the present invention to provide an image formation apparatus preventing deposition of low resistance materials produced from ozone and nitrogen oxides on a surface layer of an improved wear-resistant photo conductor by providing a developer with moderate strength to the photo conductor and thereby prevent the generation of an abnormal image having blur and decrease in resolution, which is peculiar to a high wear resistant photo conductor.
[0011] A more specific object of the present invention is to provide an image formation apparatus preventing elevation of residual potential caused by repeated use of a photo conductor including a filler in an outermost layer and preventing decrease of image density in negative or positive development.
[0012] A further specific object of the present invention is to provide an image formation apparatus preventing a reduction of electrostatic properties caused by repeated use of a photo conductor and preventing point defects (stains on image background) in negative or positive development.
[0013] The inventors actively investigated the relation among developer carrying properties, diameters of developer particles and surface roughness Rz of a development sleeve in order to solve the above mentioned problems. As a result, the inventors found that when a developer having the particle diameters within a particular range is used, the developer can be uniformly provided on a developer supporter by adjusting the relation between a development gap and a doctor gap to within a particular range, a surface of a photo conductor can be always maintained in usable condition by the developer, and there is no problem about the service life of the photo conductor.
[0014] That is, the solution of the above problem is achieved by the present inventions; (1) an image formation apparatus developing an electrostatic latent image with a two-component developer consisting of magnetic carriers and toners by using a development apparatus and a latent image supporter including a filler in an outermost layer thereof, the development apparatus having a developer supporter, which has an internally fixed magnetic body and rotates while supporting a developer on a surface thereof, and a developer quantity controller controlling a quantity of the developer which is supported by the developer supporter facing the magnetic body by controlling a height of magnetic brushes and consisting of materials having rigidity or rigidity and magnetic properties, characterized in that a ratio (Gp/Gd) of a development gap to a doctor gap between the developer supporter and a controller is from 0.7 to 1.0, and a weight-averaged particle diameter of a developer carrier is from 20 to 60 μm; (2) the image formation apparatus described in item (1) characterized in that surface roughness Rz of a development sleeve is from 10 to 30 μm; (3) the image formation apparatus described in the item (1) and (2) is characterized in that a surface of the development sleeve is processed by sand blasting; (4) the image formation apparatus described in any one of the items (1) to (3) is characterized in that a ratio (D/Rz) of the weight-averaged particle diameter (D) of the developer carrier to surface roughness (Rz) of the development sleeve satisfies a relation 2<D/Rz <3; (5) the image formation apparatus described in items 1 to 4 is characterized in that the filler included in the outermost layer of the latent image supporter is formed by a metal oxide; (6) the image formation apparatus described in items 1 to 5 is characterized in that the outermost layer of the latent image supporter includes a charge transfer material; (7) the image formation apparatus described in item 6 is characterized in that the charge transfer material is a polymer having electron-donating groups; (8) the image formation apparatus described in items 1 to 7 is characterized in that the outermost layer of the latent image supporter includes an organic compound of which acid value is from 10 to 40 (mgKOH/g); (9) the image formation apparatus described in items 1 to 8 is characterized in that a charge generating material included in the latent image supporter is a titanylphthalocyanine having at least a maximum diffraction peak at 27.2° as diffraction peak at Bragg angle 2θ (+0.2°) for characteristic X-ray of CuKa; (10) the image formation apparatus described in items 1 to 8 is characterized in that the charge generating material included in the latent image supporter is an azo pigment represented by the following structural formula (A):
[0015] wherein Cp 1 and Cp 2 are coupler residues, which are identical or different from each other; wherein R 201 and R 202 are respectively selected from a group consisting of hydrogen atom, halogen atom, alkyl groups containing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 carbon atoms, and cyano group and are identical or different from each other; wherein Cp 1 and Cp 2 are represented by the following structural formula (B)
[0016] wherein R 203 is selected from a group consisting of hydrogen atom, alkyl groups such as methyl group and ethyl group, and aryl groups such as phenyl group; wherein R 204 , R 205 , R 206 , R 207 , and R 208 are respectively selected from a group consisting of hydrogen atom, nitro group, cyano group, halogen atom such as fluorine, chlorine, bromine, and iodine, trifluoromethyl group, alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, dialkylamino group, and hydroxyl group;
[0017] wherein Z represents an atom group required for forming a substituted or non-substituted aromatic carbon ring or a substituted or non-substituted aromatic heterocyclic ring;
[0018] (11) the electro-photographic apparatus described in items 1 to 10 is characterized in that a surface of a conductive supporter of the latent image supporter is anodized; (12) the electro-photographic apparatus described in items 1 to 11 is characterized in that in the electro-photographic apparatus, a charger contacts or is closely arranged to the latent image supporter; (13) the electro-photographic apparatus described in item 12 is characterized in that the size of air gap between the charger and the latent image supporter is equal to or less than 200 μm; (14) the electro-photographic apparatus described in items 12 and 13 is characterized in that in the electro-photographic apparatus, an alternating current component is superposed on a direct current component in the charger to provide a charge to the latent image supporter; (15) the electro-photographic apparatus described in items 1 to 14 is characterized in that zinc stearate is applied on the latent image supporter; (16) the electro-photographic apparatus described in item 15 is characterized in that in the electro-photographic apparatus, zinc stearate powder is included in the toner provided to a development area.
[0019] The development method according to the present invention is a two-component contact development method carried out by using a development apparatus having a developer supporter, which has an internally fixed magnetic body and rotates while supporting a developer on a surface thereof, and a developer quantity controller controlling a quantity of the developer which is supported by the developer supporter facing the magnetic body and consisting of materials having rigidity or rigidity and magnetic properties.
[0020] At first, the development apparatus according to the present invention will be illustrated. FIG. 1 shows a cross section of a development apparatus according to the present invention. In FIG. 1, it is shown that the reference numeral 1 is a photo conductor drum, 2 is a development sleeve housing, 3 a is toner, 4 is a development sleeve, 5 is a magnet roller, 6 is a controller, 7 is a sleeve in front of a doctor, 7 a is a diaphragm, 8 is a toner hopper, 8 a is an aperture for supplying toners, 9 is a provision roller, 12 is a development area, A is a developer providing room, Gp is a development gap, and Gd is a doctor gap.
[0021] Herein, the photo conductor drum rotates in the direction indicated by the arrow, has the outermost layer including a filler on the surface of the photo conductor and forms an electrostatic latent image on the surface by a charger and an exposure device not shown in FIG. 1. The magnet roller 5 is fixed in the development sleeve being the developer supporter, has a plurality of (N), (S) magnet poles on the surface of the roller, supports the developer with the development sleeve, and carries the developer, in which the development sleeve 4 rotates in the same direction as the rotational direction of the photo conductor against the fixed magnet roller. The magnetic poles (N), (S) of the magnet roller 5 are magnetized to an appropriate magnetic flux density so that magnetic brushes consisting of the developer are formed by the magnetic force. The controller 6 controls the height and the quantity of the magnetic brushes. The distance between the controller and the development sleeve is referred to as doctor gap (Gd).
[0022] While the toner 3 provided into the apparatus is sufficiently stirred and mixed with the carriers by the provision roller 9 rotating in the direction indicated by the arrow and frictional electrification is carried out, the toner is carried to the development sleeve housing 2 , and magnetic brushes of which the height and the quantity are controlled by the controller 6 are formed on the development sleeve 4 . When the distance between the development sleeve 4 and the surface of the photo conductor drum 1 , or development gap (Gp) is set to the predetermined distance (for example, 0.7 mm) and a electrostatic latent image is developed on the photo conductor drum, the magnetic brushes formed on the surface of the development sleeve 4 are vibrating due to a change of the magnetic flux density and moved with the development sleeve 4 while the development sleeve 4 rotates, and the magnetic brushes pass smoothly through a gap in the development area and a latent image is developed by the toner. In this case, a bias voltage may be preferably applied between the development sleeve 4 and the substrate of the photo conductor drum 1 in order to carry out the development.
[0023] The development method according to the present invention satisfies the condition that in the two-component development device shown in FIG. 1, the magnetic carriers of which the weight-averaged particle diameter is from 20 to 60 μm are utilized and a ratio (Gp/Gd) of the development gap (Gp) to the doctor gap (Gd) is from 0.7 to 1.0. If Gp/Gd is less than 0.7, adhesion of carriers is easily generated since a pool of the developer occurs in the development gap. On the other hand, if it is larger than 1.0, the developer is weakly applied to the photo conductor resulting in elimination of a cleaning effect. If the diameter of the carrier particle is less than 20 μm, it is not preferable since carrier adhesion easily occurs. If it is larger than 60 μm, although there is no notable trouble, it is not preferable due to a demand for high image quality. Also, surface roughness (Rz) of the surface of the development sleeve satisfies the condition of from 10 to 30 μm. Satisfaying the condition results in not only generating more cleaning effect but also stabilizing the providing of the developer, and is effective in improving image quality.
[0024] The surface roughness Rz means ten points-averaged roughness, and for example, it may be measured by Surfcoder SE-30H produced by Kosaka Laboratory. The ten points-averaged roughness reflects the depth of fine irregularities of a solid surface. Also, a material used in a development sleeve may be one used in a normal development apparatus, non-magnetic materials such as stainless steel, aluminum, and ceramics, and a coated development sleeve may be used but is not required. The form of the development sleeve is also not particularly limited.
[0025] In the present invention, in order to adjust the surface roughness Rz of the development sleeve to within the above mentioned range, although, for example, sand blasting, groove processing, grinding, sand paper, and index saver processing may be used, it is preferable to use sand blasting in respect to the following points. That is, since sand blasting is not only easy to operate and efficient to process but also can be used for a random surface processing (coarsening), frictional resistance between the toner and the development sleeve is considered to be improved equally in all directions.
[0026] It is effective for the ratio (D/Rz) of a weight-averaged particle diameter of a carrier (D) to surface roughness (Rz) of the development sleeve to satisfy a relation 2≦D/Rz≦3, in order to improve the effect of the present invention. Even if the ratio does not satisfy the relation, there is no problem with respect to the cleaning effect of the photo conductor. However, if the ratio D/Rz is less than 2, stress applied on the carrier become larger and peeling off of carrier coating resin or carrier pollution with the toners easily occurs. On the other hand, if the ratio D/Rz is larger than 3, toner density becomes too high or a defect on carrying performance is generated a little when Q/M become too large.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Other objects, features and advantages of the present invention will become more apparent from the following detailed description when read in conjunction with the accompanying drawings, in which:
[0028] [0028]FIG. 1 shows a cross-section of a development apparatus used in the present invention.
[0029] [0029]FIG. 2 shows a cross-section of an electro-photographic photo conductor having another structure according to the present invention.
[0030] [0030]FIG. 3 shows a cross-section of an electro-photographic photo conductor having yet another structure according to the present invention.
[0031] [0031]FIG. 4 shows a cross-section of an electro-photographic photo conductor having yet another structure according to the present invention.
[0032] [0032]FIG. 5 shows a schematic to illustrate an electro-photographic process and an electro-photographic apparatus according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] The present invention will be illustrated by the embodiment described below.
[0034] Toners constituting developers with carriers for developing a latent image produced by conventional known method may be used according to the present invention. Specifically, after a mixture consisting of binder resin, a coloring agent, a polarity controlling agent and any other additives according to need is melted and kneaded by a thermal roll mill, the product is cooled and solidified, and the toners are obtained by pulverizing and classifying the product.
[0035] In this case, as for a binder resin, all well-known materials can be used. For example, a homopolymer of styrene or a substituted one thereof such as polystyrene, poly-p-styrene, polyvinyl toluene, a styrene-based copolymer such as copoly(styrene/chlorostyrene), copoly(styrene/propylene), copoly(styrene/vinyltoluene), copoly(styrene/methyl acrylate), copoly(styrene/ethyl acrylate), copoly(styrene/butyl acrylate), copoly(styrene/methyl methacrylate), copoly(styrene/ethyl methacrylate), copoly(styrene/butyl methacrylate), copoly(styrene/α-methyl chloromethacrylate), copoly(styrene/acrylonitrile), copoly(styrene/methyl vinyl ether), copoly(styrene/methyl vinyl ketone), copoly(styrene/butadiene), copoly(styrene/isoprene), copoly(styrene/maleic acid), and copoly(styrene/maleate), poly(methacrylate), polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylate resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax, etc. may be used independently or as a mixture thereof.
[0036] As for a polarity controlling agent, a conventionally known material can be used. For example, a metallic complex salt of azo dye, nitrohumic acid and a salt thereof, an amino compound of a metal complex of salicylic acid, naphthoic acid, and dicarboxylic acid with Co, Cr, and Fe etc., a quaternary ammonium compound, organic dye, etc. may be used. Consumed quantity of the polarity controlling material used for the toner is determined by the kind of binder resin, presence or absence of additives used according to need, and a method of producing the toner including dispersion method, and will vary accordingly. However, from 0.1 to 20 parts by weight of the polarity controlling agent to 100 parts by weight of a binder material is prefered. If the above mentioned polarity controlling agent proportion is less than 0.1 parts by weight, charge quantity of the toners is deficient so that such a polarity controlling agent proportion is not practical. Also, if the proportion of polarity controlling agent is larger than 20 parts by weight, the charge quantity of the toners is too large and the electrostatic attractive force between the toner and the carrier will increase, so that decrease of the fluidity of the developer and decrease of the image density will result.
[0037] As for a black coloring agent included in the toners, for example, carbon black, aniline black, furnace black, and lamp black may be used. As for a cyan coloring agent, for example, phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, and ultramarine blue may be used. As for a magenta coloring agent, for example, rhodamine 6G lake, dimethylquinacridone, watching red, rose bengal, rhodamine B, and alizarin lake may be used. As for a yellow coloring agent, for example, chrome yellow, benzidine yellow, hansa yellow, naphthol yellow, molybdenum orange, quinoline yellow, and tartrazine may be used.
[0038] Furthermore, a toner including a magnetic material can be used as a magnetic toner. As a magnetic material included in a magnetic toner, an iron oxide such as magnetite, hematite, and ferrite, a metal such as iron, cobalt, nickel or an alloy among these metals and metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and a mixture thereof may be used. The ferromagnetic material will preferably have an averaged particle diameter of about from 0.1 to 2 μm, and the quantity included in the toners is about 20 to 200 parts by weight, and more preferably 40 to 150 parts by weight combined with 100 parts by weight of resin component.
[0039] Also, as an additive added to the toner, an inorganic powder of cerium oxide, silicon dioxide, titanium oxide, silicon carbide, etc can be used. Colloidal silica is particularly preferable as a toner additive.
[0040] A carrier capable of being used in the present invention, is for example, a powder having magnetic properties such as iron powder, ferrite powder, and nickel powder and a powder of which a surface thereof is treated by resin, etc. In order to develop a latent image faithfully by stabilizing frictional electrification of the toners used in the present invention, the toners are preferably coated by a resin and/or a silicone compound. Thereby, control of toner charging can be also performed.
[0041] As for a resin to form a coating layer of a carrier, for example, a silicone-based compound and a fluorocarbon resin can be preferably used. As for a fluorocarbon resin to form a coating layer of a carrier, for example, a perfluoropolymer such as polyvinyl fluoride, polyvinylidene fluoride, polytrifluoro ethylene, polychloro trifluoro ethylene, polytetrafluoro ethylene, polyperfluoro propylene, copolymer of vinylidene flioride and acrylic monomer, copoly(vinylidene fluoride/chlorotrifluoroethylene), copoly(tetrafluoroethylene/hexafluoropropylene), copoly(vinyl fluoride/vinylidene fluoride), copoly(vinylidene fluoride/tetrafluoroethylene), copoly(vinylidene fluoride/hexafluoropropylene), and fluoroterpolymer such as terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluoridated monomer are preferably used. In formation of a coating layer of a carrier, the fluorocarbon resin described above may be used independently or as a mixture thereof. A mixture of the resin and other polymers may be used.
[0042] As for a silicon-based compound to form a coating layer of a carrier, for example, a polysiloxane such as methylpolysiloxane and methylphenylpolysiloxane is used, and a modified resin such as alkyd modified silicon, epoxy modified silicon, polyester modified silicon, urethane modified silicon, and acryl modified silicon can be also used. As for a modified form of the resin, block copolymer, graft copolymer, and wedge garft-polysiloxane can be used.
[0043] With respect to application to surfaces of actual magnetic particles, a method in which the resin is sprayed on the magnetic particles by immersing or fluid bed can be carried out.
[0044] As for a material of a substrate of the carrier used in the present invention, for example, a metal such as surface-oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, and rare earth elements, and an alloy or oxides thereof can be used. However, preferably a metal oxide, and more preferably ferrite particles, will be used. The production method is not limited. As to the proportion of the carriers and the toners according to the present invention, both particles are preferably mixed such that toner particles adhere to the surface of the carrier particles and occupy about from 30 to 90% of the surface area of the carrier particles.
[0045] Next, an electro-photographic photo conductor used in the present invention will be illustrated with attached drawings.
[0046] [0046]FIG. 2 shows a cross-section of an electro-photographic photo conductor used in the present invention. The single photosensitive layer 43 including mainly a charge generating material and a charge transfer material is laid on the conductive supporter 41 , and the protective layer 49 is laid on the photosensitive layer.
[0047] [0047]FIG. 3 shows a cross-section of an electro-photographic photo conductor having another structure used in the present invention. In FIG. 3, the photosensitive layer has a structure such that the charge generating layer 45 including mainly a charge generating material and the charge transfer layer 47 including mainly a charge transfer material are laminated, and the protective layer 49 is laid on the charge transfer layer 47 .
[0048] [0048]FIG. 4 shows a cross-section of an electro-photographic photo conductor having another structure used in the present invention. In FIG. 4, the photosensitive layer has structure such that the charge transfer layer 47 including mainly a charge transfer material and the charge generating layer 45 including mainly a charge generating material are laminated, and the protective layer 49 is laid on the charge generating layer 45 .
[0049] As for the conductive supporter 41 , a product of a plastic in the form of film or a cylinder or a paper coated with a material having conductivity specified with volume resistivity equal to or less than 10 10 Ω·cm, which is for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum or a metal oxide such as tin oxide and indium oxide, formed by vapor deposition or sputtering can be used. Also, a plate made from aluminum, aluminum alloy, nickel, or stainless etc. and a pipe which is roughly formed by extrusion and drawing process from the plate followed by surface treatment such as cutting, super finishing, and polishing. can be used. An endless nickel belt and an endless stainless belt can be used as the conductive supporter 41 , which is disclosed on Japanese Laid-Open patent application No. 52-36016.
[0050] Also, a cylindrical supporter made from aluminum, to which anodizing can be easily applied, can be best used. The referred term “aluminum” includes both pure aluminum and an aluminum alloy. Specifically, aluminum selected from JIS No.1000, 3000, and 6000 groups or an aluminum alloy is most appropriate. An oxide film on an anode is formed by anodizing each kind of metal or each kind of metal alloy in electrolyte solution. However, the coating called alumite in which aluminum or an aluminum alloy is anodized in electrolyte solution is most appropriate for a photo conductor used in the present invention. Especially, the above preferred conductive supporter excels in respect to preventing point defects (black points and stains on image background) from being generated when it is used in reverse development (negative or positive development).
[0051] Anodizing is carried out in acid solution of chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid and sulfamic acid, etc. Anodizing in a sulfuric acid bath is most appropriate. For example, anodizing is carried out under the conditions in which the concentration of sulfuric acid is 10-20%, bath temperature is 5-25° C., current density is 1-4 A/dm 2 , bath voltage is 5-30V, and time period for anodizing is about 5-60 minutes, but anodizing is not limited to these conditions. The oxidation film on an anode formed like above is porous and has high insulating property so that a surface of the film is in unstable condition. Therefore, time variation of the anodized film may occur, and a physical value for the film is likely to be varied. In order to prevent the variation, it is preferable to further apply a sealing treatment to the anodized film. As sealing treatment, several methods can be used, that is, a method to immerse the anodized film in a solution including nickel fluoride or nickel acetate, a method to immerse the anodized film in boiling water, and a method to treat the film by pressure steam. Among the methods, the method of immersion in a solution including nickel acetate is most preferable. A washing treatment is applied to anodized film following the sealing treatment. A main object of the washing treatment is to remove excess metal salt, etc., adhering as a result of the sealing treatment. If the excessive salt remains on a surface of the supporter (the anodized film), since low resistance components in the salt generally remain, the components cause generation of stains on image background as well as adverse effects on the quality of coating film formed on the surface. Although the washing treatment may be accomplished with purified water, multi-step washing is commonly performed. In this case, it is preferable for cleaning liquid to be used at final washing to be as clean (deionized) as possible. Also, it is desirable to physically rub the conductive supporter during washing by using a contact member in a process within a multi-step washing process. It is preferable that film thickness of the anodized film formed like above be about from 5 to 15 μm. If the thickness is thinner than 5 μm, the effect of barrier property of the anodized film is not enough. If the thickness is thicker than 15 μm, the time constant of the film as an electrode become too large, and generation of residual potential and deterioration of response of a photo conductor may occur.
[0052] As for the conductive supporter (41) according to the present invention, a product formed by applying a suitable binding resin in which conductive powders are dispersed on the supporter, can be used. The conductive powder may be carbon black, acetylene black, metal powder made from a metal such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder made from a metal oxide such as conductive tin oxide and ITO. As for the binding resin used at the same time, thermoplastic, thermosetting, and photo-curing resin such as polystyrene, copoly(styrene/acryronitrile), copoly(styrene/butadiene), copoly(styrene/maleic anhydride), polyester, polyvinyl chloride, copoly(vinyl chloride/vinyl acetate), polyvinyl acetate, polyvinylidene chkoride, polyarylate resin, phenoxy resin, polycarbonate, acetylcellulose resin, ethylcellulose resin, polyvinylbutyral resin, polyvinyl formal resin, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine formaldehyde resin, urethane resin, phenol resin, and alkyd resin, are given. Such a conductive layer can be formed by applying a product in which the conductive powder and the binding resin are dispersed in an appropriate solvent, for example, tetrahydrofuran, dichloromethane, ethyl methyl ketone, and toluene, on the supporter.
[0053] Further, a product formed by laying a conductive layer which is a heat contraction tube produced by adding the conductive powder to a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, ployethylene, chlorinated rubber, and Teflon, on an appropriate cylindrical substrate, can be used as for the conductive supporter 41 according to the present invention.
[0054] Next the photosensitive layer will be illustrated. The photosensitive layer may be a single layer or a laminated layer. A photosensitive layer consisting of the charge generation layer 45 and the charge transfer layer 47 is illustrated at first. The charge generation layer 45 is a layer including a charge generation material as a main component and may be made from a binder resin according to need. An inorganic material and an organic material can be used as a charge generation material.
[0055] The inorganic material may be crystal selenium, amorphous selenium, selenium-tellurium system, selenium-tellurium-halogen system, selenium-arsenic system, and amorphous silicon, etc. With respect to amorphous silicon, amorphous silicon in which dangling bond is terminated by hydrogen atom and/or halogen atoms or in which boron atom and/or phosphorus atom are doped, is used well. As for the organic material, a well-known material can be used. For example, phthalocyanine-based pigment such as phthalocyanine containing a metal ion, phthalocyanine not containing a metal ion, azulenium salt pigment, methyl squarate pigment, azo pigment having carbazole skelton, azo pigment having triphenylamine skelton, azo pigment having diphenylamine skelton, azo pigment having dibenzothiophene skelton, azo pigment having fluorenone skelton, azo pigment having oxadiazole skelton, azo pigment having bis-stilbene skelton, azo pigment having distyryloxadiazole skelton, azo pigment having distyrylcarbazole skelton, perylene-based pigment, anthraquinone-based or polycyclic quinone-based pigment, quinoneimine-based pigment, diphenylmethane and triphenylmethane-based pigment, benzoquinone and naphthoquinone-based pigment, cyanine and azomethyne-based pigment, indigoid-based pigment, bis-benzimidazole-based pigment are given. The charge generating materials may be utilized independently or as a mixture of more than one kind thereof.
[0056] Azo pigments and/or phthalocyanine pigments are effectively utilized. Especially, azo pigments represented by the following structural formula (A):
[0057] and titanylphthalocyanine (escpecially, having at least a maximum diffraction peak at 27.2° as diffraction peak at Bragg angle 2θ (±0.2°) for characteristic X-ray of CuKα) can be effectively utilized.
[0058] Cp 1 and CP 2 in the formula (A) are coupler residues, which are identical or different from each other. R 201 and R 202 are respecively selected from a group consisting of hydrogen atom, halogen atoms, alkyl groups, alkoxy groups, and cyano group, which are identical or different from each other. Also, Cp 1 and Cp 2 are represented by the following structural formula (B).
[0059] R 203 in the formula (B) is selected from a group consisting of hydrogen atom, alkyl groups such as methyl group and ethyl group, and aryl groups such as phenyl group. R 204 , R 205 , R 206 , R 207 , and R 208 are independently selected from a group consisting of hydrogen atom, nitro group, cyano group, halogen atoms such as fluorine, chlorine, bromine, and iodine, trifluoromethyl group, alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, dialkylamino group, and hydroxyl group, and Z represents an atom group required for forming a substituted or non-substituted aromatic carbon ring or a substituted or non-substituted aromatic heterocyclic ring.
[0060] Especially, an asymmetric azo pigment in which said Cp 1 and CP 2 have different structures from each other has better photosensitivity than a symmetric azo pigment in which said Cp 1 and CP 2 have structures identical to each other. The asymmetric azo pigment can respond to downsizing a diameter of a photo conductor and to speed up used process, to be effectively utilized.
[0061] Also, in titanylphthalocyanine having a maximum diffraction peak at 27.2° as diffraction peak at Bragg angle 2 θ (±0.2°), particularly, titanylphthalocyanine having a peak at 7.30 as a minimum angle can be effectively utilized.
[0062] The charge generating materials may be utilized independently or as a mixture of more than one kind thereof.
[0063] As for a binding resin used in the charge generating layer, according to need, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicon resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N-vinyl carbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, copoly(vinyl chloride/vinyl acetate), polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose based resin, casein, polyvinyl alcohol, and polyvinyl pyrrolidone etc. are given. Appropriate quantity of the binding resin is from 0 to 500 parts by weight, and preferably from 10 to 300 parts by weight, to 100 parts by weight of the charge generating material.
[0064] As for a method for forming the charge generating layer 45 , vacuum thin film process and casting process from solution and dispersion systems are mainly given. With respect to the former method, vacuum vapor deposition, glow discharge decomposition, ion plating, sputtering, reactive sputtering, and CVD method, etc., are used to form the charge generating layer 45 made from an inorganic material or an organic material described above. In order to form the charge generating layer by the latter casting method, the layer can be formed by applying an appropriately diluted dispersion liquid in which the inorganic or organic charge generating material described above is dispersed, with a binder resin if necessary, in a solvent such as tetrahydrofuran, cyclohexane, dioxane, dichloroethane, and butanone by means of ball mill, atriter, sand mill etc. As for the application, a method such as immersion coating, spray coating, bead coating, nozzle coating, spinner coating, and ring coating can be used. The film thickness of the charge generating layer 45 is appropriately about from 0.01 to 5 μm and more preferably from 0.1 to 2 μm.
[0065] The charge transfer layer 47 is formed by applying and drying the solution or dispersion liquid in which a charge transfer material and a binder resin are dissolved or dispersed into an appropriate solvent. If necessary, a plasticizer, a leveling agent, and an antioxidant may be added to the solution and the dispersion liquid.
[0066] The charge transfer materials are classified as hole transfer materials and electron transfer materials. As for the charge transfer material, for example, an electron-accepting material such as chloranyl, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno[1,2-b]thiophene-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and benzoquinone derivatives are given.
[0067] As for a hole transfer material, poly-N-vinyl carbazole and derivatives thereof, poly-γ-carbazolyl ethyl glutamate and derivatives thereof, a condensate of pyrene and formaldehyde and derivatives thereof, polyvinyl pyrene, polyvinyl phenanthrene, polysilane, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bis-stilbene derivatives, enamine derivatives, and other well-known materials are given. The charge transfer materials are utilized independently or as a mixture of more than one kind thereof.
[0068] As for a binding resin, thermoplastic or thermosetting resin such as polystyrene, copoly(styrene/acryronitrile), copoly(styrene/butadiene), copoly(styrene/maleic anhydride), polyester, polyvinyl chloride, copoly(vinyl chloride/vinyl acetate), polyvinyl acetate, polyvinylidene chkoride, polyarylate resin, phenoxy resin, polycarbonate, acetylcellulose resin, ethylcellulose resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine formaldehyde resin, urethane resin, phenol resin, and alkyd resin etc. are given.
[0069] Appropriate quantity of the charge transfer material is from 20 to 300 parts by weight, and preferably from 40 to 150 parts by weight, to 100 parts by weight of a binder resin. It is preferable that the film thickness of the charge transfer layer be about from 5 to 100 μm. As for solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexane, ethyl methyl ketone and acetone etc. are given.
[0070] Also, a polymer having electron-donating groups can be included in the charge transfer layer. A polymer having electron-donating groups includes a polymeric charge transfer material having a function as a charge transfer material and a function as a binder resin, or a polymer of which monomers or oligomers have electron-donating groups at time of film formation of the charge transfer layer and a two or three dimensional crosslinking structure is formed at last by setting reaction or crosslinking reaction after film formation. A charge transfer layer consisting of the polymeric charge transfer material or a polymer having closslinking structure excels in respect to wear resistance. Generally, in a electro-photographic process, since electric potential at the charged areas (electric potential at the unexposed areas) is constant, if a surface layer of a photo conductor is worn by repeated use, electric field strength applied to a photo conductor becomes stronger depending on the wear. Since generation frequency of stains on the background become higher with elevation of the electric field strength, high wear resistance of a photo conductor is advantageous for preventing the stains on the background.
[0071] A charge transfer layer consisting of the polymeric charge transfer materials excels in film formation property and in charge transfer efficieny since the charge transfer layer is formed to be at a high density compared to the charge transfer layer consisting of low molecular weight dispersion type polymer. Thereby, a photo conductor having a charge transfer layer formed by the polymeric charge transfer material is expected to have high speed response. As for the polymeric charge transfer material, although well-known materials can be used, a polycarbonate containing triarylamine structure in its main chain and/or its side chain is well utilized. Especially, a polymeric charge transfer material represented by the general formula (I) to (X), which will be shown below, is well used, and the embodiments of the material will also be shown below.
[0072] In the formula (I), R 1 , R 2 , and R 3 are independently selected from a group consisting of substituted or not substituted alkyl groups containing 1 to 4 carbon atoms or halogen groups. R 4 is hydrogen atom or substituted or not substituted alkyl groups containing 1 to 4 carbon atoms. R 5 and R 6 are substituted or not substituted aryl groups. o, p, and q are independently selected from integers from 0 to 4. k and j mean composition of the compound and satisfy relations 0.1≦k≦1 and 0≦j≦0.9. n means repeating units and is an integer from 0 to 5000. X is an aliphatic divalent group, alicyclic divalent group, or a divalent group represented by the following general formula.
[0073] In the above formula, R 101 and R 102 are independently selected from a group consisting of substituted or not substituted alkyl groups containing 1 to 4 carbon atoms, substituted or not substituted aryl groups and halogen atom, respectively. 1 and m are integers from 0 to 4. Y is selected a group consisting of from a single bond, alkylene groups being straight or branched chain or ring having 1 to 12 carbon atoms, —O—, —S—, —SO—, —CO—, —CO—O—Z—O—CO— in which Z is aliphatic divalent group, or
[0074] In the above formula, a is 1 or 2. b is an integer from 1 to 2000. R 103 and R 104 are substituted or not substituted alkyl groups containing 1 to 4 carbon atoms or substituted or not substituted aryl groups. Herein, R 101 and R 102 , and R 103 and R 104 are identical or different from each other.
[0075] In the above formula, R 7 and R 8 are substituted or not substituted aryl groups, and Ar 1 , Ar 2 , and Ar 3 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0076] In the above formula, R 9 and R 10 are substituted or not substituted aryl groups, and Ar 4 , Ar 5 , and Ar 6 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0077] In the above formula, R 11 and R 12 are substituted or not substituted aryl groups, and Ar 7 , Ar 8 , and Ar 9 are identical or different arylene groups. P is an integer from 1 to 5. X, k, j, and n are same as the case of formula (I).
[0078] In the above formula, R 13 and R 14 are substituted or not substituted aryl groups, and Ar 10 , Ar 11 , and Ar 12 are identical or different arylene groups. X 1 and X 2 are substituted or not substituted ethylene groups or substituted or not substituted vinylene groups. X, k, j, and n are same as the case of formula (I).
[0079] In the above formula, R 15 , R 16 , R 17 and R 18 are substituted or not substituted aryl groups, and Ar 13 , Ar 14 , Ar 15 and Ar 16 are identical or different arylene groups. Y 1 , Y 2 and Y 3 are selected from a group consisting of a single bond, substituted or not substituted alkylene groups, substituted or not substituted cycloalkylene groups, substituted or not substituted oxyalkylene groups, oxygen atom, sulfur atom, and vinylene group, and may be identical or different from each other. X, k, j, and n are same as the case of formula (I).
[0080] In the above formula, R 19 and R 20 are selected from a group consisting of hydrogen atom and substituted or not substituted aryl groups, and R 19 and R 20 have ring structures respectively. Ar 17 , Ar 18 and Ar 19 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0081] In the above formula, R 21 is selected from substituted or not substituted aryl groups, and Ar 20 , Ar 21 , Ar 22 and Ar 23 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0082] In the above formula, R 22 , R 23 , R 24 and R 25 are selected from substituted or not substituted aryl groups, and Ar 24 , Ar 25 , Ar 26 , Ar 27 and Ar 28 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0083] In the above formula, R 26 and R 27 are selected from substituted or not substituted aryl groups, and Ar 29 , Ar 30 and Ar 31 are identical or different arylene groups. X, k, j, and n are same as the case of formula (I).
[0084] The polymeric charge transfer materials may be used independently or as a mixture with more than one kind of the other polymeric charge transfer materials. Also, a low molecule weight charge transfer material can be combined with the above mentioned materials. As for other polymers having electron-donating groups, copolymers of well-known monomers, block copolymers, graft copolymers, star polymers, and crosslinking polymers having electron-donating groups, for example disclosed in Japanese Laid-Open Patent Application No.3-34001, 2000-206723, and 2001-34001 are included in the materials and can be well utilized.
[0085] In a photo conductor according to the invention, a plasticizer and a leveling agent may be added to the charge transfer layer 47 . As for a plasticizer, dibutylphthalate and dioctylphthalate etc., which are used as a general plasticizer, can be used, and the consumed quantity of the plasticizer is about from 0 to 30% by weight to a binding resin. As for a leveling agent, silicone oils such as dimethylsilicone oil and phenylmethylsilicone oil and a polymer or oligomer having perfluoroalkyl groups to side chains thereof are used, and the consumed quantity of the polymer or oligomer is about from 0 to 1% by weight to a binding resin.
[0086] Next, the case of a photo conductor having a single layer structure will be illustrated. A photosensitive layer in which at least the above mentioned charge generating material is dispersed in a binding resin can be used. A single photosensitive layer can be formed by applying and drying a liquid in which a charge generating material and a binding resin are dissolved or dispersed in an appropriate solvent. Further, the photosensitive layer may be a function separating type, to which the above mentioned charge transfer material is added, and can be used well. Also, if necessary, a plasticizer, a leveling agent, and an antioxidant can be added.
[0087] As for a binding resin, other than the binding resin used in the charge transfer layer 47 given above which may be also used itself, the binding resin used in the charge generating layer 45 given above may be mixed with the former binding resin. Of course, the polymeric charge transfer materials given above can be used well. To 100 parts by weight of a binding resin, the amount of the charge generating material is preferably from 5 to 40 parts by weight, and the amount of the charge transfer material is preferably from 0 to 190 parts by weight and more preferably from 50 to 150 parts by weight. A single photosensitive layer can be formed by applying liquid for coating in which a charge generating material and a binding resin, if necessary with the charge transfer material, are dispersed by a dispersing machine into a solvent such as tetrahydrofuran, dioxane, dichloroethane, and cyclohexane, using methods such as immersion coating, spray coating, bead coating, nozzle coating, spinner coating, and ring coating. It is appropriate for the thickness of the single photosensitive layer to be about from 5 to 100 μm.
[0088] In a photo conductor according to the present invention, an under coating layer, not shown in figures, can be inserted between the conductive supporter 41 and the photosensitive layer. Although an under coating layer generally includes resin as a main component, it is desirable for the resin to have high dissolution resistance to general organic solvents since a photosensitive layer is applied on the resin with a solvent. As for such a resin, a water soluble resin such as poly(vinyl alcohol), casein, and poly(sodium acrylate), an alcohol soluble resin such as copolyammide, and methoxymethyl nylon, a curing type resin forming three dimensional network structures such as polyurethane, melamine formaldehyde resin, phenol resin, alkyd-melamine resin, and epoxy resin are given. Also, fine powder pigment of metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide shown as examples may be added to an under coating layer to prevent generation of moire and to decrease residual potential.
[0089] The under coating layer can be formed by using appropriate solvents and coating methods as similar to the case of the above mentioned photosensitive layer. Further, as for the under coating layer according to the present invention, a silane coupling agent, a titanium coupling agent, and a chromium coupling agent etc. may be used. Al 2 O 3 produced by anodizing, an organic material such as poly(paraxylylene) (parylene) etc. and an inorganic material such as SiO 2 , SnO 2 , TiO 2 , ITO, and CeO 2 , formed by vacuum thin film production method, can be used well for an under coating layer according to the present invention. Well-known materials other than above mentioned materials can be used. The film thickness of the under coating layer is appropriately from 0 to 5 μm.
[0090] In the photo conductor according to the present invention, the protecting layer 49 as an outermost layer is formed on the photosensitive layer for protecting the photosensitive layer. As for a material employed in the protecting layer, resins such as AB resin, ACS resin, copoly(olefin/vinyl monomer), chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethyl benten, polypropylene, polyphenylene oxide, polysulfone, polysulfone, polystyrene, AS resin, copoly(butadiene/styrene), polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin are given.
[0091] As for a protecting layer, fluorocarbon resins such as polytetrafluoro ethylene, silicone resin, a material in which dispersion of an inorganic filler such as titanium oxide, tin oxide, potassium titanate, and silica or an organic filler is added to the resins can be added for improving wear resistance. A metal oxide is used well, and alumina, titanium oxide, and silica are particularly used well.
[0092] Also, it is preferable to add a charge transfer material to the protecting layer 49 for decreasing residual potential and improving sensitivity to light and response speed. As an added charge transfer material, a low molecular weight charge transfer material described with respect to the above mentioned polymeric charge transfer materials 45 is used. Furthermore, the above mentioned polymeric charge transfer material is also used well in respect to improving wear resistance and response speed. As for a method for forming a protecting layer, a normal application method is employed. It is appropriate for the thickness of a protecting layer to be about from 0.1 to 10 μm.
[0093] Furthermore, suppression for elevation of residual potential is realized by adding an organic compound having acid value from 10 to 400 (mgKOH/g). The referred term “acid value” is defined as the number of milligrams of potassium hydroxide required for neutralizing free fatty acids included in 1 g of a remarked material. As an organic compound in which acid value is from 10 to 400 (mgKOH/g), all of the generally known organic fatty acids and high acid value resins etc. can be used if the materials have acid values from 10 to 400 (mgKOH/g). However, since an organic acid and an acceptor having very low molecular weight have the capability to decrease the dispersion property of a filler, the effect of decreasing residual potential may not be exerted by using the compounds. Therefore, it is preferable to use a low molecular weight polymer and resin, copolymer, etc., and a mixture thereof in order to decrease residual potential of a photo conductor and to improve dispersion property of a filler. It is preferable for the organic compounds to have linear molecular structures and less steric hindrance. It is necessary to make both a filler and a binder resin having affinity in order to improve the dispersion property. A material having high steric hindrance decreases the affinity to degrade the dispersion property and causes many problems described above.
[0094] As for an organic compound having acid value from 10 to 400 (mgKOH/g), it is particularly preferable to use polycarboxylic acid. The polycarboxylic acid is a compound having the structure that carboxylic acids are included in a polymer or a copolymer. All of the organic compounds containing carboxylic acid and their derivatives such as polyester resin, acrylic resin, copolymers produced by using acrylic acid and methacrylic acid, and styreneacrylcopolymer can be used. It is possible to use a mixture of more than one of the compounds, and the mixture is useful. Depending on the situation, by mixing the compound and an organic fatty acid, the dispersion property of the filler and the associated effect of decreasing residual potential may be improved. The amount of the added organic compounds having acid value from 10 to 400 (mgKOH/g) is from 0.01 wt % to 50 wt %, preferably from 0.1 wt % to 20 wt % to the amount of the contained filler. However it is more preferable to add the required minimum quantity If the addition quantity is more than a minimum requirement, image blur may result. If the addition quantity is too small, the effect of decreasing residual potential is not enough sufficiently realized. Acid value of the organic compound is preferably from 10 to 400 mgKOH/g, and more preferable from 30 to 200 mgKOH/g. If the acid value is higher than a requirement, the resistance is reduced too much and the image blur becomes large. If the acid value is too small, the addition quantity has to be increased and the effect of decreasing residual potential is not sufficiently realized. Herein, it is necessary for the acid value of the organic compound to be determined depending on the addition quantity. However, the acid value of the organic compound does not directly cause the effect of decreasing residual potential, which more significantly depends on structure or molecular weight of the organic compound used and the dispersion property of a filler etc.
[0095] In the photo conductor according to the present invention, an intermediate layer, not shown in the figures, can be laid between a photosensitive layer and a protecting layer. For the intermediate layer, a binder resin is generally used as the main component. As for the resin, polyamide, alcohol soluble nylon, water soluble polyvinyl butyral, polyvinyl alcohol, etc., are given. As a formation method of the intermediate layer, normal application methods are employed as described before. It is preferable for the thickness of the intermediate layer to be from 0.05 to 2 μm.
[0096] In the present invention, an antioxidant, a plasticizer, a lubricant, an ultraviolet absorbent, a low molecular weight charge transfer material, and a leveling agent can be added to each layer for improving adaptation to the environment and particularly for preventing decrease of sensitivity and elevation of residual potential. The representative materials of the compounds are described below.
[0097] As an antioxidant capable of being added to each layer, for example, the following materials are given, but an antioxidant is not limited to these.
[0098] (a) Phenols
[0099] 2,6-di-t-butyl-p-cresol, butyklhydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3-(4′-hydroxy-3′,5′-di-t-butylphenol), 2,2′-methylene-bis-(4-methyl-6-t-butylphenol), 2,2′-methylene-bis-(4-ethyl-6-t-butylphenol), 4,4′-thiobis-(3-methyl-6-t-butylphenol), 4,4′-butylidenebis-(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[metylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, bis[3,3′-bis(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester, tocopherol, etc.
[0100] (b) Paraphenylenediamines
[0101] N-phenyl-N′-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N,N′-di-isopropyl-p-phenylenediamine, and N,N-dimethyl-N,N-di-t-butyl-p-phenylenediamine, etc.
[0102] (c) Hydroquinones
[0103] 2,5-di-t-octylhydroquinone, 2,6-didodecyl hydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, and 2-(2-octadecenyl)-5-methylhydroquinone, etc.
[0104] (d) Organic Sulfur Compounds
[0105] dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and ditetradecyl-3,3′-thiodipropionate, etc.
[0106] (e) Organic Phosphorus Compounds
[0107] triphenylphosphine, tri(nonyl phenyl)phosphine, tri(dinonyl phenyl)phosphine, trikrezylphophine, and tri(2,4-dibutyl pkenoxy)phosphine, etc.
[0108] As for a plasticizer capable of being added to each layer, for example, the following materials are given, but a plasticizer is not limited to these.
[0109] (a) Phosphate-Based Plasticizers
[0110] triphenyl phosphate, trikrezyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, krezyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, and triphenyl phosphate, etc.
[0111] (b) Phthalate-based plasticizers
[0112] dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethyl hexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, decyl octyl phthalate, dibutyl fumarate, and dioctyl fumarate, etc.
[0113] (c) Aromatic Carboxylate-Based Plasticizers
[0114] trioctyl trimellitate, tri-n-octyl trimellitate, and octyl oxybenzoate, etc.
[0115] (d) Ester of Aliphatic Dibasic Acid-Based plasticizers
[0116] dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, n-octyl-n-decyl adipate, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl sebacate, dioctyl tetrahydrophthalate, and n-octyl tetrahydrophthalate, etc.
[0117] (e) Fatty Acid Ester Derivatives
[0118] butyl oleate, grycerine monooleic acid ester, pentaerisritol ester, dipentaerisritol hexaester, triacetin, and tribuyne, etc.
[0119] (f) Oxycarboxylate-Based Plasticizers
[0120] methyl acetylricinoleate, butyl acetylricinoleate, butylphthalylbutyl glycolate, and tributyl acetylcitrate, etc.
[0121] (g) Epoxy Plasticizers
[0122] epoxidated soya bean oil, epoxidated linseed oil, butyl epoxystearate, decyl epoxystearate, octyl epoxystearate, benzyl epoxystearate, dioctyl epoxyhexahydrophthalate, and didecyl epoxyhexahydrophthalate, etc.
[0123] (h) Divalent Alcohol Ester-Based Plasticizers
[0124] diethylene glycol dibenzoate, and triethylene glycol di-2-ethyl butyrate, etc.
[0125] (i) Plasticizers Including Chlorine
[0126] chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl ester, and methoxy chlorinated fatty acid methyl ester, etc.
[0127] (j) Polyester-Based Plasticizers
[0128] polypropyrene adipate, polypropyrene sebacate, polyester, and acetylized polyester, etc.
[0129] (k) Sulfonic Acid Derivatives
[0130] p-toluene sulfonamide, o-toluene sulfonamide, p-toluene sulfonethylamide, o-toluene sulfonethylamide, toluene sulfone-N-ethylamide, p-toluene sulfone-N-and cyclohexylamide, etc.
[0131] (l) Citric Acid Derivatives
[0132] triethyl citrate, triethyl acetylcitrate, tributyl citrate, tributyl acetylcitrate, tri-2-ethylhexyl acetylcitrate, and n-octyldecyl acetylcitrate, etc.
[0133] (m) Others
[0134] terphenyl, partially hydrated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, and methyl abietate, etc.
[0135] As for a lubricant capable of being added to each layer, for example, the following materials are given, but a luburicant is not limited to these.
[0136] (a) Hydrocarbons
[0137] liquid paraffin, paraffin wax, microwax, and low grade polymerized polyethylene, etc.
[0138] (b) Fatty Acids
[0139] lauric acid, n-tetradecanoic acid, palmitin acid, stearic acid, arachic acid, and behenic acid, etc.
[0140] (c) Fatty Acid Amides
[0141] stearylamide, palmitylamide, oleinamide, methylenebisstearoamide, and ethylenebisstearoamide, etc.
[0142] (d) Esters
[0143] fatty acid lower alcohol ester, ester of fatty acid polyalcohol ester, and fatty acid polyglycol ester, etc.
[0144] (e) Alcohols
[0145] cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, and polyglycerol, etc.
[0146] (f) Metal Soap
[0147] lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, and magnesium stearate, etc.
[0148] (g) Natural Wax
[0149] carnauba wax, candelilla wax, bees wax, whale wax, ibota wax and montan wax, etc.
[0150] (h) Others
[0151] silicone compounds and fluorine compounds, etc.
[0152] As for an ultraviolet absorbent capable of being added to each layer, for example, the following materials are given, but an ultraviolet absorbant is not limited to these.
[0153] (a) Benzophenone Derivatives
[0154] 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2,′,4-trihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone, etc.
[0155] (b) Salicylates
[0156] phenyl salicylate, and 2,4-di-t-butyl-3,5-di-t-butyl-4-hydroxybenzoate, etc.
[0157] (c) Benzotriazole Derivatives
[0158] (2′-hydroxyphenyl)benzotriazole, (2′-hydroxy-5′-methylphenyl)benzotriazole, and (2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, etc.
[0159] (d) Cyanoacrylates
[0160] ethyl-2-cyano-3,3′-diphenylaccrylate and methyl-2-carbomethoxy-3-(paramethoxy)acrylate, etc.
[0161] (e) Quenchers (Metallic Complex Salts)
[0162] nickel (2,2′-thiobis(4-t-octyl)phenolate)-n-butylamine, nickel dibutyldithiocarbamate, and cobalt dicyclohexyldithiophosphate, etc.
[0163] (f) HALS (Hindered Amines)
[0164] bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]-2,2,6,6,-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro[4,5]undecane-2,4-dione, and 4-benzoyloxy-2,2,6,6-tetramethylpyridine, etc.
[0165] [0165]FIG. 5 is a schematic for illustrating an electro-photographic apparatus according to the present invention involving the variations described below. In FIG. 5, the photo conductor 11 is formed by laying a photosensitive layer and an outermost layer including a filler. The photo conductor 11 is shown in the form of a drum, but it may be in the form of a sheet or an endless belt.
[0166] The charger 18 contacts or is closely arranged to the photo conductor 11 . The charger is used well, because the charger generates less ozone and nitrogen oxide, which become a source generating low resistance materials, than the case of a coronal charger represented by corotron and scorotron. Particularly, the charger arranged in close proximity to a non-contact charged roller, in which a distance between the charger and a surface of the photo conductor is equal to or less than 200 μm (preferably, equal to or less than 100 μm), is used well, since very little pollution is produced by the charger even with repeated use. According to need, the pre-transcription charger 22 , a transcription charger, a separation charger, and the pre-cleaning charger 27 are arranged, and well-known means such as a corotron, a scorotron, a solid state charger, and a charged roller are used. When the photo conductor is charged by the charger, unevenness of charging can be effectively reduced by charging the photo conductor with an electric field formed by superposing an alternating current component on a direct current component in the charger. As for a transcription means, although the above charger can be generally used, the charger using transcription belt 25 shown in FIG. 5 can be preferably used.
[0167] As for a light source such as an image exposing unit 20 and charge removing lamp 17 , all light emitters such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, light emitting diodes (LED), semiconductor lasers, and electro luminescence can be used. For providing light only at the desired spectral region, filters such as a sharply cutting filter, a bandpass filter, a near-infrared cutting filter, dichroicfilter, an interference filter, and a conversion filter for color temperature may be used.
[0168] Such a light source illuminates the photo conductor and thereby can be used to add a process such as a transcription process, a charge removing process, a cleaning process, or pre-exposure combined with light illumination, etc. other than the process shown in FIG. 5.
[0169] Toners developed by the development unit 21 on the photo conductor 11 are transferred to the transcription paper 24 . However, not all of the toner is transferred, and some of the toner remains on the photo conductor 11 . Such toner is removed from the photo conductor by a fur brush 28 and a cleaning brush 29 . Cleaning may be performed by only a cleaning brush or by a combination such as a fur brush and a magfur brush used as a cleaning brush. A positive (negative) electrostatic latent image is formed on a surface of the photo conductor by providing a positive (negative) charge to the electro-photographic photo conductor followed by exposing the image. A positive image is obtained if a latent image is developed by negative (positive) polar toners (charge detecting particles), and a negative image is obtained if a latent image is developed by positive (negative) polar toners. A well-known means is applied to such a development means and also to such a charge removing means.
[0170] Furthermore, not shown in the figure, a member providing zinc stearate on the surface of the photo conductor may be placed. By the member providing zinc stearate on the surface of the photo conductor, it is possible to control filming which provides good wear resistance. Zinc stearate is effective for suppression of image distortion as well as for providing good wear resistance during repeated toner adhesion to the photo conductor and toner recovery by a cleaning means when the image is not formed, in the electro-photographic process using the photo conductor. As the means of providing said zinc stearate, it is very effective for zinc stearate to be included in the developer (toners) presented on the development means.
[0171] If the amount of zinc stearate provided on the photo conductor is too much, the amount of output also increases, and a fixation defect results which is not preferable. If a friction coefficient of a surface of the photo conductor is reduced to about 0.1 by providing too much zinc stearate, decrease of image density results which is not preferable. On the other hand, if the amount of zinc stearate is small, filming of toner component on the photo conductor is generated to cause image distortion or unevenness of contrast in the middle density which is not preferable. For example, when zinc stearate is included in toners to be provided on the surface of the photo conductor, it is preferable for the amount of included zinc stearate in the toners to be from 0.1 to 0.2% by weight.
[0172] In an image formation process according to the present invention, when an image is not formed, suppression of filming on a surface of the photo conductor in order to keep wear resistance high pertaining to toners adhering to the photo conductor and recovering toner at the cleaning means, and, in addition, suppression of adhesion and deposition of products due to charging, can be achieved. Achieving these preferred conditions depends on cleaning effect in removing each kind of adhesive from the toner. Removing adhesives and recovering toner is effective in the condition of the amount of adhesives in toners being in the middle density areas and the operating time being about 30 minutes (in the case that the diameter of the photo conductor is 30 mm and line speed is 125 mm/s). An amount of adhesives and an operating time more than those described above are not preferable, since burden on the cleaning means and the consumed quantity of toner are increased. If a diameter of a photo conductor and/or line speed are different from those described above, the parameters can be appropriately adjusted to achieve operation conditions similar to those described above.
[0173] <Embodiments>
[0174] The present invention will be illustrated in detail by embodiments according to the present invention and comparisons below.
[0175] (Production of Toners)
[0176] Styrene acrylic resin (Haimar 75 produced by Sanyo Chemical): 85 parts
[0177] Carbon black (#44 produced by Mitsubishi Chemical): 8 parts
[0178] Azo dye including metal (Bontron S-34 produced by Orient Chemical): 2 parts
[0179] Carnauba wax (WA-03 produced by Serarika Noda): 5 parts
[0180] After the mixture having the above described composition was melted and kneaded by using heating roll at 140° C., the mixture was cooled and solidified. Subsequently, the mixture was milled by jet mill and classified to obtain toners having average diameter about 8.0 μm. The toners used in the following embodiments were obtained by mixing 0.7% hydrophobic silica R-972 (produced by Japan Aerosil) with 100 parts by weight of the toners obtained above by henshell mixer.
[0181] (Production of Carriers)
[0182] Coating liquid was prepared by mixing 100 g of toluene with 100 g of the silicone resin (SR-2411 produced by Toray Dow Corning Silicone). The solution was applied to 1 kg of carrier heartwood (averaged particle diameter 60 μm Cu—Zn ferrite) by fluid bed method. Subsequently, they were dried for about 5 minutes, heated for 1 hour at 200° C., cooled, and sieved to produce the carriers according to the present invention. When the average diameter of particles is modified and next coated, it is necessary to adjust the amount of silicone resin converting the surface area to make the film thickness uniform.
[0183] (Production of a Developer)
[0184] The toners: 4 parts
[0185] The carriers: 96 parts
[0186] The toners and the carriers were mixed by tabler mixer.
[0187] (Production of Photo conductor A)
[0188] Coating liquid for under coating layer, coating liquid for charge generating layer, and coating liquid for charge transfer layer, which have the following compositions, in order, were applied on the aluminum cylinder (material:JIS1050) having 30 mm of the diameter and 340 mm of the length and dried to form an electro-photographic photo conductor consisting of 3.5 μm of under coating layer, 0.2 μm of charge generating layer, 22 μm of charge transfer layer and 2 μm of protecting layer.
[0189] <Coating Liquid for the Under Coating Layer>
[0190] Titanium dioxide powder: 400 parts
[0191] Melamine formaldehyde resin: 65 parts
[0192] Alkyd resin: 120 parts
[0193] 2-butanone: 400 parts
[0194] <Coating Liquid for a Charge Generating Layer>
[0195] Bisazo dye having the following structure: 8 parts
[0196] Trisazo dye having the following composition: 6 parts
[0197] Polyvinyl butyral: 5 parts
[0198] 2-butanone 200: parts
[0199] Cyclohexanone 400: parts
[0200] <Coating Liquid for the Charge Transfer Layer>A-type polycarbonate: 10 parts
[0201] The charge transfer material represented by the following structural formula: 7 parts
[0202] Tetrahydrofuran: 400 parts
[0203] Cyclohexanone: 150 parts
[0204] <Coating Liquid for the Protecting Layer>
[0205] A-type polycarbonate: 10 parts
[0206] The charge transfer material represented by the following structural formula: 8 parts
[0207] Alumina particles: 4 parts
[0208] Tetrahydrofuran: 400 parts
[0209] Cyclohexanone: 150 parts
[0210] (Production of Photo Conductor B)
[0211] The photo conductor B was obtained by a method similar to the case of the photo conductor A except that alumina paricles were not used in the coating liquid for the protecting layer of the photo conductor A.
[0212] (Production of Photo Conductor C)
[0213] The photo conductor C was produced by a method similar to the case of the photo conductor A except that tetrafluoroethylene particles as an alternative to alumina particles were used in the coating liquid for the protecting layer of photo conductor A.
[0214] (Production of Photo Conductor D)
[0215] The photo conductor D was produced by a method similar to the case of the photo conductor A except that charge transfer material was not employed in the coating liquid for the protecting layer of photo conductor A.
[0216] (Production of Photo Conductor E)
[0217] The photo conductor E was produced by a method similar to the case of the photo conductor A except that the coating liquid for the protecting layer of photo conductor A was modified to one having the following composition.
[0218] <Coating Liquid for the Protecting Layer>
[0219] Polymeric charge transfer material having the following structural formula: 18 parts
[0220] Alumina particles: 4 parts
[0221] Tetrahydrofuran: 400 parts
[0222] Cyclohexanone: 150 parts
[0223] (Production of Photo Conductor F)
[0224] The photo conductor F was produced by a method similar to the case of the photo conductor A except that the coating liquid for the protecting layer of photo conductor A was modified to one having the following composition.
[0225] <Application Liquid for the Protecting Layer>
[0226] A-type polycarbonate: 10 parts
[0227] Charge transfer material having the following structural formula: 8 parts
[0228] Alumina particles: 4 parts
[0229] Unsaturated polycarboxylic acid polymer solution: 0.lpats (acid value:180 mgKOH/g, produced by BYK Chem)
[0230] Tetrahydrofuran: 400 parts
[0231] Cyclohexanone: 150 parts
[0232] (Production of Photo Conductor G)
[0233] The photo conductor was produced by a method similar to the case of the photo conductor A except that the coating liquid for the charge generating layer of photo conductor A was modified to one having the following composition.
[0234] <Coating Liquid for Charge Generating Layer >
[0235] Phthalocyanine in which the following XD spectrum was obtained: 3 parts
[0236] Polyvinyl butyral: 2 parts
[0237] 2-butanone: 120 parts
[0238] (Production of Photo Conductor H)
[0239] In the production example for the photo conductor G, the photo conductor H was formed by anodizing the conductive supporter, followed by laying a charge generating layer, a charge transfer layer, and a protecting layer, similar to the production example for photo conductor G, but without a laying under coating layer.
[0240] <Anodizing>
[0241] After mirror polishing, degreasing, and washing were applied to the surface of the supporter, the supporter was immersed into the electrolytic bath being 15% by volume of sulfuric acid at 20° C. of solution temperature and anodizing was applied to the supporter for 30 minutes at 15V of bath voltage. Furthermore, after the supporter was washed by water, a sealing treatment was applied in 7% nickel acetate solution (at 50° C.). After that, the supporter on which oxidation film on the anode of 6 μm was produced was obtained via washing by purified water.
[0242] (Evaluation)
[0243] Carrying performance of developer was evaluated by using the developer and the photo conductors produced as described above in the copying machine (Imagio MF250 produced by RICOH) in the condition shown in Table 1. The surface roughness (Rz) of the sleeve was adjusted by changing the processing condition. The development gap (Gp) and the doctor gap (Gd) between the controller and the developer supporter were adjusted by settings of the machine.
[0244] Next, after 30000 copies were continuously produced by using A4, 6% chart, the abrasion loss of the photo conductor was measured. The surface condition of carriers was observed by SEM, and peeling of the film and pollution with the toners were evaluated.
[0245] <A method of Evaluating Carrying Performance>
[0246] Carrying performance: Five A3 black images were continuously produced and the uniformity of the black color in the fifth image was evaluated. If the developer was not carried well, the black color was diluted or the image having some lines was generated.
TABLE 1-1 Particle diameter of Surface Used photo NO. carrier (D) (μm) roughness (Rz) (μm) conductor 1 50 10 A 2 50 10 A 3 50 10 A 4 50 10 B 5 50 10 A 6 50 10 A 7 50 30 A 8 50 25 A 9 60 20 A 10 50 5 A 11 50 50 A 12 50 10 C 13 50 10 D 14 50 10 E 15 50 10 F 16 50 10 G 17 50 10 H
[0247] [0247] TABLE 1-2 Gp Gd Development sleeve NO. (μm) (μm) Gp/Gd D/Rz processing method 1 0.7 0.7 1.0 5.0 Sand blast 2 0.7 1.0 0.7 5.0 Sand blast 3 0.7 1.0 0.7 5.0 Grinding 4 0.7 1.0 0.7 5.0 Sand blast 5 0.7 0.5 1.4 5.0 Sand blast 6 0.6 1.0 0.6 5.0 Sand blast 7 0.7 0.9 0.78 1.7 Sand blast 8 0.7 0.9 0.78 2.0 Sand blast 9 0.7 0.9 0.78 3.0 Sand blast 10 0.7 1.0 0.7 10.0 Sand blast 11 0.7 0.9 0.78 1.0 Sand blast 12 0.7 1.0 0.7 5.0 Sand blast 13 0.7 1.0 0.7 5.0 Sand blast 14 0.7 1.0 0.7 5.0 Sand blast 15 0.7 1.0 0.7 5.0 Sand blast 16 0.7 1.0 0.7 5.0 Sand blast 17 0.7 1.0 0.7 5.0 Sand blast
[0248] [0248] TABLE 1-3 Developer Abrasion carrying loss No. performance (μm) Others 1 2 to 3 0.5 2 2 to 3 0.8 3 3 0.8 4 2 to 3 3.5 Image density decrease 5 2 0 Photo conductor filming 6 4 2.2 Carriers adhesion 7 2 1.3 8 1 1.0 9 1 0.5 10 4 0 Photo conductor filming 11 2 2.5 Carrier film peeling off 12 2 to 3 1.1 13 2 to 3 1.3 Image density slight decrease 14 2 to 3 0.4 15 2 to 3 0.8 Potential at exposed area decreasing comprared to comparison 2. Good filler dispersion in protecting layer. Good resolution. 16 2 to 3 0.8 Quantity of light could be reduced compared to comparison 2. Good resolution. (Very) good image density 17 2 to 3 0.8 Background was uniform compared to comparison 2.
EXAMPLE NO.18
[0249] The charger of the copying machine used in example 2 was modified and adapted to a scorotron charger as an alternative to the charged roller and 30000 copies were continuously produced similar to example 2. Herein, the electric potential at an unexposed area of the photo conductor was adjusted to be the same (−800V) as example 2.
EXAMPLE NO.19
[0250] The charger of the copying machine used in example 2 was modified and adapted to the charged roller described below as an alternative to the contact charged roller and 30000 copies were continuously produced similar to example 2. Additive voltage was only a DC component similar to example 2.
[0251] <Charged Roller>
[0252] A closely arranged charged roller was formed by wrapping teflon tape having a thickness of 100 μm around areas (which are not image formation areas) of 0 to 5 mm measured from both edges of the charged roller used in example 2.
EXAMPLE NO.20
[0253] Continuous copying was carried out similar to example 19, except that the charging condition of example 19 was changed as follows.
[0254] <Charging Condition>
[0255] The electric potential at an unexposed area: −800V −1.5V measured as peak to peak was applied as an AC component.
[0256] As described above, after 30000 copies were continuously produced in example 2, 18-20 half tone images were outputted under high temperature and high humidity (30° C., 90% RH) and the images were evaluated. The result of the evaluation is shown in table 2.
TABLE 2 No. Half tone image Remark 2 Stains on image background resulting from dirty of charged roller was generated a little. 18 Resolution was decreased a In continuously little. copying, odor of ozone was strong. 19 Uneven density based on uneven charging was generated a little. 20 Good
[0257] Although all of the trouble points in examples 2, 18, and 19 were not a troublesome level for actual use, the condition in example 20 was best.
<EXAMPLE NO.21
[0258] 50000 copies were continuously produced in the condition of example 2.
EXAMPLE NO.22
[0259] The copying machine used in example 21 was adapted to set the zinc stearate providing unit between the cleaning unit and the charging unit, wherein the structure of the zinc stearate providing unit was such that zinc stearate in the form of a bar was applied for 10 minutes every 100 copies. In terms of conditions, the endurance test was performed similar to example 21.
EXAMPLE NO.23
[0260] The endurance test was performed similar to example 21 except that 0.15% zinc stearate powder was added to the toner provided to the development area.
EXAMPLE NO.24
[0261] The endurance test was performed similar to example 23 except that in example 24, every time after producing 1000 papers, exposure to the electric potential of bright areas, the image not being formed process, toner development on the development area formed by the above exposure, and repetition of only recovering toner from the surface of the photo conductor by the cleaning unit were carried out for 20 minutes.
[0262] After executing examples from 21 to 24, the output of the images was performed under the conditions of high temperature and high humidity. After the experiment was finished, the surfaces of the photo conductors were observed and the results are shown in Table.3.
TABLE 3 Image (after 50000 No. copies) Others 21 Lack of image Filming occurred a little. was generated a little. 22 Good Filming did not occur. Nice image was obtained. 23 Good Filming did not occur. Nice image was obtained. After run, as image was outputted at high temperature and high humidity, image blur occurred a little. 24 Good Filming did not occur. Nice image was obtained. Image blur did not occur even at high temperature and high humidity.
[0263] Under the conditions of example 21, as an endurance test was performed to 50000 copies, filming occurred on the surface of the photo conductor a little, and the lack of image occurred in association with the filming, however, the lack of image was not a troublesome level. On the other hand, filming could be prevented by providing zinc stearate on the surface of the photo conductor as in examples 22 and 23 . Further, the image blur could be completely eliminated even at high temperature and high humidity (30° C. 90%RH) by cleaning the surface of the photo conductor as in example 24.
[0264] As it is clear that the present invention has excellent effects from the above detailed and concrete illustrations, according to the present invention, abrasion loss of a photo conductor could be suppressed by satisfying a relation Gp/Gd=0.7 to 1.0 and using a photo conductor having a protecting layer including a filler, a good balance with the carrying performance of a developer could be struck, the effects were enhanced by using a sand blasting process, and carrying performance could be improved by satisfying a relation 2≦D/Rz≦3.
[0265] Elevation of electric potential at exposed areas originating from repeated use of a photo conductor can be suppressed and nice images can be obtained, by combining a charge transfer material or an organic compound having particular acid value with a protecting layer including a filler.
[0266] Adhesion of low resistant material to a surface of a photo conductor can be reduced by selecting an appropriate charging condition of a photo conductor in an image formation apparatus, and the effect of the present invention can be more significant.
[0267] The effect of the present invention can be more significant by including the means providing zinc stearate on a surface of a photo conductor.
[0268] The present invention is not limited to the specifically disclosed embodiments, and variations and modifications may be made without departing from the scope of the present invention.
[0269] The present application is based on Japanese priority applications No.2000-387939 filed on Dec. 20, 2000 and No.2001-380525 filed on Dec. 13, 2001, the entire contents of which are hereby incorporated by reference. | An image formation apparatus develops an electrostatic latent image with a two-component developer consisting of magnetic carriers and toners by using a development apparatus and a latent image supporter including a filler in an outermost layer thereof, the development apparatus having a developer supporter, which has an internally fixed magnetic body and rotates while supporting a developer on a surface thereof, and a developer quantity controller controlling a quantity of the developer which is supported by the developer supporter facing the magnetic body and controlling a height of magnetic brushes and consisting of materials having rigidity or rigidity and magnetic properties, wherein a ratio (Gp/Gd) of a development gap to a doctor gap between the developer supporter and the controller is from 0.7 to 1.0, and a weight-averaged particle diameter of a developer carrier is from 20 to 60 μm. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119 to U.S. Application No. 60/745,829, filed Apr. 27, 2006, the disclosure of which is incorporated by reference as if fully set forth herein.
INCORPORATION BY REFERENCE
[0002] All publications and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference
BACKGROUND OF THE INVENTION
Neuropathy and Spinal Cord Stimulation (“SCS”)
[0003] Neuropathic pain is prevalent in the US in approximately 1.5% of the population, 1% in the UK, and at a comparable level in Canada (“Spinal Cord Stimulation for Neuropathic Pain, Health Technology Literature Review,” Ministry of Health and Long Term Care, Toronto, Ontario, Canada, 2005). In 2002, it was reported that between 6 and 10 million Americans were afflicted with Neuropathic pain (P. S. Staats, “Intrathecal Therapy for Neuropathic Pain,” Proceedings of the 18 th Annual Meeting of the American Academy of pain Medicine ( AAPM ), San Francisco, 2002). Neuropathic pain is generally caused by a dysfunction in the nervous system and is a known complication of diabetes mellitus, which represents 6% of the US population. About 15 percent of patients with diabetes have both symptoms and signs of neuropathy, but nearly 50 percent have evidence of peripheral nerve damage as judged by nerve conduction abnormalities (A. H. Ropper, R. H. Brown, ADAMS AND VICTOR'S PRINCIPLES OF NEUROLOGY, Eighth Edition, The McGraw-Hill Companies, Inc, 2005, ch.46). People suffering from neuropathic pain are generally considered to have chronic pain, which can lead to loss of productivity, depression and reduction in Quality of Life. Neuropathy presents as Failed Back Surgery Syndrome (FBSS), Complex Regional Pain Syndrome (CRPS), and postherpetic neuralgia. For each of these conditions, Spinal Cord Stimulation (SCS) is considered as a viable therapy only after failure of treatments with pharmacological, nonpharmacological and surgical treatments.
[0004] SCS systems are comprised of an implantable pulse generator and a lead with electrodes at the distal end surgically positioned in the epidural space, posterior to the spinal cord. SCS treatment is considered weakly to moderately effective in the treatment of chronic pain due to neuropathy when all else fails. SCS works by passing impulses through a nerve fiber that is either inhibiting the pain signal, or disrupting a nerve fiber that is conducting the pain signal.
SCS Limitations
[0005] For patients studied between 2000 and 2005, about 1.2% had complication due to infection and another 1.2% due to dural puncture and 11% technical failures due to electrode migration or malpositioning. Additionally, SCS electrodes used to be implanted in a less conductive medium than that of the Cerebral Spinal Fluid (CSF), percutaneously, but complications with fibrosis altered device behavior (K. M. Alo, “Recent Advances in Neurostimulation Analgesia,” Techniques in Regional Anesthesia and Pain Management, Vol. 5, No. 4, 2001, pp: 142-151). Since the CSF is highly conductive, it acts as a shunt, requiring electrode guarding techniques and increase in number of stimulation sites to four in order to obtain adequate current focusing. This approach is highly sensitive to electrode placement due to the need to focus the electric current across the stimulated axon, and over time, the electrodes migrate in the epidural space, decreasing the effectiveness of the treatment.
Nociceptive Pain
[0006] More generally, chronic pain (CP) that is nociceptive has been poorly defined and documented until recently and is considered widely undertreated. According to the International Association for the Study of Pain (IASP), CP prevalence ranges from 10.5% to 55.2%. The American College of Rheumatology (ACR) estimated CP prevalence at 10.1% to 13%. Studies show that there is little variation of prevalence in populations, ranging from 8% in children to approximately 11% in Adults. CP is generally defined as pain that persists beyond the normal time of healing and may be associated with a disease where healing may never occur (M. Ospina and C. Harstall, “Prevalence of Chronic Pain: An Overview,” Alberta Heritage Foundation for Medical Research, Health Technology Assessment, Edmonton, Alberta, Canada, (2002)). Different associations have generally defined CP to present as chronic if it persists beyond the range of one to six months, with many agreeing on three.
[0007] Treatment of nociceptive pain that is acute, post-surgical or chronic is generally done with analgesics. In particular, chronic pain has given rise to patient-controlled-analgesic infusion pumps (PCA's) (see U.S. Pat. No. 5,630,710), which are capped to limit amount of opiates and reduce dependency. In addition, transcutaneous electrical neural stimulators (TENS) devices (see, e.g., U.S. Pat. No. 4,121,594) demonstrated moderate impact on the suppression of pain, but were never used alone to suppress severe pain. Many TENS devices are commonly used for massage, where they pass electrical current through large muscle fiber, contracting it and in essence stimulating ascending large fiber neurons which were thought to suppress pain. SCS devices are deployed when all pharmacological solutions are exhausted in patients with intractable pain. Studies have also shown that intermittent stimulation of the spinal cord in sessions provides relief for both nociceptive and neuropathic pain, allowing of the scheduling of stimulation sessions using non-implantable subcutaneous needle electrodes.
Mechanisms of Pain
[0008] Pain, whether introduced nociceptively by tissue damage, or neuropathically by nerve damage, is conducted through the peripheral nervous system and transmitted to the spinal cord via Aδ and C-fibers. C fibers are small, non-myelenated and slow conducting in the range of 0.5-1.2 m/s. C-fiber diameter is in the order of 1 mm and has a membrane time constant of 0.25-3 ms. Some Aδ fibers are faster conducting 12-36 m/s and have membrane time constants that range to 0.1 ms (L. R. Squire, F. E. Bloom, S. K. McConnell, J. L. Roberts, N. C. Spitzer, M. J. Zigmond, Fundamental Neuroscience, Second Edition, Academic Press, Elsevier Science, San Diego Calif., 2003, ch. 25).
[0009] Aδ fibers, the faster conductors of pain, are carriers of the “first pain” sensation that is very highly localized. First pain is much more tolerable than the sustained second pain, and is the trigger to a reflexive withdrawal to cutaneous pricking, for instance. Aδ fibers are also mechanoceptors that respond to application of heat with very high threshold. Repeated application of heat stimuli on Aδ mechanoceptors receptor sites decreases the threshold, increases the response, thus leading to sensitization.
[0010] C fibers are polymodal, responding to tissue deformation, noxious stimuli and heat. They are responsible for the second pain which is poorly localized and poorly tolerated. In general, they transmit burning sensations. Aβ fibers are larger mechanoceptors, synapsing more anteriorally within the spinal cord to Aδ and C fibers. These larger fibers are considered by some researchers to be responsible for the “Gate Control Theory,” where their stimulation is responsible for neuromodulation, or suppression, of pain sensation in the smaller fiber group. Many have refuted this finding, yet it is known that muscle contraction of pain-sites using TENS devices decreases pain response and provides prolonged relief.
Neuromagnetic Stimulation
[0011] Devices and methods for performing neurostimulation using a combination of a magnetic field and ultrasound have been described. See., e.g., U.S. Pat. No. 5,476,438. Such systems purport to stimulate nerves by applying a magnetic field generally to the nerve and simultaneously focusing an ultrasound beam on the nerve.
SUMMARY OF THE INVENTION
[0012] The present invention relates to a device and method for non-invasive stimulation of nerves for, e.g., treating pain, controlling nerve function or performing mapping studies. In some aspects, the present invention relates to devices and methods that stimulate nerves non-invasively within the human body, and more particularly, Aδ-fibers and C-fibers for pain control, with improvements on Transcutaneous Electrical Nerve Stimulation (TENS); spinal cord stimulation (SCS) for inducing anesthesia and controlling pain; any deep-brain stimulation (DBS) including any part of the cortex, hippocampus, basal ganglia, the subthalamic nucleus, the caudate and the dentate; pudendal nerve for controlling urinary incontinence; and the vagal nerve for inducing parasympathetic modulation. Some aspects of the method relate to improved non-invasive stimulation of any target site, nerve or muscle that is deeply or superficially located utilizing localized Hall Effect phenomenon. The device induces Hall Effect stimulation by combining ultrasound delivered by an external transducer, with a magnetic fields delivered by external electromagnets, boosted by a subthreshold electric field delivered transcutaneously utilizing surface electrodes.
[0013] The device and method of this invention may be used for the following indications: post-surgical acute pain, nociceptive acute and chronic pain, neuropathic chronic pain, localized anesthesia, and substitute for epidural during surgery and caesarian delivery. The device could be used in conjunction with analgesics to reduce dosage of barbiturates and long-term dependency on opiates.
[0014] In another aspect of this invention, the device and method may be used by neurosurgeons for brain mapping prior to permanent implantation of deep-brain stimulator (DBS) devices. DBS is indicated for the control of: epilepsy, Parkinson's disease, Essential Tremor, severe migraines, phantom limbs and chronic pain, depression, dementia due to Alzheimer's and other intractable conditions requiring technological and surgical interventions. In current procedures, following MRI, stereotactic intraoperative mapping is employed to localize DBS targets while the skull is open and the patient is awake, providing psychophysical and instrumented feedback. The results of such procedures are often suspect since drugs are used to block patient pain throughout the procedure, present a transient response, compounded by the presence of a single-unit mapping electrode. Permanent electrode target localization is a lengthy process that requires multiple insertions of single-unit electrodes through a cannula. Repeated insertions of mapping electrodes are known to produce nerve damage in the insertion path. Using this invention, mapping is conducted prior to operating, without the insertion of the mapping electrode, thereby allowing the neurosurgeon to reduce or eliminate intraoperative brain mapping prior to permanent electrode placement and test stimulation parameters of DBS devices to determine in advance the efficacy of such technological interventions.
[0015] In another aspect, the device and method of this invention are intended for stimulation-induced lipolysis for regulation of long-term energy balance cycle in obese patients. The preferred target is the lateral cutaneous femoral nerve. Such use may supplement future implanted obesity devices that focus on short-term satiety measures, but do not address endocrine modulators such as leptin, that may relate to suppression of natural lipolysis in morbidly obese patients.
[0016] In yet another aspect of this invention, the device and method serve as research tools for new implantable stimulators intended for nerve or muscular targets, for, e.g., the control of urinary incontinence by targeting the pudendal nerve, obesity by targeting the vagus nerve or nerves controlling intestinal peristalsis, and other systemic endocrine processes regulated by the autonomic nervous system that may benefit from such non-invasive stimulation. The research devices would allow clinicians and regulating agencies to determine prior to implantation whether permanent implants would result in favorable outcomes.
Mechanism of Stimulation
[0017] The mechanism of stimulation utilizes the superposition of electric currents introduced by the following electric field sources:
[0018] (1) Hall Effect due to the interaction of Ultrasound and Magnetic Fields (see, S. J. Norton, “Can Ultrasound be Used to Stimulate Nerve Tissue?” Biomedical Engineering Online, (2003); Angelo Campanella, “Investigations of Sound Waves Generated by the Hall Effect in Electrolytes”, J. Acoust. Soc. Am., Vol 111, No.5, 2002, pp. 2087-2096; H. Wen, E. Bennett, J. Shah, R. S. Balaban, “An Imaging Method Using the Interaction between Ultrasound and Magnetic Field,” IEEE Ultrasonics Symposium, 1997, pp. 1407-1410);
[0019] (2) Magnetic induction of electric current due to oscillating magnetic fields, as is the case with coil electrodes or Transcranial Magnetic Stimulation (TMS) (see, W. J. Fry, “Electrical Stimulation of Brain Localized without Probes—Theoretical Analysis of a Proposed Method,” J. Acoust. Soc. Am., Vol 44, No.4, 1968, pp. 919-931; Ruohonen, P. Ravazzani, J. Nilsson, M. Panizza, F. Grandori, G. Tognola, “A volume-conduction analysis of magnetic stimulation of peripheral nerves,” IEEE Trans. Biomed. Eng., vol. 43, pp. 669-677 (1996); K. Davey, C. M. Epstein, “Magnetic Stimulation Coil and Circuit Design,” IEEE Trans. Biomed. Eng., Vol. 47, No. 11, 2000, pp. 1493-1499; F. Grandori, P. Ravazzani, “Magnetic stimulation of the motor cortex-Theoretical considerations,” IEEE Trans. Biomed. Eng, Vol. 38, No.2 1991 pp. 180-191; B. J. Roth et al., “A theoretical calculation of the electric field induced in the cortex during magnetic stimulation,” Electroencephalography and Clinical Neurophysiology, Vol. 81, 1991, pp. 47-56); and
[0020] (3) Transcutaneous Electrical Neural Stimulation (TENS) devices.
[0021] This invention entails localization of electric fields via spatial focusing of power over a small biological target. The spatial focusing is limited only by the wavelength of the ultrasonic wave and, in the presence of a magnetic field, creates a Lorentz Force in an electrolytic medium. The induced current due to the Lorentz Force (see, B. S. Guru, H. R. Hiziroglu, Electromagnetic Field Theory Fundamentals, Second Edition, Cambridge University Cambridge, UK, 2004, ch. 6-7) is:
[0000] {right arrow over (J)}=σ{right arrow over (v)}×{right arrow over (B)} (1)
[0022] where,
J is the current density vector in A/m 2 , σ is the conductivity of tissue in S/m, v is the velocity of particle motion due to the ultrasonic wave pressure in m/s, and B is the magnetic flux density in T.
[0027] Current traveling through a coil activates the magnetic field. The coil may be wound on a ferromagnetic core (or a similar magnetic material, such as an iron-cobalt alloy) to enhance the magnetic field, or could be a simple set of wire loops without any core. The magnetic field oscillates at a frequency that is equal or less than that of the ultrasound, and could theoretically be a constant DC field. Oscillating magnetic field amplitudes within the range of 0-3 T may be generated, and for practical reasons, dampened sinusoids or pulses are selected. This disclosure, however, covers any frequency or amplitude sufficient to introduce an incremental Hall Effect electric field sufficient to stimulate tissue.
[0028] A secondary effect of oscillating magnetic fields is an induced current density in the conductive tissue, which is derived from Faraday's induction law and Lenz's law, is described below:
[0000]
J
→
=
σ
E
→
=
σ
(
K
φ
t
)
=
σ
K
μ
N
(
I
t
)
∫
A
s
→
(
2
)
[0029] where,
[0030] J is the current density vector in A/m 2 ,
[0031] E is the electric field in V/m,
[0032] σ is the conductivity of tissue in S/m,
[0033] K is the effective mutual inductance between the coil and the biological medium,
[0034] Φ is the magnetic flux through the coil
[0035] N is the number of turns on the coil,
[0036] I is the current in the coil windings,
[0037] ds is an element of the cross-sectional area of the electromagnet producing the coupled magnetic field,
[0038] and μ is the core permeability.
[0039] This current is much less localized than that of the one induced by the Hall Effect phenomenon, yet it provides a subthreshold component to which the Hall Effect current is added. This generalized current could play an important role in lowering the total required energy delivered by ultrasonic stimulation and is an added benefit of using switched oscillating current to achieve the desired magnetic field strengths required for the Localized Hall Effect of this invention to operate. Many published simulations using the Hodgkins-Huxley model have shown that nerve stimulation would occur in induced electric fields ranging from 6 V/m−100 V/m (see, e.g., F. Grandori, P. Ravazzani, “Magnetic stimulation of the motor cortex—Theoretical considerations,” IEEE Trans. Biomed. Eng., Vol. 38, No.2 1991 pp. 180-191; J. P. Reilly, “Peripheral nerve stimulation by induced electric currents: exposure to time-varying magnetic field,” Medical and Biological Engineering and Computing, Vol. 27, 1989, 101-110; P. Tofts, “The distribution of induced currents in magnetic stimulation of the nervous system”, Phys. Med. Biol. Vol. 35, 1990, 1119-1128; P. J. Maccabee, S. S. Nagarajan, V. E. Amassian, D. M. Durand, A. Z. Szabo, A. B. Ahad, R. Q. Cracco, K. S. Lai, L. P. Eberle, “Influence of pulse sequence, polarity and amplitude on magnetic stimulation of human and porcine peripheral nerve,” J. Physiology, vol. 513.2, 1998, pp. 571-585; B. J. Roth, P. J Basser, “Model of the Stimulation of a Nerve Fiber by Electromagnetic Induction,” IEEE Trans. Biomed. Eng, vol. 37, 1990, 588-597). Based on experience, adequate recruitment in the cortex with invasive electrodes requires around 100 V/m at frequencies exceeding that of the membrane time constant requirements and is estimated to be significantly less in large myelinated nerves.
[0040] The third component in this approach entails the widely utilized concept of Transcutaneous Electric Neural Stimulation (TENS), introduced by surface electrodes. The surface electrodes are needed only in some cases and provide a baseline electric current component, which is non-localized, at a subthreshold level. The addition of all three currents provides deep neural stimulation of any targeted axon with electric field gradients that are dictated by the wavelength of the ultrasonic carrier frequency.
[0041] Hall Effect generation of Lorentz forces was successfully demonstrated by Wen for use as a novel imaging modality, called Hall Effect Imaging (HEI). For imaging, the reverse approach is applied where large pulses of electric field are generated across an electrolytic medium, resulting in pressure waves. The strength of the resultant ultrasonic source is proportional to the electrical conductivity of the medium. The ultrasonic wave is then detected by a hydrophone. In this way, an image of tissue conductivity can be built up.
Ultrasound Demodulation and Wave Interaction
[0042] High spatial resolution requires high-frequency ultrasound, resulting in small wavelengths. In DBS applications, spatial separation between electrodes is in the order of 1-5 mm. The Hall Effect phenomenon generates electric fields that are at the same frequency of ultrasound within a DC, or a much slower oscillating magnetic field. To obtain high spatial resolution, an ultrasound frequency on the order of several hundred kHz to MHz or above is required, depending on the clinical application.
[0043] Non-destructive amplitudes for nerve stimulation tend to be at periods close to the natural membrane time constant and shown repeatedly in the literature on strength duration curves (see L. A. Geddes, L. E. Baker, Principles of Applied Biomedical Instrumentation, Third Edition, John Wiley & Sons, New York, 1989). Such periods equate to frequencies of 1-10 kHz for SCS and DBS applications.
[0044] Fatemi and Greenleaf published a breakthrough discovery in 1998 documenting that MHz-frequency ultrasound could be utilized to measure elasticity and other mechanical characteristics of biological targets, that have natural frequencies that are orders of magnitude lower than those of the carrier signals. (See M. Fatemi, J. F. Greenleaf, “Ultrasound-Stimulated Vibro-Acoustic Spectrography,” Science, VOL. 280, 1998, pp. 82-85.) The concept involves two incident waves, at slightly different frequencies, introduced by con-focal ultrasonic transducers, and later by sector arrays (see G. T. Silva, S. Chen, A. C. Frery, J. F. Greenleaf, M. Fatemi, “Stress Field Forming of Sector Array Transducers for Vibro-Acoustography,” IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control, 2005, vol. 52, no. 11, pp. 1943-1951). The two co-incident waves interact in a non-linear manner and produce a detectable sonic wave at the difference frequency. Their imaging method is called vibro-acoustography and was demonstrated as useful in the detection of breast cancer, since tumors have different mechanical characteristics than the surrounding tissue.
[0045] The device disclosed herein uses difference frequency approaches to demodulate MHz-range ultrasound in some embodiments for stimulation purposes. The difference frequency method will allow the generation of 1-10 kHz electric field potential, transmitted deep into the body and modulated by two co-incident ultrasonic sources operating in the MHz range.
Neural Stimulation using Hall Effect
[0046] As indicated earlier, the device and method of this invention has three components to its current, added with superposition:
[0047] (1) Current due to the Hall Effect localized at a small target region within an ultrasonic wavelength and perpendicular to the magnetic field. The current may be induced at the fundamental frequency of the ultrasound with long wavelengths, or at difference frequencies from two separate sources. We define the current density due to Hall Effect as {right arrow over (J)} HE .
[0048] (2) Current inducted by Lenz's and Faraday's laws due to the use of oscillating magnetic fields, since large magnetic fields created by DC current in the windings may be impractical. We refer to current density due to magnetic oscillation as {right arrow over (J)} mg .
[0049] (3) Current conducted by the application of electrodes around the stimulation site utilizing TENS. We refer to current density due to surface electrodes as {right arrow over (J)} SE .
[0050] The total current density is therefore,
[0000] {right arrow over (J)} TOT ={right arrow over (J)} HE +{right arrow over (J)} mg +{right arrow over (J)} SE . (3)
[0051] {right arrow over (J)} HE is defined in equation (1) and {right arrow over (J)} mg is defined in equation (2) above. The current density between two electrodes, positioned on the z-axis, with separation distance, d, and current, I, obeys Laplace's equation and is represented as:
[0000]
J
→
SE
(
0
,
0
,
z
)
=
I
4
π
[
1
(
z
+
d
2
)
2
+
1
(
z
-
d
2
)
2
]
z
^
.
(
4
)
[0052] The final component is the Hall Effect current density, derived from equation (1) above, and assuming a magnetic field that is perpendicular to the propagation of ultrasound, it can be expressed in scalar form as:
[0000] J=σvB. (5)
[0053] Let the particle velocity function be a sinusoid with frequency, ω a , wave constant, k, and peak velocity ν 0 , then time-averaged J along the x-axis is expressed as:
[0000]
J
(
x
)
=
σ
T
∫
0
T
V
0
sin
(
ω
a
t
-
kx
)
B
(
t
)
t
(
6
)
[0054] One embodiment of the device of this invention operates in a manner such that {right arrow over (J)} HE is direct current (DC). We can obtain DC current density by setting B(t)=sin(ω a t), in which case (6) becomes:
[0000]
J
dc
(
x
)
=
1
2
σ
v
0
B
0
cos
(
ikx
)
(
7
)
[0055] The DC current may be turned on and off to achieve optimal modulation or pulse train stimulation.
[0056] In another embodiment, a current density oscillating at a low frequency (rather than DC) can be achieved by varying the magnetic field at a slighting different frequency than the ultrasonic frequency. In this case, one sets B(t)=sin((ω a +Δω)t). Using this in Eq. (6) gives a current density similar to Eq. (7), but with a temporal modulation at the frequency Δω. This frequency could be selected for optimal stimulation (e.g., approximately 10 kHz).
[0057] One aspect of the invention provides a method of stimulating a nerve in tissue of a patient. The method includes the following steps: applying a focused ultrasound beam to the tissue; applying a first magnetic field to the tissue; and applying a second magnetic field to the tissue, the second magnetic field differing from the first magnetic field, the ultrasound beam and the first and second magnetic fields combining to stimulate the nerve. In some embodiments, the nerve is in a dorsal spinal root or dorsal column, and in such embodiments the method could includes the step of stimulating the nerve to treat pain. In some embodiments the nerve is a peripheral nerve, and in such embodiments the method could include the step of controlling the function of the peripheral nerve. In some embodiments the nerve is in the deep brain, and in such embodiments the method could include the step of stimulating the nerve to perform a mapping study.
[0058] In some embodiments, the first magnetic field is a DC field. In other embodiments, the step of applying a first magnetic field includes the step of pulsing or oscillating the first magnetic field at a frequency from, e.g., about 0.5 Hz to about 300 Hz.
[0059] In some embodiments, the step of applying a first magnetic field includes the step of applying the first magnetic field at a first polarity and the step of applying a second magnetic field includes the step of applying the second magnetic field at a second polarity opposite to the first polarity. In other embodiments, the first and second magnetic fields are applied at the same polarity. The first and second magnetic fields may generate a substantially toroidal magnetic field in the tissue. In some embodiments, the spacing between first and second magnetic fields sources may be changed.
[0060] In some embodiments, the method includes the step of applying an electric voltage, or controlled current, to a surface of the tissue (such as, e.g., the patient's skin) using electrodes that are spaced apart from the nerve yet create electric fields that encompass the nerve. In such embodiments, an electrode may be adhered to the tissue surface. The electric field may be applied with a TENS device and may be applied to the nerve may be less than a stimulation threshold for the nerve.
[0061] In some embodiments, the step of applying a focused ultrasound beam includes the step of applying a continuous wave ultrasound beam. In other embodiments, the step of applying a focused ultrasound beam includes the step of applying a pulsed ultrasound beam. In some embodiments a second focused ultrasound beam is applied to the tissue, and the first and second ultrasound beams may be at different frequencies.
[0062] Yet another aspect of the invention provides a method of stimulating a nerve in tissue of a patient, the method including the steps of applying a focused ultrasound beam to the tissue; applying a first magnetic field to the tissue; applying a second magnetic field to the tissue; and applying an electric field to a tissue surface spaced apart from the nerve (such as a skin surface), the ultrasound beam, the first and second magnetic fields and the electric field combining to stimulate the nerve. In some embodiments, the electric field is applied with a TENS device.
[0063] Another aspect of the invention provides a nerve stimulation device having two magnetic coils of opposite polarity each adapted to generate a magnetic field in a patient's tissue, the coils being positioned to generate a substantially toroidal magnetic field within the patient's tissue; and an ultrasound source adapted to transmit a focused ultrasound beam into the patient's tissue. In some embodiments, the device also includes a first electrode adapted to be applied to a surface of the patient's tissue and a power source adapted to provide a voltage between the first electrode and a second electrode. The device may also include a controller adapted to control the voltage and/or current between the electrodes.
[0064] In some embodiments, the device has a second ultrasound source adapted to transmit a focused ultrasound beam into the patient's tissue. In some embodiments, the device includes a controller adapted to control operation of the magnetic coils and the ultrasound source. The controller may include a user control adapted to adjust an operation parameter of at least one of the magnetic coils and the ultrasound source.
[0065] Further details of the device and method of the invention will be described with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0066] The novel features of the invention are set forth with particularity in the claims that follow. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:
[0067] FIG. 1 is a schematic drawing of a patient/device interface according to one embodiment of the invention.
[0068] FIG. 2 shows the architecture of a stimulator system according to one embodiment of the invention.
[0069] FIG. 3 is a schematic drawing of a magnetic coil drive circuit for use with this invention.
[0070] FIG. 4 is a computer-generated representation of an ultrasound array factor suitable for use with this invention.
[0071] FIG. 5 is a block diagram showing beam forming architecture for use with this invention.
[0072] FIG. 6 is the block diagram of a TENS drive circuit for use with this invention.
[0073] FIG. 7 shows strength duration curves for nerve stimulation.
DETAILED DESCRIPTION OF THE INVENTION
[0074] FIG. 1 shows schematically an interface between a stimulation device and a patient. The interface 10 has two magnetic coils 12 and 14 with opposite polarity which together generate a magnetic field in the shape of a torus. In this embodiment, the distance between the two magnetic coils may be varied as desired. In other embodiments, the distance between the magnetic coils may be fixed. Coils 12 and 14 connect to a controller (not shown) via conductors 16 and a conduit 18 . In use, coils 12 and 14 may be adhered to the skin or other tissue surface of the patient.
[0075] One or more ultrasound sources are disposed in the center of interface 10 . In some embodiments, the ultrasound sources will be focused on the axon of interest to create a Hall Effect current. The ultrasound source may be a single transducer, a con-focal transducer, two separate transducers, or two separate arrays operating at slightly different frequencies, with a resultant wave at the difference frequency representing the stimulation profile. The embodiment shown in FIG. 1 employs two ultrasound sources, 20 and 22 , connected to the controller via conduit 18 . Holes (not shown) may be provided beneath the ultrasound sources to provide room for gel application. In use, the ultrasound sources may be adhered to the patient's skin or other tissue surface.
[0076] This embodiment also uses surface electrodes 24 and 26 to add a baseline electric field in order to decrease the stimulation amplitudes required by the localized Hall Effect phenomenon. Electrodes 24 and 26 communicate with the controller via conductors 28 and 30 , respectively. In use, these surface electrodes are adhered to the patient's skin or other tissue surface and may use conductive gel to create electric current uniformity at the electrode/tissue interface.
[0077] FIG. 2 shows the architecture of a stimulator system 200 according to one embodiment of the invention. The device architecture is that of a host-controller model. The host 202 provides a user interface allowing the clinician to alter stimulation parameters for the magnetic coils 206 , the ultrasound sources 208 , and the transcutaneous electrodes 210 comprising the patient interface 212 . The host is comprised of software running on a personal computer. The controller 204 is an embedded processor, interfaced with the host via a communication port 214 , with a processor that controls each of the three modalities. Once the stimulation parameters are downloaded, the host 202 and controller 204 could be disconnected. A simple user interface 216 is provided via buttons and LEDs on the controller front panel.
[0078] Other elements of the system of this embodiment include a power supply 218 , a DC step up 220 , an ultrasound beamformer circuit 222 , a TENS generator 224 , a magnetic coil drive circuit 226 and flash ROM 228 .
[0079] In one embodiment, shown in FIG. 3 , the magnetic coil drive circuit 300 is a simple DC charge capacitor circuit powered by a step-up transformer 302 via a full-wave rectifier 304 . The two coils 306 and 308 are powered via a silicone controlled rectifier (SCR) which discharges the capacitor into the windings of the coils. The coils may possibly be wound around a ferromagnetic core to enhance the field strength, or could simply be a wire loop with multiple turns. The ferromagnetic core may have any shape such that the flux at its end or side is optimized for the clinical application. The microprocessor allows the circuit to oscillate once at its natural frequency using the SCR and another transistor switch 310 . The voltage source, not shown in this figure, is an amplified voltage controlled oscillator driven by a digital potentiometer that the microprocessor programs through a serial connection.
[0080] Up to two ultrasonic beamformers could be used in this device, and as few as one transducer depending on the clinical application. In one embodiment, each beam former is operating at a slightly different frequency than the other. As documented earlier by Fatemi and Greenfield, the interaction of the two co-incident waves results in a third wave generated non-linearly at the difference frequency. There is a fourth wave that is not of interest to this application oscillating at the sum of the two frequencies. A typical array factor pointing at 180 degrees is shown in FIG. 4 . The image was generated in MATLAB from 20 different elements, simulating a phased-array antenna. Other embodiments of this invention may produce an array factor that is different than the one shown in FIG. 4 .
[0081] Beam forming architecture is shown in the block diagram shown in FIG. 5 . In this embodiment, the beam forming architecture includes a microprocessor 502 providing phase control to a series of phase shifters 504 , the output of which are amplified with amplifiers 506 , which are connected to a DC step up circuit 508 to power the ultrasound transducers 510 . A digital potentiometer 512 operating with a VCO 514 provide the raw signals driving each of the transducers and processed by the phase shifter block.
[0082] The ultrasound sources are intended to operate in continuous wave mode, thus justifying the use of programmable phase shifters. In another embodiment, pulsed ultrasound may also be used to generate a dampened sinusoidal response. With pulsed ultrasound, the microprocessor drives the transducers through an array of FET push-pull transistor-pairs, with each pulse delayed as a function of the transducer phase angle.
[0083] The third modality of the device of this invention is that of the transcutaneous neural stimulator. As mentioned earlier, this modality is only used to provide subthreshold stimulation, aiding the Hall Effect to trigger action potentials in the targeted axons. In DBS applications, for example, the use of surface electrodes may generate undesirable outcomes, while in spinal cord and peripheral applications, it may be programmed in a complex manner to exhibit a variety of neuromodulation mechanisms.
[0084] The surface electrodes could produce a variety of waveforms commonly used in neural stimulation, such as trapezoidal, asymmetric, and half-wave. The waveforms are generated by the host and downloaded into memory. The microcontroller reads the digitized waveforms, converts them to analog and sends them to the electrode pair, via current-controlled amplifiers.
[0085] FIG. 6 shows the block diagram of a TENS drive circuit. In this embodiment, a microprocessor 602 obtains waveforms from flash memory 604 . A microcontroller 606 (possibly communicating with RAM 608 ) provides the current waveform to the electrodes 614 through an amplifier 610 and DC step up circuit 612 . A separate patient ground 616 may also be provided. In another embodiment, isolation transformers or push-pull mechanisms are used to activate the surface electrodes.
[0086] In operation, the system is first set up by connecting the three major modules together: the device to the PC-host and the device to the patient-interface module. Both device and host are powered up, and the Graphical User Interface (GUI) software is run on the PC-host. The GUI contains a mathematical model that estimates magnetic induced current density due to magnetic coil operating parameters. The following parameters are then set for the magnetic drive circuit shown in FIG. 3 :
[0087] (1) Amplitude of input voltage (Amc);
[0088] (2) Frequency of input voltage (Fmc);
[0089] (3) Discharge output voltage (Vo); and
[0090] (4) Discharge repetition rate (DRR).
[0091] Both Amc and Fmc influence the operation of the charging circuit and are limited by a model of that circuit for optimal and safe operation. Vo and DRR determine the physiologic response to the magnetic coils. Larger Vo results in larger coil currents, thus introducing larger fluctuation in magnetic flux. The induced current in the target membrane is proportional to dB/dt. DRR determines the steady-state response of the axon, and may result in the following physiologic effects: (1) subthreshold stimulation; (2) hyperpolarization; and/or (3) sensitization. The preferred operation of the system is the first response so that subthreshold non-localized stimulation of many nerves in the magnetic field is aided by an incremental addition of the Hall Effect voltage introduced by the ultrasound sources at the target.
[0092] Next, the ultrasound sources are programmed for continuous operation. In one embodiment, a single ultrasound source operates at a stimulation frequency much greater than the fluctuation frequency of the magnetic flux density, but is considered effective for the targeted axon according to the nerve stimulation strength-duration curve shown in FIG. 7 .
[0093] In another embodiment, two ultrasound sources, whether single element or phased arrays, are programmed to operate at a wavelength that achieves desired localization. Ultrasound propagating in an axis transverse to that of the magnetic field, as shown in equation (1), will introduce a Hall Effect electric current. This localized phenomenon acts similar to a physical electrode, referred to herein as a “virtual electrode.” The two sources operate at slightly different frequencies, and the difference of the two is the stimulation frequency determined by the strength-duration curve shown in FIG. 7 .
[0094] Depending on the clinical application, stimulation sites may be too responsive to the induced current by the magnetic coils, thus requiring a decrease in flux density to a point where the Hall Effect voltage strength becomes less dominant. This situation may require the assistance of another subthreshold stimulation source, generated by the surface electrodes shown in FIG. 1 . The next step in setting up the device would be to program the stimulation current in these electrodes according to a predetermined mathematical model, such that the total current due to the surface electrodes and those of the magnetic coils result in the desired non-localized physiologic effect. The added current by the Hall Effect phenomenon resulting from ionic disturbance in the magnetic field by the ultrasound pressure waves induces the incremental effect of stimulation, only at the target site within the mentioned “virtual electrode” target region. | One aspect of the invention provides a method of stimulating a nerve in tissue of a patient. The method includes the following steps: applying a focused ultrasound beam to the tissue; applying a first magnetic field to the tissue; and applying a second magnetic field to the tissue, the ultrasound beam and the first and second magnetic fields combining to stimulate the nerve. Another aspect of the invention provides a nerve stimulation device having two magnetic coils of opposite polarity each adapted to generate a magnetic field in a patient's tissue, the coils being positioned to generate a substantially toroidal magnetic field within the patient's tissue; and an ultrasound source adapted to transmit a focused ultrasound beam into the patient's tissue. | 0 |
PRIORITY CLAIM
[0001] The present invention claims priority to U.S. Provisional Application Ser. No. 61/334,234 filed on May 13, 2010 and entitled, “Bone Screw Assembly and Implantation of the Same,” the entire disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention generally relates to bone screw assemblies and instruments for implantation of the same as well as to an associated method for implantation of the bone screw assembly using the instruments. More particularly, the invention relates to a bone screw including a second screw and insertion instruments for implantation of the same as well as to a method for implantation of the bone screw and the second screw by using the insertion instruments.
BACKGROUND
[0003] In the field of orthopedic surgery bone fixation devices using bone screws are commonly used. These bone fixation devices include bone plates, intervertebral implants or intramedullary nails by means of which two or more bones or bone fragments are fixed relative to each other. Typically, the bone fixation devices comprise bone anchors mostly in the form of bone screws, pins or nails by means of which the bones or bone fragments are fixed to the bone plate, intervertebral implant or intramedullary nail and consequently fixed relative to each other. One problem that can arise in case of the above mentioned bone fixation devices is that the bone screws, pins or nails can for instance become dislodged in the bone or in the bone plate, intervertebral implant or intramedullary nail during normal movements of the patient.
[0004] Thus, there remains a need for an improved bone anchor device for use in bone fixation that allows to drill a hole for a securing screw into a bone under a particular angle with respect to the axis of a bone fastener and to insert the securing screw in a guided manner.
SUMMARY OF THE INVENTION
[0005] The present invention relates to a bone screw with a screw head configured to be releasably coupled to a surgical instrument or tool such that the surgical instrument or tool is coaxially supported in a first position and can be pivoted in a guided manner about an axis extending diametrically to the screw head into a second position.
[0006] According to an exemplary embodiment of the present invention, the bone screw comprises a screw axis, a shaft to be anchored in a bone and screw head including a through hole with a through hole axis cutting the axis of the bone screw at an acute angle wherein the through hole is adapted to receive a second screw that can be anchored in the bone as well. The screw head comprises a transverse channel with a channel axis extending diametrically across the screw head and wherein the transverse channel is open at the rear end of the bone screw. The screw head of the bone screw further includes a recess which has—in at least a cross-section orthogonal to the channel axis—a circularly curved edge with a centre located at the point where the through hole axis cuts the screw axis.
[0007] One of the advantages of the bone screw according to the invention is that the configuration of the transverse channel and the recess permits an aiming guide with a complementarily configured tip to be attached to the screw head and rotated about a rotation axis from a first position aligned with the screw axis into a second position aligned with the through hole axis. Another advantage of the bone screw is the pivotable joining of the screw head and the aiming guide. The aiming guide can be inserted into the incision coaxially to the screw axis of the bone screw by using a tissue protection tube and/or a guide wire and attached to the screw head. After removing the tissue protection tube and/or the guide wire the aiming guide can be rotated about the rotation axis. In addition, the aiming guide can then be rotated into a second position in which the longitudinal axis of the aiming guide is aligned with the through hole axis of the through hole in the screw head so that a bore hole for the second screw can be drilled into the bone which is exactly aligned with the through hole in the screw head; the bore hole for the second screw can be drilled in a completely guided manner and the second screw can be positioned in a guided manner by means of the aiming guide. Another advantage is that the transverse channel and the recess allow to attach a complementarily formed tip of a screwdriver to the bone screw in such a manner that the screwdriver is positioned coaxially to the screw axis of the bone screw.
[0008] In an exemplary embodiment of the bone screw, the through hole axis cuts the screw axis at a depth T>0 measured from the rear end of the bone screw towards the screw shaft.
[0009] In another exemplary embodiment of the bone screw, the recess has a constriction at the rear end of the bone screw. Thus, the recess forms a female connector for a snap-lock connection with a respective male connector arranged at a surgical instrument or tool.
[0010] In a further exemplary embodiment of the bone screw, the through hole comprises an internal thread, preferably a conical internal thread. This allows the advantage that the second screw can be firmly connected to the screw head of the bone screw.
[0011] In another exemplary embodiment of the bone screw, the internal thread has a thread pitch P and a threaded length L T and wherein the ratio L T /P is minimum 2.0, preferably minimum 2.3. This configuration of the internal thread allows a rigid and angularly stable anchorage of the screw head of the second screw in the screw head of the bone screw.
[0012] In yet another exemplary embodiment of the bone screw, the recess has a spherical shape with a radius of the sphere R. This configuration of the recess allows a surgical instrument or tool to be pivoted about an axis which extends through the point where the through hole axis and the screw axis intersect so that the instrument or tool can be pivoted from a first position aligned with the screw axis to a second position aligned with the through hole axis.
[0013] In a further exemplary embodiment, the bone screw further comprises a second screw insertable into the through hole coaxially to the through hole axis.
[0014] In another exemplary embodiment of the bone screw, the second screw has a conically threaded head engagable with the conical internal thread in the through hole.
[0015] In yet a further exemplary embodiment of the bone screw, the recess includes a depression traversing the constriction and forming a wall portion with the shape of a surface section of a cylinder, cone or prism the axis of which coincides with the through hole axis. By means of the depression a stop for the rotation of an instrument or tool inserted in the recess in the screw head of the bone screw is provided so that the instrument or tool can be exactly aligned with the through hole for the second screw.
[0016] In another exemplary embodiment of the bone screw, the angle α amounts to minimum 10°, preferably to minimum 20°.
[0017] In yet another exemplary embodiment of the bone screw, the angle α amounts to maximum 70°, preferably to maximum 35°.
[0018] In again another exemplary embodiment of the bone screw, the transverse channel has a U-shape in a cross-section orthogonal to the channel axis. The U-shaped channel can have a semicircular bottom with a radius of curvature r C , wherein the centre of the semicircular edge of the transverse channel is located on the channel axis. The channel axis can be located at a depth T C measured from the rear end of the bone screw towards the screw shaft, wherein the depth T C is equal or greater than the depth T of the point where the through hole axis cuts the screw axis. In a particular configuration of the transverse channel the channel axis cuts the screw axis through the point where the through hole axis and the screw axis intersect, i.e. T C =T. In this case the semicircular bottom defines a seat coaxially to the recess for rotatably receiving cylindrical pins of an aiming guide which have a pin diameter equal to twice the radius of curvature r C of the semicircular bottom of the transverse channel. In case of a spherical recess the rotatable movement of the aiming guide is limited to a uniaxial pivot movement due to the pins engaging the transverse channel.
[0019] In a further exemplary embodiment of the bone screw, the channel axis cuts the screw axis through the point at which the screw axis and the through hole axis intersect.
[0020] In yet another exemplary embodiment of the bone screw, the screw head of the bone screw comprises an external thread designed in such a manner that the bone screw can be counter-sunk in a bone. The external thread on the screw head is preferably_conical so that it allows to countersink the screw head in the bone. This configuration is particularly useful if the bone screw is used as a locking screw for an intramedullary nail.
[0021] In another exemplary embodiment of the bone screw, the screw head of the bone screw has a longitudinal slot so that the screw head is radially elastically expandable. The screw head can have the shape of a segment of a sphere so that the bone screw can be inserted into a complementarily shaped hole in a bone plate or other implant under a surgeon desired angle. Once the bone screw is correctly positioned the second screw can be inserted until the head of the second screw expands the screw head of the bone screw in the hole so allowing to secure the bone screw in a surgeon selected angle relative to a bone plate or other implant.
[0022] In accordance with another aspect of the present invention, a screwdriver is provided for screwing the above bone screw into a bone. The screwdriver essentially comprises a male connector terminally arranged at the front end which is suitable to be coupled to the recess in the screw head of the bone screw. Further, the connector includes a tip constricting towards the front end of the screwdriver and two driving protrusions diametrically projecting over the tip in either direction and defining a central axis which extends orthogonal to the longitudinal axis of the screwdriver. The driving protrusions fit in the transverse channel in the screw head of the bone screw. In at least a cross-section orthogonal to the central axis the tip has a circularly curved periphery with a radius R and a centre located on the longitudinal axis. The driving protrusions can have the shape of pins or blades. In case of blade-shaped driving protrusions the tips of the blades define the central axis. In case of pin-shaped driving protrusions the axes of the pins define the central axis.
[0023] In an exemplary embodiment, the screwdriver further comprises a longitudinal slot extending parallel to the longitudinal axis and which is open at the front end so that the connector is radially elastically compressible. Further, the tip has a constriction towards the shaft which forms at least in a cross-section orthogonal to the central axis a curved contact shoulder. Thus, the connector forms a male connector for a snap-lock connection with a respective female connector arranged at the bone screw.
[0024] In a further exemplary embodiment of the screwdriver, the tip has a spherical shape with a radius of the sphere R and with a centre located on the longitudinal axis.
[0025] In a further exemplary embodiment of the screwdriver, the two driving protrusions are circular-cylindrically shaped wherein the central axis orthogonally cuts the longitudinal axis through the centre of the spherical tip.
[0026] In another exemplary embodiment of the screwdriver, the male connector further comprises an axial stop located at a distance T measured from the central axis towards the shaft so that the stop contacts the rear end of the bone screw when the connector is coupled to the recess in the screw head. Thus, the screwdriver is kept exactly coaxially to the screw axis of the bone screw when the stop abuts the rear end of the bone screw.
[0027] In yet another exemplary embodiment of the screwdriver, the male connector further includes a nose projecting over the tip in a direction towards the front end and at an acute angle with respect to the longitudinal axis of the screwdriver. This configuration allows the advantage that the screwdriver can only be inserted in one orientation into the seat in the screw head of the bone screw.
[0028] In again another exemplary embodiment, the screwdriver further comprises a coaxial through bore penetrating through the shaft and the male connector and having an internal thread for engaging an external thread arranged on a locking pin which is insertable in the through bore in such a manner that the locking pin can be advanced towards the front end of the screwdriver to prevent the tip from radially collapsing.
[0029] In accordance with a further aspect of the present invention, an aiming guide is provided for drilling a hole in the bone the axis of which coincides with the through hole axis of the through hole in the screw head of the bone screw. The aiming guide essentially comprises a guide sleeve, a coaxial through bore and a male connector terminally arranged at the front end which is suitable to be coupled to the recess in the screw head of the bone screw. The connector includes a tip a width of which decreases towards the front end of the aiming guide and two pins diametrically projecting over the tip in either direction and coaxially arranged on a central axis which extends orthogonal to the longitudinal axis. In at least a cross-section orthogonal to the central axis the tip has a circularly curved periphery with a radius R and a centre located on the longitudinal axis.
[0030] In an exemplary embodiment, the aiming guide further comprises a longitudinal slot extending parallel to the longitudinal axis and which is open at the front end so that the connector is radially elastically compressible. Additionally, a curved contact shoulder is formed at the proximal end of the tip. Specifically, the curved contact shoulder is formed by a constriction at the proximal end of the tip (adjacent the guide sleeve) where a cross-sectional area of the tip in a plane orthogonal to the central axis of the tip is reduced relative to a maximum diameter portion of the tip distal thereto. This configuration allows the connector to operate as a male connector for a snap-lock connection with a respective female connector arranged in the bone screw.
[0031] In another exemplary embodiment of the aiming guide, the tip has a spherical shape with a radius of the sphere R and with a center located on the longitudinal axis.
[0032] In a further exemplary embodiment of the aiming guide, the two pins are circular-cylindrically shaped and wherein the central axis orthogonally cuts the longitudinal axis through the centre of the spherical tip. The circular cylindrical pivot pins are coaxially and rotatably insertable in the transverse channel.
[0033] In yet another exemplary embodiment of the aiming guide, a cylindrical or conical collar is arranged between the tip and the guide sleeve coaxially to the longitudinal axis of the aiming guide.
[0034] In again another exemplary embodiment of the aiming guide, the collar has a radius r≦R.
[0035] In a further exemplary embodiment, the aiming guide further comprises a drill guide which can be inserted into the through hole.
[0036] In another exemplary embodiment of the aiming guide, the drill guide has a conical tip. The conical tip is shaped in such a manner that it fits into the tapered through hole in the bone screw. This allow to lock the drill guide aligned to the through hole axis of the through hole for the second screw.
[0037] In accordance with yet another aspect of the present invention, an assembly including a bone screw, a screwdriver and an aiming guide is provided. This assembly can be used if a standard locking screw which is commonly available can be inserted into the through hole in the bone screw.
[0038] In accordance with again another aspect of the present invention, an assembly including a bone screw, a tissue protection tube, an aiming guide and a screwdriver is provided.
[0039] In accordance with still another aspect of the present invention, a method for bone fixation using an intramedullary nail including a number of proximal and distal locking holes and a number of bone screws with a second screw each is provided. The method essentially comprises the steps of:
a) performing an incision into the tissue surrounding a bone to be treated; b) positioning an intramedullary nail in the bone; c) coupling an aiming device to the intramedullary nail; d) inserting a tissue protection tube into a selected guide bore in the aiming device coaxially to one of the locking holes; e) drilling a first bore hole into a bone for insertion a bone screw by using the aiming device, wherein the first bore hole is aligned with the selected proximal or distal locking hole; f) coupling a bone screw to the connector of the screwdriver; g) advancing the bone screw through the tissue protection tube; h) screwing the bone screw into the bone using the screwdriver; i) removing the screwdriver; j) inserting the aiming guide through the tissue protection tube; k) attaching the aiming guide to the bone screw in such a manner that the longitudinal axis of the aiming guide is aligned with the screw axis of the bone screw; l) removing the tissue protection tube; m) repeating steps d) to l) until a bone screw each is inserted in all or in the selected proximal and/or distal locking holes of the intramedullary nail; n) removing the aiming device from the intramedullary nail; o) pivoting the aiming guide about the central axis until the collar of the aiming guide abuts a stop in the recess in the screw head of the bone screw so that the longitudinal axis of the aiming guide is aligned with the through hole axis of the through hole in the bone screw; p) inserting the drill guide into the through bore in the aiming guide; q) drilling a second bore hole into the bone using the drill guide as a guide for the drill bit; r) removing the drill guide; s) inserting the second screw through the through bore in the aiming guide; t) advancing the second screw into the bone; u) removing the aiming guide; v) repeating steps o) to u) until a second screw each is anchored in the bone passing through the through hole of each of the bone screws; and w) closing the incision.
[0063] Instead of subsequently performing steps d) to l) for one bone screw and repeating the sequence for each bone screw to be inserted each step can be repeated for all or for the selected number of bone screws to be inserted. Similarly, each step for inserting the second screw can be repeated for all or for the selected number of bone screws instead of subsequently performing steps o) to u) for one bone screw and repeating the sequence for each bone screw to be inserted.
[0064] In an exemplary embodiment, the stop is formed by the wall portion of the depression in the recess in the screw head of the bone screw.
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] An exemplary embodiment of the present invention will be described in the following by way of example and with reference to the accompanying drawings in which:
[0066] FIG. 1 illustrates a longitudinal section of an embodiment of the bone screw according to the invention;
[0067] FIG. 2 illustrates a lateral view of the embodiment of the bone screw of FIG. 1 ;
[0068] FIG. 3 illustrates a perspective view of an embodiment of the screwdriver according to the invention;
[0069] FIG. 4 illustrates a longitudinal section of the embodiment of the screwdriver of FIG. 3 ;
[0070] FIG. 5 illustrates a lateral view of the embodiment of the screwdriver of FIG. 3 ;
[0071] FIG. 6 illustrates a lateral view of the embodiment of the screwdriver of FIG. 3 which is orthogonal to the lateral view of FIG. 5 ;
[0072] FIG. 7 illustrates a lateral view of another embodiment of the screwdriver according to the invention;
[0073] FIG. 8 illustrates a lateral view of the embodiment of the screwdriver of FIG. 7 which is orthogonal to the lateral view of FIG. 7 ;
[0074] FIG. 9 illustrates a partial section through the embodiment of the screwdriver of FIGS. 7 and 8 and a bone screw attached thereto;
[0075] FIG. 10 illustrates a perspective view of an embodiment of the aiming guide according to the invention;
[0076] FIG. 11 illustrates a longitudinal section through the embodiment of the aiming guide of FIG. 10 and a bone screw coaxially attached thereto;
[0077] FIG. 12 illustrates a longitudinal section through the embodiment of the aiming guide of FIG. 10 and a bone screw attached thereto under the angle α;
[0078] FIG. 13 illustrates a longitudinal section through the embodiment of the aiming guide of FIG. 10 and a bone screw attached thereto under the angle α and together with a drill guide inserted in the aiming guide and a drill bit;
[0079] FIG. 14 illustrates a section through the aiming device and the drill guide of FIG. 13 ;
[0080] FIG. 15 illustrates a longitudinal section through the embodiment of the aiming guide of FIG. 10 and a bone screw attached thereto under the angle α and together with a second screw inserted in the aiming guide;
[0081] FIG. 16 illustrates a longitudinal section through the embodiment of the aiming guide of FIG. 10 and a bone screw attached thereto under the angle α and together with a second screw firmly secured in the through hole in the screw head of the bone screw; and
[0082] FIG. 17 illustrates an intramedullary nail together with a bone screw and a second screw according to an embodiment of the method for bone fixation according the invention.
[0083] FIG. 18 illustrates a lateral view of a system according to an alternate embodiment of the present invention, in a first configuration.
[0084] FIG. 19 illustrates a lateral view of the system of FIG. 18 , in a second configuration.
[0085] FIG. 20 illustrates a cross-sectional lateral view of the system of FIG. 18 , in the second configuration.
[0086] FIG. 21 illustrates an enlarged cross-sectional lateral view of a portion of the system of FIG. 18 .
DETAILED DESCRIPTION
[0087] The present invention may be further understood with reference to the following description and the appended drawings, wherein like elements are referred to with the same reference numerals. The present invention relates to bone screw assemblies and instruments for implantation of the same as well as to an associated method for implantation of the bone screw assembly using the instruments. In particular, the invention relates to a system and method facilitating implantation of a first bone screw, including a through hole extending through a head portion thereof along a through hole axis, and a second screw inserted into the through hole along the through hole axis such that the first and second bone screws are implanted into a bone in a stable configuration.
[0088] FIGS. 1 and 2 illustrate an embodiment of the bone screw 1 with a screw head 2 comprising a conical external thread 29 . The bone screw 1 includes a screw axis 6 , a threaded shaft 10 , a screw head 2 and a rear end 8 at a proximal end thereof. The screw head 2 comprises a through hole 9 penetrating through the screw head 2 and having a through hole axis 7 cutting the screw axis 6 under an acute angle α. The through hole axis 7 cuts the screw axis 2 at a depth T measured from the rear end 8 of the bone screw 1 . The through hole 9 has a conical internal thread 11 . A second screw 50 ( FIGS. 16 and 17 ) can be inserted into the through hole 9 coaxially to the through hole axis 7 . The second screw 50 has a conically threaded head 51 which is engagable with the conical internal thread 11 in the through hole 9 . The screw head 2 includes a concave seat 14 for releasably coupling a surgical instrument or tool to the bone screw 1 . The concave seat 14 comprises a transverse channel 5 and a centrally located recess 3 . The transverse channel 5 comprises a channel axis 101 located at a depth T C measured from the rear end 8 of the bone screw 1 and diametrically extending across the screw head 2 . The channel axis 101 cuts the screw axis 6 through the point where the through hole axis 7 cuts the screw axis 6 . Further, the transverse channel 5 is open at the rear end 8 of the bone screw 1 and the transverse channel 5 has a U-shaped cross-section with a semicircular bottom 100 orthogonal to the channel axis 101 . The semicircular bottom 100 has a radius of curvature r C wherein a center of an edge the semicircular bottom 100 of the transverse channel 5 is located on the channel axis 101 . The depth T C is equal to the depth T of the point where the through hole axis 7 cuts the screw axis 1 . The semicircular bottom 100 defines a seat coaxially to the recess 3 for rotatably receiving cylindrical pins 25 of an aiming guide 23 ( FIG. 10 ) which have a pin diameter equal to twice the radius of curvature r c of the semicircular bottom 100 of the transverse channel 5 .
[0089] The recess 3 has a spherical shape with a radius of the sphere R and a centre 4 coinciding with the point at which the screw axis 6 and the through hole axis 7 intersect. So the recess 3 forms a pivot bearing for rotatably supporting and guiding a complementarily spherically shaped male connector 232 of an aiming guide 23 ( FIG. 10 ). Due to the facts that the channel axis 101 cuts the screw axis 6 at the point where the centre 4 of the spherically shaped recess 3 is located on the screw axis 6 and that the pivot pins 25 of the aiming guide 23 fit in the transverse channel 5 rotatably about the channel axis 101 the polyaxial pivot bearing formed by the ball-and-socket joint is limited to an uniaxial pivot bearing. When the aiming guide 23 is coupled to the bone screw 1 the aiming guide 23 can only pivot about the channel axis 101 which is orthogonal to a plane defined by the screw axis 6 and the through hole axis 7 of the through hole 9 for the second screw 50 . This allows to position the aiming guide 23 in a first position coaxial to the screw axis 6 of the bone screw 1 and in a second position coaxial to the through hole axis 7 of the through hole 9 for the second screw 50 . Thus, it will be understood by those of skill in the art, that the second screw 50 may be precisely inserted into the through hole 9 along through hole axis 7 , increasing a stability of the screws 1 , 50 in situ.
[0090] Furthermore, the recess 3 has a constriction 31 at the rear end 8 of the bone screw 1 so that the recess 3 forms a female connector for a snap-lock connection. Additionally, the recess 3 includes a depression 12 which forms a wall portion 121 with the shape of a surface section of a circular cylinder with a radius r≦R. The axis of the circular cylinder coincides with the through hole axis 7 of the through hole 9 . The depression 12 forms a stop for the rotation of an aiming guide 23 about the channel axis 101 when the aiming guide 23 is coupled to the screw head 2 of the bone screw 1 . By means of the stop the aiming guide 23 can be exactly aligned with the through hole 9 .
[0091] FIGS. 3 to 6 illustrate an embodiment of the screwdriver 13 to be used with the bone screw 1 according to FIGS. 1 and 2 . The screwdriver 13 comprises a longitudinal axis 130 , a shaft 131 , a front end 135 at a distal end thereof and a male connector 132 which can be coupled to the above embodiment of the bone screw 1 . In order to releasably couple the screwdriver 13 to the bone screw 1 the connector 132 is essentially complementarily formed to the concave seat 14 in the screw head 2 of the bone screw 1 . The connector 132 includes a partially spherical tip 17 the cross-sectional area of which in a plane perpendicular to the longitudinal axis decreases toward the shaft 131 (i.e., toward the front end 135 ). Thus, a cross-sectional area of the spherical tip 17 at an end adjacent to the shaft 131 and at the front end 135 is smaller than a cross-sectional area of a mid-section of the spherical tip 17 . The tapering of the spherical tip 17 towards the shaft 131 forms a curved contact shoulder 138 which abuts the constriction 31 of the recess 3 at the rear end 8 of the bone screw 1 . The screwdriver 13 further comprises a longitudinal slot 20 open at the front end 135 to form the tip 17 as an elastic male connector for a snap-lock connection between the tip 17 and the recess 3 in the screw head 2 of the bone screw 1 . The longitudinal slot 20 is arranged orthogonal to a plane defined by the longitudinal axis 130 and the central axis 136 and penetrates through the shaft 131 . The connector 132 further includes two driving protrusions 18 extending laterally from the spherical tip 17 in either direction and which are coaxially arranged on a central axis 136 . The driving protrusions 18 are circular-cylindrically shaped with a cylinder axis coinciding with the central axis 136 . The connector 132 additionally comprises an axial stop 21 which is located between the shaft 131 and the connector 132 at a distance T measured from the central axis 136 towards the shaft 131 . The axial stop 21 abuts the rear end 8 of the bone screw 1 allowing to keep the screwdriver 13 exactly coaxially to the screw axis 6 of the bone screw 1 . The shaft 131 and the connector 132 comprise a coaxial through bore 134 with an internal thread 137 for engaging an external thread arranged on a locking pin 35 ( FIG. 4 ) which is insertable in the through bore 134 in such a manner that the locking pin 35 can be advanced towards the front end 135 of the screwdriver 13 in order to prevent the tip 17 from radially collapsing so that it can be firmly kept in the recess 3 in the screw head 2 of the bone screw 1 .
[0092] The embodiment of the screwdriver 13 illustrated in FIGS. 7 to 9 differs from the embodiment of FIGS. 3 to 6 only therein that the male connector 132 further includes a nose 34 extending from the tip 17 in a direction towards the front end 135 . The nose 34 has a nose axis 38 extending under the angle α with respect to the longitudinal axis 130 of the screwdriver 13 . Thus, the screwdriver 13 can be coupled to the bone screw 1 in only one rotative position, namely the one position where the nose 34 engages the through hole 9 in the bone screw 1 in such a manner that the nose axis 38 coincides with the through hole axis 7 .
[0093] FIG. 10 illustrates an embodiment of the aiming guide 23 to be used with the bone screw 1 according to FIGS. 1 and 2 . The aiming guide 23 comprises a longitudinal axis 230 , a coaxial through bore 28 , a guide sleeve 26 , a front end 235 and a male connector 232 terminally arranged at the front end 235 . To releasably couple the aiming guide 23 to the bone screw 1 the connector 232 is essentially complementarily formed to the seat 14 in the screw head 2 of the bone screw 1 . The connector 232 includes a spherically shaped tip 231 which tapers inward toward the front end 235 and toward the guide sleeve 26 forming a ball-and-socket joint with the recess 3 of the above described embodiment of the bone screw 1 . The spherically shaped tip 231 has a radius of the sphere R and a centre 233 located on the longitudinal axis 230 . Additionally, the connector 232 includes two pins 25 diametrically projecting over the tip 231 in either direction and which are coaxially arranged on a central axis 234 which extends orthogonal to the longitudinal axis 230 and which cuts the longitudinal axis 230 through the centre 233 of the spherically shaped tip 231 . The pins 25 are circular-cylindrically shaped with a cylinder axis coinciding with the central axis 234 so as to form axles coaxially and rotatably insertable in the transverse channel 5 in the screw head 2 of the bone screw 1 . The aiming guide 23 further comprises a longitudinal slot 27 open at the front end 235 to form the tip 231 as an elastic male connector for a snap-lock connection between the aiming guide 23 and a the spherical recess 3 in the screw head 2 of the bone screw 1 . The longitudinal slot 27 is arranged orthogonal to a plane defined by the longitudinal axis 230 and the central axis 234 and penetrates through the guide sleeve 26 . Between the tip 231 and the guide sleeve 26 a cylindrical collar 33 is arranged coaxially to the longitudinal axis 230 and which has a radius r≦R.
[0094] As illustrated in FIGS. 13 and 14 a drill guide 36 can be inserted in the through bore 28 in the aiming guide 23 . The drill guide 36 has a conical tip 37 which fits into the tapered through hole 9 in such a manner that the drill guide 36 is exactly aligned with the through hole axis 7 of the through hole 9 in the bone screw 1 .
[0095] FIGS. 11 to 17 show an embodiment of the method for bone fixation by using an intramedullary nail 300 and bone screws 1 along with second screws 50 , which are briefly described in the following section. The intramedullary nail 300 comprises a nail axis 303 , a proximal end 305 , a peripheral surface 304 , a number of proximal locking holes 301 with a most proximal locking hole 302 and a number of distal locking holes 306 . The proximal and distal locking holes 301 , 306 extend transverse to the nail axis 303 . The intramedullary nail 300 is inserted into the intramedullary canal of a long bone in such a manner that the portion of the intramedullary nail 300 containing the distal locking holes 306 is located in a distal bone fragment and the portion containing the proximal locking holes 301 is located in the proximal bone fragment. In order to lock the intramedullary nail 300 in the bone a bone screw 1 each is driven through all or a number of selected proximal and distal locking holes 301 , 306 . Using the bone screw 1 according to the invention the bone screws 1 can be driven through all or the selected proximal and distal locking holes 301 , 306 and the second screws 50 can be anchored in the bone. It should be appreciated that instead of driving the bone screws 1 into the proximal and distal locking holes 301 , 306 the second screws 50 could be driven into the proximal and distal locking holes 301 , 306 and the bone screws 1 could be anchored in the bone.
[0096] The method for inserting the bone screws 1 into the nail 300 and anchoring the second screws 50 into the bone comprises the steps of making an incision into the tissue surrounding a bone to be treated and positioning an intramedullary nail 300 in the bone. An aiming device (not shown) to the proximal end 305 of the intramedullary nail 300 , wherein the aiming device has guide bores for inserting guide sleeves and/or tissue protection tubes 40 coaxially to each of all or of a number of selected proximal and/or distal locking holes 301 , 306 . A tissue protection tube 40 ( FIGS. 9 and 11 ) is inserted into a selected guide bore in the aiming device coaxially to one of the proximal and distal locking holes 301 , 306 until the front end of the tissue protection tube 40 contacts the surface of the bone. A first bore hole is then drilled into a bone for insertion of a bone screw 1 through the selected proximal or distal locking hole 301 , 306 by using the aiming device, wherein the first bore hole is aligned with the selected proximal or distal locking hole 301 , 306 . Further, the bore hole extends on either side of the intramedullary nail 300 in such a manner that a bone screw 1 can penetrate through the selected proximal or distal locking hole 301 , 306 of the intramedullary nail 300 when the bone screw 1 is anchored in the bone. The bone screw 1 is coupled to the connector 132 of the screwdriver 13 by using the snap-lock connection between the bone screw 1 and the screwdriver 13 and advancing the bone screw 1 through the tissue protection tube 40 . The bone screw 1 is then screwed into the bone using the screwdriver 13 . Once the bone screw 1 is screwed into the bone, the screwdriver 13 may be removed. The above-described steps may be repeated until a bone screw 1 has been inserted into all of the desired proximal and/or distal locking holes 301 , 302 .
[0097] The aiming guide 23 is then inserted through the protection tube 40 , as shown in FIG. 11 , to attach the aiming guide 23 to the bone screw 1 using the snap-lock connection between the tip 231 of the aiming device 23 and the recess 3 in the screw head 2 of the bone screw 1 such that the longitudinal axis 230 of the aiming guide 23 is aligned with the screw axis 6 of the bone screw 1 . The tissue protection tube 40 and the aiming device may be removed and the and the aiming guide 23 pivoted about the central axis 234 defined by the pins 25 arranged at the connector 232 of the aiming guide 23 until the collar 33 of the aiming guide 23 abuts a stop in the recess 3 in the screw head 2 of the bone screw 1 so that the longitudinal axis 230 of the aiming guide 23 is aligned with the through hole axis 7 of the through hole 9 in the bone screw 1 ( FIG. 12 ). The stop is formed by the wall portion 121 of the depression 12 in the recess 3 in the screw head 2 of the bone screw 1 . The drill guide 36 is then inserted into the through bore 28 in the aiming guide 23 ( FIG. 13 ) and a second bore hole is drilled into the bone using the drill guide 36 as a guide for the drill bit 39 . Once the second bore hole has been drilled, the drill guide 36 is removed and the second screw 50 is inserted through the through bore 28 in the aiming guide 23 ( FIG. 15 ) and advanced through the second screw 50 into the bone ( FIG. 16 ). The aiming guide 23 may then be removed and the steps described above repeated until a second screw 50 each is anchored in the bone passing through the through hole 9 of each of the bone screws 1 . Once all of the desired bone screws 1 and second screws 50 have been inserted into the bone, the incision may be closed.
[0098] As shown in FIGS. 18-21 , an alternate embodiment of the assembly of the present invention is substantially similar to the assembly described above in regard to FIGS. 1-17 , comprising a first bone screw 1 ′, a second bone screw 50 ′ and a screwdriver 13 ′. The screwdriver 13 ′, however, combines elements of the screwdriver 13 and the aiming guide 23 , as described above, such that two separate devices are not required for insertion of the first bone screw 1 ′ and for aiming the second bone screw 50 ′. In addition, the screwdriver 13 ′ includes a connector 132 ′ at a distal end 135 ′ thereof, which extends around a head 2 ′ of the first bone screw 1 ′ rather than within a recess thereof.
[0099] The first bone screw 1 ′ extends along a first axis 6 ′ and includes a head 2 ′, which has an exterior surface that is at least partially spherical. The exterior surface may also include portions that are substantially planar permitting a torsional force to be applied thereto via the screwdriver 13 ′. Similarly to the bone screw 1 , the first bone screw 1 ′ includes a through hole 9 ′ extending along a second axis 7 ′ to receive the second screw 50 ′ therein. The second screw 50 ′ is substantially similar to the second screw 50 ′ described above.
[0100] The screwdriver 13 ′ includes a shaft 131 ′ extending along a longitudinal axis 130 ′ with a connector 132 ′ formed at the distal end 135 ′ thereof. The screwdriver 13 ′ also includes a channel 28 ′ extending therethrough along the longitudinal axis 130 ′ sized and shaped to permit the second bone screw 50 ′ to be inserted therethrough. The connector 132 ′ includes a partially spherical interior surface 231 ′ sized and shaped to receive the head 2 ′ of the first bone screw 1 ′ therein. In one embodiment, the connector 132 ′ may be keyed (e.g., include planar portions corresponding to the planar portions of the head 2 ′) permitting the screwdriver 13 ′ to apply torsional forces to the bone screw 1 ′ while also permitting the first bone screw 1 ′ to pivot with respect to the screwdriver 13 ′ via the partially spherical surfaces of the connector 132 ′ and the head 2 ′. The interior surface 231 ′ may receive the head 2 ′ via, for example, a snap fit.
[0101] In an alternative embodiment, the head 2 ′ may include pins extending radially outward therefrom, which are substantially similar to the pins 25 of the connector 232 of the aiming guide 23 , and the connector 132 ′ may include a transverse channel diametrically extending thereacross similarly to the channel 5 of the bone screw 1 , as described above. It will be understood by those of skill in the art that such a configuration also permits the first bone screw 1 ′ to be rotated via the screwdriver 13 ′ while also permitting the first bone screw 1 ′ to be pivoted relative thereto.
[0102] The first and second bone screws 1 ′, 50 ′ and the screwdriver 13 ′ may be used in a manner substantially similar to the method described above. In particular, the first bone screw 1 ′ may be inserted into a desired one of the proximal and/or distal locking holes 301 , 306 of an intramedullary nail 300 inserted into the bone. A first bore hole may be drilled through the desired one of the first and second holes 301 , 306 to accommodate the first bone screw 1 ′. As described above, the screwdriver 13 ′ is coupled to the first bone screw 1 ′ by receiving the head 2 ′ within the connector 132 ′. In an initial configuration, the longitudinal axis 130 ′ of the screwdriver 13 ′ is coaxially aligned with the first axis 6 ′ of the bone screw 1 ′. The first bone screw 1 ′ is screwed into the desired one of the holes 301 , 306 and the first bore hole via the screwdriver 13 ′. Once the first bone screw 1 ′ has been inserted, as desired, the screwdriver 13 ′ is pivoted with respect to the first bone screw 1 ′ about the head 2 ′ until the channel 28 ′ thereof is coaxially aligned with the second axis 7 ′ of the through bore 9 ′. A second bore hole may be drilled into the bone through the channel 28 ′ and through bore 9 ′ to accommodate the second bone screw 50 ′. The second bone screw 50 ′ may then be guided through the channel 28 ′ and into through bore 9 ′ to be advanced into the second bore hole in the bone. It will be understood by those of skill in the art that the above-described steps may be repeated, as desired, until a desired number of first and second bone screws 1 ′, 50 ′ have been inserted into the bone.
[0103] Although the invention and its advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, composition of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention.
[0104] It will be appreciated by those skilled in the art that various modifications and alterations of the invention can be made without departing from the broad scope of the appended claims. Some of these have been discussed above and others will be apparent to those skilled in the art. | A bone screw includes a screw shaft extending longitudinally along a screw axis and a screw head extending from a proximal end of the screw shaft and configured to be releasably coupled to a surgical tool. The bone screw also includes a through hole defining a through hole axis and extending through the screw head, the through hole axis intersecting the screw axis at an acute angle α, the through hole being adapted to receive therein a second screw and tapering from a first end at a proximal end of the screw head to a second end opening to an outer surface of the screw head. | 0 |
The present invention is directed to an improved tool for spreading compound such as dry wall compound, plaster, cement, spackle, grout, bond compound or the like, upon generally flat planar surfaces such as drywall, tile, vertical wall, or horizontal surfaces and, more particularly, using spreader tools that have improved formations applying and spreading compound to such surfaces with minimal manual effort and maximum smoothing effect.
BACKGROUND OF THE INVENTION
In the finishing operations of drywall construction, tape is usually applied between adjacent pieces of drywall. Thereafter, compound such as plaster or joint compound is spread over the tape covering the drywall seams and over adjacent portions of the adjoining drywall pieces, to thereby fuse together the previously separate sections of drywall. Thereafter, in the usual fashion, joint compound or the like is applied over the remainder drywall surface area, where needed, to provide a finished product.
The conventional tool for the application of the joint compound over the tape adjoining adjacent drywall pieces has been a simple flat, straight knife made of metal. In using this conventional knife in the application and spreading of the joint compound over the tape and adjoining drywall segments, a multiple-step operation is necessary. The multiple-step operation has been necessitated by the fact that the knife in current use must be used to apply a large amount of the joint compound on the drywall segments, thereafter spreading it in an uneven fashion and, after that, smoothing it out which, by itself, takes usually two or more separate operations of sanding and spreading more compound to refill shrinkage of the previously applied layer of compounds. Thus, the actual spreading of the joint compound or the like over the tape, adjacent drywall segments, and the rest of the drywall as needed, has been tedious, time consuming and a multiple-step operation.
The very same knife that has been used to apply the joint compound or the like to the tape and adjoining wall portions has also been used to apply spackle to fill in cracks in a wall or ceiling before the painting of the surfaces. This also is a time consuming and multi-step operation, in the same manner as the above-described application of joint compound to drywall. In the application of the spackle to a crack, what is most important is to fill the crack with the spackle, and to thereafter insure that the wall portions adjacent on either side of the crack are made smooth. Using the conventional knife, this has been, as described above, a difficult task, since the application of the spackle is not done consistently and evenly over the crack and adjoining wall portions thereto.
U.S. Pat. Nos. 4,731,258 and 4,654,919 disclose the tool and method for spreading joint compound, cement or spackle on planar surfaces including drywall, upon which the present improvement invention is based. These patents teach the use of a spreader tool having two surfaces, a flat surface and a concave surface. The present invention improves upon the prior art by providing a flexible application edge, variable spreader surface rigidity, and an improved surface curvature to enhance single application compound use, and to improve upon the utility and maintenance features of the prior art spreader tools. Additionally, the flexible application edge can be removable and replaceable to adjust to varying surfaces and varied compound spreading needs.
SUMMARY OF THE INVENTION
The main objective of the present invention is to provide an improved tool for spreading compound such as drywall compound, plaster, cement, and spackle to planar surfaces such that the amount of time required to do so is considerably shortened, the number of steps in order to accomplish the spreading is considerably reduced, and the use and maintenance of the tool is improved.
Another objective of the present invention is to provide such a spreading tool for the application of compound such as drywall joint compound, cement, plaster and spackle to planar surfaces such that it may be done in a very simple, easy and efficient manner.
Still another objective of the present invention is to provide an improved spreading tool for applying compound such as drywall joint compound, plaster, cement and spackle to planar surfaces such that the actual spreading and smoothing out may be accomplished in substantially one independent step.
Another objective of the present invention is to provide an improved spreading tool having a flexible application edge for applying bonding compound to a wide variety of planar surfaces, which edge may also be removable and replaceable to work on varying surfaces and with various compounds.
Yet another objective of the present invention is to provide such a spreading tool that is easy to manufacture, easy to use repeatedly, easy to clean after use, that is durable and long lasting, lightweight, not susceptible to damage upon dropping, and rust proof.
It is another objective of the present invention to provide an improved spreading tool for the application of compound such as drywall joint compound, cement, plaster, or the like on flat wall surfaces in order to finish them in a faster, easier and more expedient manner.
Still another object of the present invention is to provide an improved spreading tool for applying compound to planar surfaces including but not limited to drywall using drywall or joint compound, plaster, spackle, durabond or the like, to automobiles using such compounds as bondo or to cement surfaces using cement, foundation, floor or pavement compounds.
Toward these and other ends, the spreading tool of the present invention is provided in a first embodiment thereof with an applicator having a concave face and a back face, said applicator having a removable resilient outer edge connected thereto. Bonding compound or the like is applied to the planar surface using the applicator. The curvature of the concave face allows for the application of a substantial amount of bonding compound to the planar surface, concentrated in the middle, which thereafter may be applied by one stroke and smoothed out by pressing in along the concave face, so that the removable outer edge of the applicator substantially takes a flat planar shape to, thus firstly spread out the bonding compound during any stroke of the tool thereof and, at the same time, distribute the bonding compound in a uniform and smooth manner over the planar surface. The applicator preferably is made of rigid plastic, with the removable outer edge preferably being made of a flexible resinous material or plastic. The removable outer edge is integrally molded to form a stepped configuration having a flange which cooperatively associates with the applicator at its outer edge end. The removable outer edge is inserted into rigid yet removable interlocking fit with the outer edge end of the applicator, whereby the flexible outer edge assumes the concave formation of the applicator. The applicator has a handle for gripping. The applicator may also be made of an appropriate pliable metal that may yield to planar form upon the application of sufficient force in the manner described above.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be more readily understood with reference to the accompanying drawings, wherein:
FIG. 1 is a top plan view of the spreader tool of the center crown embodiment of the present invention;
FIG. 2 is a side elevational view taken along line 2--2 of FIG. 1;
FIG. 3 is a cross-sectional view taken along line 3--3 of FIG. 1;
FIG. 4 is a top plan view of an alternate, end crown embodiment of the spreader tool of the present invention;
FIG. 5 is a side elevational view taken along line 5--5 of FIG. 4; and
FIG. 6 is a cross-sectional view taken along line 6--6 of FIG. 4;
FIG. 7 is a bottom plan view of an alternate embodiment of the present invention having blade members of variable rigidity but no crown or removable outer blade edge;
FIG. 8 is a top plan view of the embodiment of the invention depicted in FIG: 7;
FIG. 9 is a side elevational view taken along line 9--9 of FIG. 7;
FIG. 10 is a top plan view of an alternate embodiment of the present invention showing a smaller scale improved spreader tool for patching having blade members of variable rigidity but no crown or removable outer blade edge;
FIG. 11 is a bottom plan view of the embodiment of the invention depicted in FIG. 10;
FIG. 12 is a side elevational view taken along line 12--12 of FIG. 10.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings in greater detail, the spreading tool for spreading compound such as drywall joint compound, plaster, and the like, on a planar surface such as drywall is indicated generally by Reference Numeral 10 in FIGS. 1 through 12. The tools shown in FIGS. 1 through 12 constitute the preferred embodiments of the present invention.
In FIGS. 1 through 3, the tool 10 includes a handle 12 formed in the conventional manner by which a hand may grip the tool 10. The forward front portion 13 of the handle 12 mounts the applicator 14 having an application face or a concave face 15 and a back face 16, both of which are fixedly mounted within the front portion 13 of the handle 12, as clearly shown in FIG. 3. The applicator 14 is integrally molded to form the concave face 15 and the back face 16. The outer edge end 17 of the applicator 14 projects outwardly as shown in FIGS. 1 and 3, and is comprised of a long arm 18, a short arm 19, and a cavity 20 between said arms 18 and 19. The removable outer edge 40 is of generally linearly stepped configuration (as shown in FIG. 3) and is cooperatively associated with said outer edge end 17 by inserting the cavity end 42 of said outer edge 40 into the cavity 20 of outer edge end 17, as shown in FIG. 3. The exterior face 44 of the removable outer edge 40 and the arms 18 and 19 of the outer edge end 17 constitute the drywall compound plaster, cement or spackle smoothing surface for applying same to drywall segment or the like. The applicator 14 is made of a rigid material, preferably plastic, although an appropriate metal may also be used. The removable outer edge 40 is made of a flexible plastic such as 1/8 inch silicon rubber urethane, although a resilient metal may be used.
Each of the faces 15 and 16 is curved such that, when viewing FIG. 1, each face 15 and 16 projects out of the plane of the page. For purposes of description, such curvature shall be termed concave, since it is being viewed from above the plane of FIG. 1. In FIG. 2, such curvature is clearly shown. The center of the curvature for each of the faces 15 and 16 is about a plane substantially dividing the handle 12 longitudinally thereof when viewing FIG. 1. Such plane projects perpendicularly to the surface shown in FIG. 1 and into the page thereof. While, for purposes of description, the curvature of the faces 15 and 16 has been described as concave, it is to be understood that such curvature need not be perfectly concave, but may be meniscus-shaped or the equivalent thereof, as long as there is an offset from the central longitudinal portion of the applicator 14 as compared to the end tips 30 and 31 thereof. This allows for the outer edge end 17 and the inserted outer edge 40 to be flexed inwardly upon sufficient pressure thereto via handle 12, so that the central longitudinal portion 33 lies co-planar with the end tips 30 and 31 thereof when applying the plaster or the like to drywall in order to spread it out evenly, to this form a flat edge-surface. The midsection of the concave face 15 is indicated by Reference Numeral 35 in FIG. 2, while the midsection of the back face 16 is indicated by Reference Numeral 36 in FIG. 2. Thus, it is within the scope and purview of the present invention to provide a center crown curvature of the applicator 14 and faces 15 and 16 that are parabolic or of other arcuate extension.
When using the improved spreading tool of FIGS. 1 through 3, the bonding compound, or the like, is first placed upon the concave face 15 of the applicator 14. The concave face 15 of the applicator 14 is placed against a planar surface such as drywall at the portion thereof where the tape has been applied, or where the crack is located, and the handle 12 is used to force the tool 10 inward toward the concave face 15, so that the midsection 35 thereof becomes co-planar with the end tips 30 and 31 of the applicator 14 and co-extensive therewith to form a flat, projecting surface. Thereafter, the tool 10 is dragged along the drywall surface, either vertically or horizontally or a combination thereof, with the application of sufficient pressure causing the outer edge 17 and the outer edge 40 to force the plaster to fill in the crack or to cover the tape that had been applied, while simultaneously causing the plaster lying directly adjacent to the outer edge 40 to be forced to spread outwardly from the midsection 35 of the concave face 15, toward the end tips 30 and 31, to cause it to be smooth and evenly distributed, all in one stroke. Thus, with just one stroke, the bonding compound is applied to the planar surface directly over a crack or tape, and is simultaneously spread out in an even and smooth manner. Thus, no additional applications or strokes of the tool are necessary to accomplish the application-spreading of the plaster at a crack or at a portion at which tape has been applied. The applicator 14 is of sufficient stiffness and strength so as to prevent the flattening of the concave face 15 other than at the outer edge end 17 and outer edge 40 by which the joint compound or the like is applied over the area to be worked and spread out smoothly therefrom. Regarding the curvature of the applicator 14, such may take different forms as described above, with preferably the angle indicated by Reference Numeral 33 in FIG. 2 generally falling within the range of between 3 and 15 degrees, the angle 33 being subtended by the tangent to the midsection portion 35 of the concave face 15 and a tangent to the end tip 30 of the same concave face 15, as shown in FIG. 2. The applicator 14 is made preferably of a rigid plastic, although metal may also be used. Flexible outer edge 40 is easily removed from applicator 14 for cleaning or replacement after or between uses.
FIG. 4 through 6 show an alternate embodiment of the invention. FIGS. 4 through 6 show a handle portion 50 and an applicator 60 having a concave face 61 and a back face 62. The back face 62 is integrally molded to the concave face 61 and the front portion 52 of the handle 50, but differs from the embodiment of FIGS. 1 through 3 in its blade curvature. The outer edge end 63 of the applicator 60 projects outwardly as shown in FIGS. 4 and 6, and is comprised of a long arm 64, a short arm 65, and a cavity 66 between said arms 64 and 65. The removable outer edge 40 is of generally Y-shaped configuration (as shown in FIG. 6) and is cooperatively associated with said outer edge end 63 by inserting the cavity end 42 of said outer edge 40 into the cavity 66 of outer edge end 63, as shown in FIG. 6.
The exterior face 44 of the removable outer edge 40 serves the same smoothing surface function as associated with arms 64 and 65 in the FIGS. 4-6 embodiment as it does in the FIGS. 1-3 embodiment, but for the unique blade curvature of the respective embodiments. In FIGS. 4-6, each of the faces 61 and 62 is curved such that, when viewing FIG. 4, only approximately half of the faces 61 and 62 are contoured or curved, thereby forming an end crown as opposed to the center crown shown in FIGS. 1-3. The end crown curvature of FIGS. 4-6 is depicted by Reference Numerals 70 and 71 in FIG. 5. Although in FIG. 5 it is shown that the curvature of each of the faces 61 and 62 of the laminate starts a distance somewhat spaced from the midsections 74 and 75 of faces 61 and 62, respectively, it is within the scope and purview of the present invention to allow such curvature from the substantial mid-longitudinal section of each respective layer, in a manner shown in FIG. 2 of the first embodiment. The embodiment of the invention shown in FIGS. 4-6 is particularly advantageous for use in corner applications of compound whereby the end crown 70 and 71 of the applicator 60 applies compacted compound toward an inside corner without mess or interference with the intersecting wall. Additionally, the embodiment of the invention depicted by FIGS. 4-6 is useful for smoothing compound over large surface areas as opposed to drywall joints or cracks, and for feathering, spackling and finishing of compound spreading particularly for great surface areas.
FIGS. 7-9 show a third alternate embodiment of the invention having a handle portion 80 formed in the conventional manner by which a hand may grip the tool 10. The front portion 81 of the handle 80 mounts the applicator 85 having an application face 86 formed of a resilient material, preferably flexible plastic affixed to a back face 87 formed of more rigid but still resilient material. A rigid member 82 is affixed to application face 86 for additional support. Said application face 86, back face 87 and rigid member 82 are fixedly mounted within the front portion 81 of the handle 80, as clearly shown in FIGS. 7-9. The outer edge end 88 of the applicator 85 is comprised of the edge end 89 of application face 86 which extends in length beyond back face 87 to form the flexible outer edge end 88.
When using the improved spreading tool of FIGS. 7-9, bonding compound or the like is first placed upon application face 86 of the applicator 85. Application face 86 then is placed against a planar surface such as drywall or, preferably for this embodiment, ceramic tile or wallpaper, and the handle 80 is used to force the tool 10 inward to exert pressure on the application face 86 and, in particular, the edge end 89. Thereafter, the tool 10 is dragged along the planar surface with sufficient pressure to cause the edge end 89 and application face 86 to force the bonding compound smoothly into place over and/or in crevices, joints or the like, of the planar surface, leaving a smooth finish without forming ridges or other interruptions of spread compound frequently formed by metal spreading tools.
FIGS. 10--12 show a fourth alternate embodiment of the invention similar to the embodiment shown in FIGS. 7-9 but smaller and tapered particularly for spackling, patching, wallpapering, and grouting work. In this embodiment, the tool 10 has a handle portion 90 formed in a conventional manner by which a hand may grip the tool 10. The front portion 91 of the handle 90 mounts the applicator 95 having base application section 96 formed of resilient material, preferably flexible plastic. A rigid member 92 is affixed to the base application section 96. Rigid member 92 and base application section 96 are fixedly mounted within the front portion 91 of the handle 90, as clearly shown in FIGS. 10-12. The outer edge end 98 of the applicator 95 is comprised of the edge end section 99 forming a flexible outer edge having a smaller width than the remainder applicator 95 by virtue of tapers 100 and 105 of the applicator 95. Edge end section 99 of applicator 95 is preferably made of a resilient material that is more flexible and softer than base application section 96. In effect, applicator 95 is merely a flat blade having two sections. Two different plastic recipes will be used and the two sections will be either bonded or interlocked together at joint 97 to appear as a simple flat blade with edge end section 99 being more flexible than the rest of applicator 95. Joint 97 can be any suitable joint to connect base application section 96 and end edge section 99. For example, joint 97 may be a flat joint, a simple notch and groove, a step shaped joint, etc. The tool 10 shown in FIGS. 10-12 is [modified in size and shape] compared to the tool 10 of FIGS. 7-9, but has similar advantages, properties and methods of use as that disclosed above for tool 10 of FIGS. 7-9.
While specific embodiments of the invention have been shown and described, it is to be understood that numerous changes, alterations and modifications thereof may be made without departing from the scope, spirit, and intent of the invention as defined in the appended claims. | An improved tool for spreading bonding compound, or the like, on planar surfaces which, in a first embodiment, includes a contoured surface having two end tip portions and a midportion contained in a plane spaced between the end tip portions. The tool includes a back which gives structural integrity to the tool, and a flexible application outer edge connected to the application face. In use, the bonding compound is applied to the planar surface, and the projecting flexible outer edge of the application face is forced against the wall and pulled along to obtain a flat surface to spread the plaster out along the planar surface to spread the bonding compound evenly and smoothly over the planar surface. The flexible outer edge can be removable and replaceable for adjusting to varying surfaces and for easy maintenance. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for sensing a water level and vibration of a washtub for a washing machine based the amount of a laundry, and in particular, to a method and apparatus for accurately sensing a water level and vibration by detecting an abnormal vibration caused by an inclination of the laundry during a dehydration process of a washing control mode as a LC resonant frequency for thereby optimizing a washing control operation and implementing an accurate detection of a water level and vibration of a washing machine.
2. Description of the Background Art
Generally, a washing machine is designed to detect the amount of a laundry in a washtub. When the amount of the laundry is detected, the water level, the amount of a detergent, and the entire washing time are determined based on the thusly detected amount of the laundry.
Based upon the total washing time required, the washing machine executes a washing operation in which the water within the washtub swirls based on the operation of a pulsator to form a frictional force against the laundry for thereby washing the laundry.
After the washing operation, the washing machine discharges the polluted water to the outside of the washtub and then execute a rinsing operation in which a fresh water is supplied into the washtub to rinse the laundry by the preset number of times.
After the rinsing operation, the washing machine discharges the water to the outside of the washtub and then executes a dehydration operation in which an induction motor rotates at a certain high speed for thereby dehydrating the laundry based on a centrifugal separation force.
In the washing operation control of the washing machine, at an initial washing stage, the washing machine opens a water supply valve to receive a certain amount of water in accordance with the amount of the laundry within the washtub, until the water level reaches a set water level. At this time, as a water level sensing method, there is known a sensing method in which a LC resonant frequency is varied based on the pressure of water supplied within the washtub.
By way of example, if the pressure of water supplied within the washtub is varied, the LC resonant frequency is varied correspondingly thereto. Then, after the varied LC resonant frequency has been measured, the water level corresponding to the amount of the laundry is determined and the water supply valve is closed to stop the supply of water for thereby implementing a proper water level.
During the dehydration operation, since the motor is typically set to rotate at a high speed of about 1700 rotations per minute, a great centrifugal force is generated and drastically affects the laundry within the dehydration tub to thereby cause a strong vibration or noise. Meanwhile, the vibration can not be fully absorbed by means of a balancing device such as a snubber bar which is installed at an upper end portion of the washtub.
In addition, the rotation of the dehydration tub is stopped in accordance with a control of the induction motor. However, since the rotating force caused due to inertia is varied in accordance with the amount of the washing water, the rotation of the dehydration tub is temporarily decreased. In the case that the induction motor is stopped, it is gradually increased. Accordingly, it fails to control the rotation of the dehydration tub to prevent the generation of the vibration and noises.
To overcome the above problems, an improved washing machine capable of sensing the water level and vibration within the washtub during the washing operation is disclosed.
The above improved washing machine has a water level sensor and a vibration sensor. For instance, during the washing and rinsing operations, the water level sensor serves to supply and sense the optimal water level within the washtub, and during the dehydration operation, the vibration sensor functions to sense the vibration generated in the washing machine.
FIGS. 1 to 6 illustrate a conventional washing machine in which a water level sensor and a vibration sensor are installed independently.
As shown therein, the washing machine including a water level sensor and a vibration sensor includes a tank 100 installed within a casing 102 and having an opened top portion and a closed bottom portion, a snubber bar 107 lying between dampers 108 which are respectively assembled at the upper portion of the casing 102 and the lower portion of the tank 100 for absorbing the impact of the tank 100 , a washing and dehydration tub (hereinafter, called as a washtub) 101 installed in the interior of the tank 100 and mounted in a coaxial state with the tank 100 to execute the washing and dehydration operations, the washtub forming a plurality of conically shaped holes on the surface thereof, an induction motor 103 installed at a lower portion of the outer surface of the tank 100 for implementing a reverse rotation, a clutch 104 assembled with the induction motor 103 by means of a pulley belt 105 for delivering and decelerating the rotating force of the induction motor 103 , a pulsator 106 rotatably installed on the inner bottom surface of the washtub 101 and interposed between the washtub 101 and the clutch 104 for swirling the water within the washtub 101 , a water supply valve 109 connected with a water supply path installed at the upper portion of the tank 100 for supplying the water into the washtub 101 , a water discharging valve 110 installed on the bottom surface of the tank 100 for discharging the polluted water to the outside of the washtub 101 , a vibration sensor 112 installed on the inner surface of one side of the upper portion of the casing 102 for sensing the vibration formed by the contact with the tank 100 due to an eccentric rotation of the washtub 101 in accordance with an eccentrically formed laundry in a certain direction, a water pressure transfer path 113 having one end connected to the lower surface of the tank 100 and the other end vertically extended to the upper portion of the tank 100 for transferring the water pressure generated in accordance with the variation of the water level within the washtub 101 , a water level sensor 111 installed at the other end of the water pressure transfer path 113 for changing and outputting an inherent inductance in accordance with the transferred water pressure, a waveform shaping unit 116 for applying a fixed capacitance to the changed value of the inherent inductance to thereby generate a resonant frequency and for then stabilizing the generated resonant frequency with a voltage waveform to thereby amplify and output the resonant frequency, and a microprocessor 114 for determining the vibration and the water level with the vibration sensed by the vibration sensor 112 and the voltage waveform inputted through the waveform shaping unit 116 and for controlling the operation of the induction motor 103 using a motor driving member 115 and the opening and closing operation of the water supply and discharging valves 109 and 110 and a valve driving member 117 in accordance with the determined vibration and the water level. FIGS. 2 and 3 illustrate the detailed configuration of the water level sensor 111 as shown in FIG. 1 .
The water level sensor 111 is comprised of a cylindrical housing 10 which has a through hole connected through the water pressure transfer path 113 to the tank 100 at one side thereof and an opening hole at the other side thereof, a bellows 11 which is installed within the housing 10 and is connected to the water pressure transfer path 113 to be extended or expanded in accordance with the pressure of water within the washtub 101 , a shielding member 12 which is sealed at the top portion of the bellows 11 and have a hook shape to shield the water pressure, a cylindrical coil 14 having an inherent inductance value, which is installed at the center portion of the inner wall of the housing 10 to be separated by a predetermined distance in a vertical direction from the shielding member 12 , a cylindrical core 13 which is hooked at the upper portion of the shielding member 12 and moves vertically in the internal space of the coil 14 in accordance with the extension and expansion of the bellows 11 to thereby vary the inherent inductance value of the coil 14 , a cylindrical support member 16 which is assembled at the top end portion of the coil 14 and serves to support the coil 14 against the housing 10 , a cap 17 which is adapted to cover the opening at the top end portion of the support member 16 , and a coil shape spring 15 which is interposed between the top surface of the core 13 and the bottom surface of the cap 17 to restore the core 13 to the original position thereof.
The waveform shaping unit 116 , as shown in FIG. 6, is comprised of an amplifier 116 a which amplifies an input voltage to a substantial voltage size to provide the amplified voltage to the microprocessor 114 , and condensers C 1 and C 2 which are respectively connected in serial with the input and output terminals of the amplifier 116 a via resistors R 1 and R 2 and feed back the output voltage from the amplifier 116 a to the input voltage thereof. In this case, the waveform shaping unit 116 is operated based on a LC resonant circuit configuration in such a manner that both terminals a and b of the coil 14 are respectively connected in parallel with the condensers C 1 and C 2 , and the core 13 moves vertically in the internal space of the coil 14 .
The vibration sensor 112 such as a safety switch or a limit switch, as shown in FIG. 5, is comprised of first and second voltage discontinuous members 22 and 23 which are respectively installed at the upper portion of the casing 102 and is electrically short-circuited or opened, a switch leg 20 which is hinged to the first voltage discontinuous member 22 to be separated at a predetermined distance from the tank 100 and rotates by the striking of the tank 100 according to the rotation radius of the washtub 101 to electrically short-circuit the first and second voltage discontinuous members 22 and 23 , and a spring 21 which restores the switch leg 20 to the original position thereof to electrically open the first and second voltage discontinuous members 22 and 23 . An explanation of the operation of the conventional washing machine in which the water level sensor and the vibration sensor are installed, respectively will be discussed in detail with reference to FIGS. 1 to 6 .
Firstly, if an operation is started after the washing operation has been set through an operational panel (not shown), the microprocessor 114 controls the water supply valve 109 , the water discharging valve 110 and the induction motor 103 through the valve driving member 117 and the motor driving member 115 to thereby execute the washing, rinsing and dehydration operations in a scheduled sequence.
At this time, the microprocessor 114 receives an input signal, which is generated in accordance with the operation states of the water level sensor 111 sensing the water level of the washtub 101 and the vibration sensor 112 sensing the vibration of the washtub 101 , and then outputs a control signal in response to the input signal.
In this case, the microprocessor 114 meets the following conditions. It recognizes the state where the core 13 of the water level sensor 111 , as will be described in detail, is not advanced into the internal space of the coil 14 , as the state where the water is not retained within the washtub 101 , i.e. the water level of zero, and contrarily, recognizes the state where the core 13 of the water level sensor 111 moves vertically the internal space of the coil 14 , as the state where the water is retained within the washtub 101 based upon the movement of the core 13 .
Under the above conditions, the microprocessor 114 controls, for the purpose of supplying the water within the washtub 101 upon an initial washing operation, the valve driving member 117 to open the water feeding valve 109 such as an electronic control valve in accordance with the amount of the laundry retained within the washtub 101 .
If the water is fed into the washtub 101 , the water pressure becomes high. Then, the water pressure is applied, through the water pressure transfer path 113 connected to the tank 100 , to the bellows 11 within the housing 10 of the water level sensor 111 . At this time, the shielding member 12 , which is sealed at the upper portion of the bellows 11 , prevents the water pressure from being continuously increased. This results in the generation of pressure expansion. Thereby, the pressure expansion renders the bellows 11 expanded in proportion to the water pressure.
Referring to FIG. 4, if the bellows 11 is expanded, the cylindrical core 13 , which is assembled with the shielding member 12 , moves in the internal space of the coil 14 upwardly in the vertical direction, in step ST 10 . The coil 14 has a diameter larger than that of the core 13 and includes the inherent inductance value. The inherent inductance value is varied in accordance with the upward movement of the core 13 , in step ST 20 . For example, the inherent inductance value is increased as the core 13 moves in the internal space of the coil 14 in the upward direction.
The inductance variation value of the coil 14 is multiplied by a capacitance value of the condensers C 1 and C 2 of the waveform shaping unit 116 of FIG. 6 to be produced as a predetermined resonant frequency. The resonant frequency is shaped into a voltage waveform by the waveform shaping unit 116 and is then supplied to the microprocessor 114 .
In other words, the both terminals a and b of the coil 14 of the water level sensor 111 are respectively connected in parallel with the condensers C 1 and C 2 of the waveform shaping unit 116 . As a result, the waveform shaping unit 116 is operated based on a single LC resonant circuit configuration by the arrangement of the coil 14 and the condensers C 1 and C 2 , thus to generate the resonant frequency, at step ST 30 .
Conventionally, the resonant frequency f 0 of the LC resonant circuit is calculated under the following equation: f 0 = 1 2 π LC [ Hz ]
The resonant frequency f 0 is amplified by the amplifier 116 a to a substantial voltage size, and the amplified voltage waveform is provided to the microprocessor 114 .
The microprocessor 114 measures the water level within the washtub 101 on the basis of the resonant frequency f 0 of the waveform shaping unit 116 generated based on the inductance variation value of the water level sensor 111 . Then, it determines as to whether the measured water level is optimal to correspond with the amount of the laundry detected. If determined as optimal, it controls the valve driving member 117 to close the water supply valve 107 .
Thereafter, it controls the motor driving member 115 to alternatively electrify the induction motor 103 , which renders the pulsator 106 to be forwardly and reversely rotated in turn.
As a result, the water within the washtub 101 is swirled, which causes the frictional force against the laundry to be generated, thus to execute the washing operation.
If the washing operation is completed, the microprocessor 114 controls the valve driving member 117 to open the water discharging valve 110 and discharges the polluted water to the outside of the washtub 101 . At the time, the water level sensor 111 senses whether the polluted water within the washtub 101 is completely discharged.
In other words, during the discharging operation, the water pressure is decreased as the water level within the washtub 101 is low. Accordingly, if the water pressure is increasingly decreased, the bellows 11 is expanded, based upon the elastic force of the spring 15 , which is interposed between the cap 17 and the core 13 of the water level sensor 111 . Moreover, the core 13 gradually descends vertically in the internal space of the coil 14 , thereby returning to the initial position thereof.
If the core 13 is returned to the initial position thereof, the inductance value of the coil 14 is also decreased. Hence, the resonant frequency f 0 , which is obtained by multiplying the inductance variation value of the coil 14 by the capacitance value of the condensers C 1 and C 2 , is changed to the initial value thereof and then inputted to the microprocessor 114 . As a result, the microprocessor 114 determines the completion time of the discharging operation.
After the completion of the washing operation, the rinsing operation is implemented through the water feeding and discharging to/from the washtub 101 , as mentioned above.
For the dehydration operation after the washing and rinsing operations are performed, the microprocessor 114 controls the induction motor 103 to be rotated at a set rotation speed and senses the vibration generated within the washtub 101 due to the rotation of the induction motor 103 by means of the vibration sensor 112 as shown in FIG. 5 .
During the dehydration operation, an appropriate balance or an undesirable vibration within the tank 100 is generated in accordance with the collection of the laundry in a certain direction.
If the laundry is uniformly disposed at the internal wall of the washtub 101 , the vibration within the washtub 101 caused due to the rotation speed of the induction motor 103 is not generated after a little amount of vibration has been generated. As a result, the washtub 101 finally reaches a normal dehydration speed, while having the same rotation radius centering around the concentric axis. This creates a balancing state where no vibration within the tank 100 is generated, thus to execute the normal dehydration operation during the set time period.
On the other hand, if the laundry is inclined at a certain corner of the wall of the washtub 101 , the washtub 101 eccentrically rotates in every direction as the rotation speed is high, and if the eccentric rotation is severe, the tank 100 undesirably strikes against the washtub 101 .
The vibration width is increased in accordance with the strength of the striking at the tank 100 , and as shown in FIG. 5, the switch leg 20 of the vibration sensor 112 such as the safety switch or the limit switch is struck at every rotation. Thereby, the switch leg 20 electrically short-circuits or opens the first and second voltage discontinuous members 22 and 23 , while rotating counterclockwise or clockwise by means of the spring 21 .
If the microprocessor 114 inputs an electrical signal from any one of the first and second voltage discontinuous members 22 and 23 , it controls the water supply valve 109 to supply the water within the washtub 101 and thus executes an untwisting operation for the laundry during a predetermined time period. Thereby, the laundry can be uniformly disposed on the wall surface of the washtub 101 to thereby reduce the strength of the vibration formed.
If the vibration is decreased, the microprocessor 114 controls the motor driving member 115 to rotate the induction motor 103 at a high speed, thereby completing the dehydration operation.
Meanwhile, if the microprocessor 114 continuously inputs the electrical signal from the corresponding voltage discontinuous member, after the untwisting operation for the wash, it halts the induction motor 103 to thereby prevent the generation of the over-vibration.
It can be appreciated that the water level and vibration sensing device in the conventional washing machine is capable of sensing, during the washing operation for the wash, the water level of the washtub using the LC resonant circuit in which an inductance variation value of the coil within the water level sensor is calculated and sensing, during the dehydration operation for the wash, the vibration within the washtub using the separate vibration senor such as a limit switch.
As known, however, since the conventional washing machine should include independent water level sensor and vibration sensor, there are some problems in that the production cost is high and a manufacturing process is complicate.
In addition, since the vibration sensor uses mechanical contact points and a spring, there is a problem in that malfunctions may be generated due to the aged deterioration or corrosion of the contact points. Furthermore, it is impossible for the conventional vibration sensor to accurately sense the vibration within the washtub because of the necessity of the adjustment of the intervals of the contact points and the decrement of the restoring force of the spring.
By way of example, if the vibration sensor is installed adjacent to the tank, it senses a slight vibration of the tank, which causes the washing machine to execute an unnecessary operation. However, if installed at some distance, it does not sense the vibration until the vibration becomes severe. Therefore, so as to dispose the initial position of the vibration sensor in an accurate manner, an additional production cost should be required and a productivity efficiency may be degraded.
Accordingly, there is a need to provide an improved water level and vibration sensing device which can solve the above problems experienced in the conventional washing machine and cam be manufactured with relative low production cost and high reliability.
SUMMARY OF THE INVENTION
Accordingly, the present invention is directed to a method and apparatus for sensing the water level and vibration in a washing machine that substantially obviates one or more of the problems due to limitations and disadvantages of the related arts.
An object of the invention is to provide a method and apparatus for sensing the water level and vibration in a washing machine which installs a unitary sensor to accurately sense both the water level and the vibration, thereby achieving an optimal washing operation, wherein the method is comprised of the step of sensing the excessive vibration within the washing machine only with an output of existing water level sensor, without having a mechanical vibration sensor.
Another object of the invention is to provide a method and apparatus for sensing the water level and vibration in a washing machine in which an active control in washing and dehydration operations is made by monitoring and suppressing the vibration state and the water level of the washtub therein, wherein the apparatus is comprised of a unitary sensor which is miniaturized and simply configured to accurately sense both the water level and the vibration of the washtub.
Still another object of the invention is to provide a method and apparatus for sensing the water level and vibration in a washing machine which can measure the vibration of a washtub, not in one-way direction, but in three-dimensions, to suppress a vibration error rate and can install control members for measuring the vibration in three-dimensions, while maintaining existing water level sensor function.
According to an aspect of the present invention, there is provided a method for sensing the water level and vibration in a washing machine which comprises the steps of measuring a resonant frequency, when a water level of a washtub corresponds to the water level of zero and there is no wash within the washtub, in a water level sensor which converts the variation of water pressure according to the water level of the washtub into the resonant frequency and senses the water level as the converted resonant frequency, setting the measured resonant frequency as a reference resonant frequency, measuring the resonant frequency from the water level sensor, during a dehydration operation among washing operations, and obtaining a deviation of the measured resonant frequency from the reference resonant frequency, and comparing the deviation of the measured resonant frequency from a deviation of the reference resonant frequency to determine whether the dehydration operation is continued.
According to another aspect of the present invention, there is provided a method for sensing the water level and vibration in a washing machine comprises the steps of moving the internal space of a coil by the variation of water pressure according to the water level of a washtub, during a washing operation, to vary an inherent inductance of the coil, moving the internal space of the coil by the vibration in a horizontal direction according to an eccentric rotation of the washtub, during a dehydration operation, to vary the inherent inductance of the coil, adding a predetermined capacitance value to the inherent inductance variation value, to thereby vary a resonant frequency, and determining the water level and the vibration within the washtub, on the basis of the variation amount of the resonant frequency.
Preferably, the amount of variation of the inherent inductance of the coil is defined as ΔL 1 , during the washing operation and as ΔL 2 , during the dehydration operation, under the conditions ΔL 1 >ΔL 2 .
According to still another aspect of the present invention, there is provided a method for sensing the water level and vibration in a washing machine comprises the steps of moving the internal space of a coil by the variation of water pressure according to the water level of a washtub, the coil having at least two or more inherent inductance values, to thereby vary any one inherent inductance value of the coil, freely moving a sliding member centering around a support member in which variation area and non-variation area are divided, according to an eccentric rotation of the washtub, to thereby vary at least one or more inherent inductance of the coil including the inherent inductance value for movement in a vertical direction, adding a predetermined capacitance value to the varied inherent inductance variation value, to thereby vary an inherent resonant frequency, and determining the water level and the vibration within the washtub, on the basis of the variation amount of the resonant frequency.
Preferably, the non-variation area is occupied by the portion to which the center of the support member is adjacent, and the variation area is occupied by the portion from which the center of the support member is far. In this case, as the sliding member moves toward the variation area, the inherent inductance value of the coil gradually increases.
Assuming that the left and right directions relative to a concentric axis of the washtub is designated as ‘X’, the before and behind directions as ‘Y’, and the top and bottom directions as ‘Z’, preferably, the coil has the inherent inductance value in the directions X, Y and Z, respectively.
It is desirable that any one of the directions X, Y and Z of the coil is designated as a water level sensing direction and the other as a vibration sensing direction.
Assuming that the vibration in the directions X, Y and Z is denoted as Vx, Vy and Vz, and the inherent inductance values in each direction are as Lx, Ly and Lz, the vibration in each direction is given by the following expressions: Vx=f 1 (Lx, Lz), Vy=f 2 (Ly, Lz), and Vz=f 3 (Vz), where coefficients f 1 , f 2 and f 3 are optional functions.
According to yet another aspect of the present invention, there is provided an apparatus for sensing the water level and vibration in a washing machine which comprises a sealing state maintaining member installed within a housing connected via a water pressure transfer path to a tank and moving vertically due to the variation of water pressure according to a water level of a washtub, a substantially cylindrical coil unit installed in the center portion of the internal wall of the housing and having an inherent inductance value, a magnetic media assembled on the upper surface of the sealing state maintaining member and moving vertically the internal space of the coil unit according to the variation of the water pressure to thereby vary the inherent inductance value of the coil unit, an inclined support member by a predetermined angle disposed to be separated by a predetermined distance from the top end portion of the magnetic media on the internal space of the coil unit and moving vertically according to the variation of the water pressure, along with the magnetic media, a sliding member made of a predetermined material, having a predetermined diameter, and moving vertically along the inclined surface of the support member according to an eccentric rotation of the washtub, to thereby vary the inherent inductance value of the coil unit, and a waveform shaping unit for adding a predetermined capacitance value to the varied inherent inductance variation value of the coil unit to thereby generate a resonant frequency and stabilizing the resonant frequency in a voltage waveform to selectively measure the amounts of water level and eccentricity in each direction.
According to yet still aspect of the present invention, there is provided an apparatus for sensing the water level and vibration in a washing machine which comprises a sealing state maintaining member installed within a housing connected via a water pressure transfer path to a tank and expanding and moving vertically due to the variation of water pressure according to a water level of a washtub, a coil unit installed at the center portion of the internal wall of the housing and having at least two or one inherent inductance values, a magnetic media hook-assembled on the upper surface of the sealing state maintaining member and moving vertically the internal space of the coil unit according to the variation of the water pressure to thereby vary any one of the inherent inductance values of the coil unit, a support member disposed to be separated by a predetermined distance from the top end portion of the magnetic media on the internal space of the coil unit and moving vertically according to the variation of the water pressure, along with the magnetic media, the support member having the upper surface on which a variation area and a non-variation area are divided on the basis of the center portion thereof, a sliding member made of a predetermined material, having a predetermined diameter, and moving freely to the variation area and the non-variation area of the support member according to an eccentric rotation of the washtub, to thereby vary any one of the inherent inductance values of the coil unit, and a waveform shaping unit for adding a predetermined capacitance value to the varied inherent inductance variation value of the coil unit to thereby generate a resonant frequency and stabilizing the resonant frequency in a voltage waveform to selectively measure the amounts of water level and eccentricity in each direction.
Assuming that the left and right directions relative to a concentric axis of the washtub is designated as ‘X’, the before and behind directions as ‘Y’, and the top and bottom directions as ‘Z’, preferably, the coil unit takes a substantially square hexahedral shape and is comprised of a coil which winds horizontally in the directions X, Y and Z, respectively, on the square hexahedron in a predetermined winding ratio.
Preferably, any one of the coils in the directions X, Y and Z varies the inductance value by the water level and vibration, and the other coils vary the inductance values according to the amount of eccentricity of the washtub, together with the one coil.
The upper surface of the support member is formed to have the portions in the left and right directions inclined to have the same angle as each other, on the center portion thereof, to thereby sense the eccentricity in the direction of X in the washtub, where the inclined angle is 20 degrees.
Preferably, the upper surface of the support member is rounded to have a smooth inclined surface in a radial direction, on the center portion thereof, to thereby form a spherical inner rounded surface, on which the sliding member moves freely in the radial direction.
Assuming that the vibration in the directions X, Y and Z is denoted as Vx, Vy and Vz, and the inherent inductance values in each direction are as Lx, Ly and Lz, the vibration in each direction is given by the following expressions: Vx=f 1 (Lx, Lz), Vy=f 2 (Ly, Lz), and Vz=f 3 (Vz), where coefficients f 1 , f 2 and f 3 are optional functions.
It can be from the above description understood that the unitary sensor according to the present invention can sense, during the washing and dehydration operations, both the water level of the washtub and an amount of vibration according to the eccentric rotation of the washtub.
As a result, a method and apparatus for sensing the water level and vibration in a washing machine according to the preferred embodiments of the present invention has the following advantages: a) a precise measuring result for the water level and vibration within the washtub can be extracted; b) an error probability of the vibration sensing value and a time period required for the dehydration can be all reduced; and c) installation of a mechanical vibration sensor is not needed.
Additional advantages, objects and features of the invention will become more apparent from the description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 illustrates a side view of a schematic configuration of a conventional washing machine in which a water level sensor and a vibration sensor are installed independently of each other;
FIG. 2 illustrates an enlarged sectional view taken in a vertical direction of the water level sensor in FIG. 1;
FIG. 3 illustrates an enlarged view of a coil provided to the water level sensor of FIG. 2;
FIG. 4 is an exemplary view showing the principles for measuring the water level within the washtub through an amount of variation of the frequency of the water level sensor of FIG. 2;
FIG. 5 illustrates a detailed side view of the vibration sensor in FIG. 1;
FIG. 6 illustrates a block diagram of a system for controlling a washing operation in accordance with the action of the water level sensor and the vibration sensor in FIG.
FIG. 7 illustrates a sectional view taken in a vertical direction of a unitary water level and vibration sensor in a washing machine according to a first embodiment of the present invention;
FIG. 8 illustrates an enlarged sectional view of a first support member of FIG. 7, in which a first sliding member moves in every direction according to the left and right impact of the tank and thus senses the vibration within the tank;
FIG. 9 illustrates a sectional view taken in a vertical direction of a unitary water level and vibration sensor in a washing machine according to a second embodiment of the present invention;
FIG. 10 illustrates an enlarged sectional view of a second support member of FIG. 9, in which a second sliding member moves in every direction according to the left and right impact of the tank and thus senses the vibration within the tank;
FIG. 11 illustrates a sectional view taken in a vertical direction of a unitary water level and vibration sensor in a washing machine according to a third embodiment of the present invention;
FIG. 12 illustrates an enlarged perspective view of a third support member of FIG. 11, in which a third sliding member moves freely along the inner rounded surface of the third support member according to the impact in every direction of the tank;
FIG. 13 illustrates a sectional view taken in a line I—I of FIG. 12;
FIG. 14 illustrates an enlarged view of a coil embodied in the second and third embodiments of the present invention;
FIG. 15 illustrates a block diagram of a system for controlling a washing operation by sensing both the water level and the vibration at one time through an inductance variation value of the coil embodied in the second and third embodiments of the present invention; and
FIGS. 16A and 16B illustrate graph diagrams in which a method for sensing the water level and vibration in a washing machine according to a fourth embodiment of the present invention is applied to FIGS. 2, 3 and 6 , wherein FIG. 16A is a graph diagram illustrating a resonant frequency measurement result during a no-load dehydration and FIG. 16B is a graph diagram illustrating a resonant frequency measurement result in case of a large amount of the wash.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
The present invention includes, of course, a plurality of embodiments, but hereinafter, an explanation on some preferred embodiments of the present invention will be in detail discussed.
In the drawings, like numbers indicate the same or similar elements and an explanation of them will be excluded in this detailed description for the sake of brevity.
FIG. 7 illustrates a sectional view taken in a vertical direction of a unitary water level and vibration sensor in a washing machine according to a first embodiment of the present invention, and FIG. 8 illustrates an enlarged sectional view of a first support member of FIG. 7, in which a first sliding member moves in every direction according to the left impact of the washing machine and thus senses the vibration therein.
In the first embodiment of the present invention, a water level and vibration sensor 200 includes a cylindrical housing 10 perpendicularly installed at an outer wall of a casing and engaged via a tank 100 and a water pressure transfer path 113 , a bellows 11 installed in the housing 10 , connected with the water level transfer path 113 , and retracted and elongated in accordance with a variation of the water pressure based on the water level in the washtub 101 , a shielding member 12 shielded at an upper portion of the bellows 11 and having a hook shape for shielding the transfer of the water pressure, a circular coil 14 having a certain inductance and installed at an inner wall of the housing 10 , a cylindrical core 13 hooked to the upper surface of the shielding member 12 and vertically moving in the interior of the coil 14 in accordance with a retracting is and elongating operation of the bellows 11 for varying a certain inductance of the coil 14 , a cylindrical support member 16 engaged to an upper portion of the coil 14 for supporting the coil to the housing 10 , a cap 17 for capping an open portion of the support member 16 , a coil shape spring 15 vertically engaged at an upper surface of the core 13 and a lower surface of the cap 17 for returning the position of the core 13 to its original position, a first support member 201 installed in the interior of the coil 14 at a certain distance from the upper portion of the core 13 , vertically moving together with the core 13 based on the retracting and elongating operation of the bellows 11 and having its upper surface having an inclination 201 a , and a first sliding member 202 having a diameter of about 3 mm through 5 mm, horizontally and vertically moving along the inclination surface 201 a of the first support member 201 by an eccentric rotation of the washtub 101 and varying the inductance of the coil 14 . Both terminals a and b of the coil 14 are parallely connected between the condensers C 1 and C 2 as shown in FIG. 6, so that a waveform shaping unit 116 operates as a LC resonant circuit when the core 13 and the first sliding member 202 vertically move in the interior of the coil 14 and along the inclination surface 201 a of the first support member 201 .
The water level and vibration sensing apparatus according to the first embodiment of the present invention operates as follows with respect to the detection of the vibration level due to the water level and an inclination of the laundry without a sensing error during a washing and dehydration process in the washing control operation.
The first embodiment of the present invention will be explained in more detail with reference to the accompanying drawings.
First, when a washing process, a rinsing process, and a dehydration process are set using an operation panel (not shown), the microprocessor 114 controls the water supply valve 109 , the dehydration valve 110 , and the induction motor 103 based on the valve driving unit 117 and the motor driving unit 115 for thereby implementing the set washing, rinsing and dehydration processes. At this time, at an initial stage of the washing process, the microprocessor 114 opens the water supply valve 109 using the valve driving unit 117 based on the amount of the laundry in the washtub 101 and supplies water into the washtub 101 .
When water is supplied into the washtub 101 , the water pressure is applied to a certain shielding state maintaining unit such as the bellows 11 installed in the housing 10 via the water pressure transfer path 113 connected with the tank 100 .
At this time, the transfer of the water pressure is blocked by the shielding member 12 which shields the upper portion of the bellows 11 . In this state, the bellows 11 is elongated in proportion to the water pressure.
When the bellows 11 is elongated, namely, the bellows 11 is upwardly moved, the magnetic medium such as a cylindrical core 13 hooked to the shielding member 12 and the first support member 201 are vertically moved in the interior of the coil 14 . At this time, the first sliding member 202 which is formed of a magnetic material is not vertically moved in the leftward and rightward directions along the inclination surface 201 a of the first support member 201 but vertically moved in a state that the same is positioned at the rightward portion of the first support member 201 as shown in FIG. 8 . Here, the inductance variation of the coil 14 based on the vertical movement of the first support member 201 is neglected. Namely, the inductance of the coil 14 is varied based on the vertical moving distance of the core 13 . As the core 13 is moved in the upward direction in the interior of the coil 14 , the inductance value of the coil 14 is increased.
The inductance variation value of the coil 14 is multiplied by the capacitances C of the condensers C 1 and C 2 of the waveform shaping unit 116 as shown in FIG. 6 and is generated as a certain resonant frequency. The thusly varied resonant frequency is amplified to a certain level by an amplification device 116 a of the waveform shaping unit 116 and is provided to the microprocessor 114 .
Since both terminals a and b of the coil 14 are parallely connected between the condensers C 1 and C 2 of the waveform shaping unit 116 , the waveform shaping unit 116 operates as a LC resonant circuit by the coil 14 and the condensers C 1 and C 2 for thereby generating a resonant frequency.
The microprocessor 114 compares the variation value of the resonant frequency inputted from the LC resonant circuit with a water level variation for thereby judging the water level of the washing tub 101 . If the judged water level is the optimum water level corresponding to the sensed amount of the laundry, the water supply valve 109 is closed by the valve driving unit 117 , and the washing process is performed.
When the washing process is completed, the dehydration valve 110 is opened by the valve driving unit 117 for thereby discharging a polluted water from the washtub 101 .
In the water draining mode, as the water level is decreased in the washtub 101 , the water pressure is decreased. When the water pressure is gradually decreased, the bellows 11 is retracted by an elastic force of the coil shape spring 15 engaged between the magnetic medium such as the cap 17 and the core 13 , and the core 13 and the first support member 201 are vertically and downwardly moved in the interior of the coil 14 .
When the core 13 and the first support member 201 are returned to their original positions, the inductance of the coil 14 is decreased. The resonant frequency based on the decreased inductance and the capacitances of the condensers C 1 and C 2 are changed to the initial values and are inputted into the microprocessor 114 for thereby judging the completion time of the water draining process.
When the washing process is completed, the rinsing process is performed after the water supply and draining processes are performed based on the water level sensing method.
After the washing and rinsing processes are performed, the microprocessor 114 operates the inductance motor 103 at a high speed for thereby performing a dehydration process.
In the dehydration process, since the water level of the washtub 101 is a zero level, the water pressure applied to the water level sensor becomes the resonant frequency at the time when the water level is zero.
In addition, in the dehydration process, when the laundry is uniformly arranged in the washtub 101 , the washtub 101 is uniformly rotated with respect to the co-axis, so that an optimized operation is implemented without vibration of the tank 100 .
When the tank 100 is in the balanced state without vibration, as shown in FIG. 8, the first sliding member 202 such as a ball formed of a magnetic material is not moved in the leftward and rightward directions along the inclination surface 201 a of the first support member 201 . Namely, the same is positioned at the rightward portion of the inclination surface 201 a.
When the first sliding member 202 which is formed of a magnetic material is positioned at the rightward portion of the first support member 201 , the inductance of the coil 14 is not varied. Therefore, the same resonant frequency is generated from the LC resonant circuit and is provided to the microprocessor.
The microprocessor 114 recognizes the balanced state of the tank 100 using a voltage wave form with respect to the continuously inputted same resonant frequency and accelerates the inductance motor 103 using the motor driving unit 115 during a certain dehydration time for thereby dehydrating the laundry in the washtub 101 .
If the laundry is inclined at a certain wall of the washtub 101 , the washtub 101 is eccentrically rotated, and the tank 100 is unbalanced based on the eccentric rotation, so that the tank 100 is vibrated in the every direction.
When the tank 100 is vibrated, as the first sliding member 202 formed of a magnetic material having a diameter of 3 mm through 5 mm is moved, the upper surface of the first support member 201 is moved in the leftward and rightward directions along the inclination surface 201 a at an angle range of 0° through 40°, namely, in the ±X directions and the vertical ±Z direction.
For example, as shown in FIG. 8, if a certain force (vibration) is applied in the leftward direction, the first sliding member 202 is moved in the −X direction along the inclination surface 201 a of the first support member 201 by a reaction operation and is moved in the +Z direction. Namely, the first sliding member 202 is moved in the vertical direction (+Z) direction in accordance with the inclination angle of the first support member 201 . Here, the diameter of the first sliding member 202 is about 4 mm, and the inclination angle of the first support member 201 is 20°. The height D from the lower surface of the first support member 201 to an initial position of the inclination angle is about 0 mm.
Continuously, when the first sliding member 202 is moved in the horizontal and vertical directions along the inclination surface 201 a of the first support member 201 in accordance with the vibration of the tank 100 , the inductance of the coil 14 is changed.
When the tank 100 is greatly vibrated, the first sliding member 202 is greatly moved in the vertical direction along the inclination surface 201 a , and then is fallen by the gravity. Therefore, the inductance of the coil 14 is greatly changed. As a result, the resonant frequency of the LC resonant circuit is changed and is inputted into the microprocessor 114 .
Therefore, the microprocessor 114 detects the vibration of the tank caused by the eccentric rotation of the washtub 101 using the water level and vibration sensor 200 , and the rinsing and dehydration processes are performed in the above-described manner.
In the washing process, assuming that the inductance variation of the coil 14 due to the water level variation of the washtub 101 is Δ 1 , and the inductance variation of the coil 14 due to the vibration of the washtub 101 is ΔL 2 , the variation level of the inductance is ΔL 1 >ΔL 2 .
In the washing process, since the vertical direction movement distance that the core 13 is moved in the coil 14 by the pressure of the water supplied based on the amount of the laundry in the washtub 101 is great, the inductance of the coil 14 is greatly changed. In the dehydration process, the vibration is most greatly generated. The first sliding member 202 is moved as long as the length of the inclination surface 201 a of the first support member 201 . The variation of the inductance of the coil 14 is smaller than the movement of the core 13 .
FIGS. 9, 10 and 13 illustrate the second embodiment of the present invention.
The water level and vibration sensor 300 according to the second embodiment of the present invention includes a cylindrical housing 10 vertically installed at an outer wall of the upper portion of the casing 102 and connected via the tank 100 and the water pressure transfer path 113 , a bellows 11 installed in the housing and connected with the water pressure transfer 113 and implementing a retraction and elongation movement by the water pressure based on the water level in the washtub 101 , a shielding member 12 having a hook shape and shielding the transfer of the water pressure at the upper portion of the bellows, a coil unit 303 for installed at an inner center portion of the housing 10 and having more than at least three inductances, a cylindrical core 13 which is hooked at the upper portion of the shielding member 12 and is vertically moved in the inner space of the coil unit 303 in accordance with a retracting and elongating operation of the bellows 11 and varies an inductance of the coil unit 303 , a cylindrical support member 16 engaged to the upper portion of the coil unit 303 and supporting the coil unit, a cap 17 for covering the upper open portion of the support member, a spring 15 vertically engaged on the upper surface of the core 13 and the lower surface of the cap 17 and being formed in a spring shape for returning the core 13 to its original position, a second support member 301 installed in the inner space of the coil unit 303 spaced apart from the upper portion of the core 13 and vertically moving together with the core 13 based on the retracting and elongating operation of the bellows 11 and having its inclination surfaces 301 a and 301 b , a second sliding member 302 having a diameter of amount 3 mm through 5 mm and vertically moving along the inclination surfaces 301 a and 301 b at the center portion of the upper surface of the second support member 301 by the eccentric rotation of the washtub 101 and varying an inductance of the coil unit 303 and being formed of a magnetic material, and a waveform shaping unit 304 for providing a fixed capacitance to the inductance of the coil unit 303 based on the vertical movement of the core 13 and the movement of the second sliding member 302 , generating a resonant frequency, and stabilizing and outputting the resonant frequency to a voltage waveform.
FIG. 14 illustrates the construction of the coil unit 303 according to the second embodiment of the present invention.
The coil unit 303 is formed in a cubic shape and includes coils 303 a through 303 c which are wound in the X, Y and Z directions.
Namely, The coils 303 a and 303 b are wound in the X and Y direction, and the coil 303 c is wound in the Z direction into or onto the coils 303 a and 303 b.
The Z-direction coil 303 c is directed to detecting the vertical movement of the core 13 based on the water level, and the X and Y direction coils 303 a and 303 b are directed to detecting the current position of the second sliding member 302 based on the two-dimensional manner.
As shown in FIG. 15, the waveform shaping unit 304 according to the second embodiment of the present invention includes an amplification device 304 a for amplifying an input voltage and providing the amplified voltage to the microprocessor 114 and condensers C 1 and C 2 connected in series with resistors R 1 and R 2 at the input and output terminals of the amplification device and feeding back the output voltage of the amplification device as an input voltage. The terminals (a,b), (c,d) and (e,f) of the coil unit 303 are parallely connected with the condensers C 1 and C 2 , so that when the core 13 and the second sliding member 302 are moved in the vertical and horizontal directions in the inner space of the coil unit 303 and along the upper surface of the second support member 301 , the waveform shaping unit 304 operates as a LC resonant circuit.
The operation of the water level and vibration detection apparatus for a washing machine according to the second embodiment of the present invention will be explained with reference to the accompanying drawings.
When a water is supplied into the washtub 101 , the water pressure of the thusly supplied water is applied to the bellows 11 in the housing 200 of the water level and vibration sensor 300 via the water pressure transfer path 113 connected with the tank 100 .
When the water pressure is increased, the pressure of the bellows is increased. When the bellows 11 is upwardly moved, the second sliding member 302 which is formed of a magnetic material and is positioned at the center position of the support member is vertically and upwardly moved in the inner space of the coil unit 303 onto which the coils 303 a through 303 c are wound in the X, Y and Z directions.
The inductance of the X direction coil 303 c is varied at the coil unit 303 based on the vertical movement distance of the second support member 301 and the second sliding member 302 . The inductance of the X and Y direction coil 303 a and 303 b are not varied.
As shown in FIG. 14, since the X and Y direction coils 303 a and 303 b are installed in the vertical direction, even when the core 13 , the second support member 301 and the second sliding member 302 are moved in the vertical direction, the X and Y direction coils 303 a and 303 b do not receive any effects. Therefore, the inductance of the coils 303 a and 303 b do not vary.
However, since the Z direction coil 303 c is installed in the horizontal direction, and the core 13 , the second support member 301 and the second sliding member 302 are moved in the vertical direction in the inner space of the horizontally installed Z direction coil 303 c , only the inductance of the Z direction coil 303 c is varied.
As the core 13 , the second support member 301 and the second sliding member 302 are upwardly moved in the inner space of the Z direction coil 303 c , the inductance of the Z direction coil 303 c is increased.
The inductance variation value of the Z direction coil 303 c is multiplied by the capacitance C of the condensers C 1 and C 2 of the waveform shaping unit 304 as shown in FIG. 15 and is changed to a certain resonant frequency. The thusly obtained resonant frequency is fully amplified to its limit level by the amplification device 304 a of the waveform shaping unit 304 and is supplied to the microprocessor 114 .
Namely, both terminals a and b of the Z direction coil 303 c are parallely connected between the condensers C 1 and C 2 of the waveform shaping unit 304 , the waveform shaping unit 304 operates as a LC resonant circuit by the Z direction coil 303 c and the condensers C 1 and C 2 for thereby generating a resonant frequency. Therefore, it is possible to measure the water level during the washing and rinsing processes using the thusly changed resonant frequency in the same manner as the first embodiment.
After the washing and rinsing processes are performed, the microprocessor 114 operates the inductance motor 103 at a high speed for thereby implementing a dehydration process.
At this time, if the laundry is uniformly provided in the walls of the washtub 101 , the washtub 101 is uniformly rotated based on the same radius, so that any vibration of the tank 100 does not occur for thereby implementing a balanced rotation.
If the tank 100 is not vibrated in the balanced state, as shown in FIG. 10, the second sliding member 302 does not move in the leftward and rightward directions along the inclination surfaces 301 a and 301 b of the second support member 301 , namely, in the −X and +X directions, and is positioned in the non-vibration area.
Since the second sliding member 302 is positioned in the non-vibration area of the second support member 301 , and the core 13 is not vertically moved by the zero water level of the washtub during the dehydration process, the inductance of the X direction coil 303 a is not varied.
If the second sliding member 302 is continuously positioned in the non-vibration area of the second support member 301 based on the balanced position of the laundry, the same resonant frequency is continuously generated from the LC resonant circuit.
The microprocessor 114 recognizes the balance state of the tank 100 based on the voltage wave form with respect to the same resonant frequency and accelerates the inductance motor 103 using the motor driving unit 115 during a set dehydration time for thereby implementing a dehydration process in the washtub 101 .
However, if the laundry is non-uniformly provided at the wall of the washtub 101 , the washtub 101 is eccentrically rotated, and the tank 100 is vibrated based on the degree of the eccentric rotation and is leaned in the direction of the eccentrically positioned laundry.
When the tank 100 is vibrated, the second sliding member 302 having a diameter of 3 mm through 5 mm slides along the inclination surfaces 301 a and 301 b from the upper surface of the second support member 301 at an angle range of zero trough 40° based on the degree of the vibration. Namely, the second sliding member 302 slides in the direction of the vibration area (±X directions).
As shown in FIG. 10, when a certain force (vibration) is applied from the right portion, the second sliding member 302 is moved in the rightward direction (±X) via the inclination surface 301 b from the center portion (non-vibration area) of the second support member 301 , namely, in the vertical direction (±Z) in the vibration area. On the contrary, if a certain force (vibration) is applied from the left portion, the second sliding member 302 is moved in the left direction (−X) via the inclination surface 301 a from the center portion of the second support member 301 , namely, in the vertical direction (±Z) in the vibration area.
As shown in FIG. 14, in a state that the X direction coil 303 a is installed in the vertical direction, and the Z direction coil 303 c is horizontally installed, the second sliding member 302 is moved in the horizontal and vertical directions (in the vibration area) along the inclination surfaces 301 a and 301 b of the second support member 301 . As a result, the inductance of the X direction coil 303 a and the Z direction coil 303 c is changed.
In the second embodiment of the present invention, the diameter of the second sliding member 302 is about 4 mm, and the inclination angle of the inclination surfaces 301 and 301 b is about 20°.
The variation value of the inductance of the X direction coil 303 a and the Z direction coil 303 c is changed to a resonant frequency based on the condensers C 1 and C 2 as shown in FIG. 15 . Therefore, it is possible to obtain a X direction vibration by a certain function with respect to the X and Z direction inductance variations by the microprocessor 114 based on the thusly obtained variation value.
Assuming that the vibration in the X and Z directions are V X and V Z , the X direction vibration V X =f 1 (L X , L Z ) where f 1 is a certain function.
If the X direction vibration occurs, the laundry soaking and dehydration processes are continuously performed.
In the second embodiment of the present invention, since the second support member 301 is formed on the inclination surfaces 301 a and 301 b (vibration area) at a certain angle in the ±X directions at the upper surface center portion (non-vibration area), the X direction coil 303 a of the coil unit 303 is not used. Namely, a horizontally arranged cylindrical coil 14 as shown in FIG. 3 is additionally used for thereby computing the direction vibrations.
As shown in FIG. 3, when adapting the coil 14 , the second sliding member 302 is moved in the vertical direction with respect to the horizontally installed coil based on the inclination angle of the inclination surfaces 301 a and 301 b of the second support member 301 .
FIGS. 11 through 13 illustrate the third embodiment of the present invention.
FIG. 11 is a vertical cross-sectional view illustrating a water level and vibration sensing apparatus according to a second embodiment of the present invention, and FIG. 12 is a perspective view illustrating the third support member of FIG. 11, and FIG. 13 is a cross-sectional view taken along the line I—I of FIG. 12 .
The third support member 401 of the water level and vibration sensor 400 according to the third embodiment of the present invention includes a three dimensional spherical shape rounded surface having its upper surface which is radially rounded from its center portion for thereby implementing a radial direction free movement of the third sliding member 402 and is directed to detecting the vibrations in the forward and backward directions and the upward and downward directions.
In this case, the Z direction coil unit 303 is capable of detecting the movement of the core 13 based on the water level of the washtub during the washing process and is capable of measuring the water level and the upward and downward direction vibrations of the third sliding member 402 .
In view of the ±Z direction movements, there are two types of the movements. Namely, the third sliding member 402 formed of a magnetic material is moved in the upward and downward directions at the third support member 401 , and the third sliding member 402 is moved based on an inclination angle at the rounded surface 401 a of the third support member 401 .
Continuously, the X and Y direction coils 303 a and 303 b are capable of measuring the current position of the third sliding member 402 which is moved in the forward and backward directions at the rounded surface 401 a of the third sliding surface 401 in two dimension.
Therefore, it is possible to measure the X, Y and Z direction vibrations by measuring the X and Y direction vibrations in the above-described manner.
At this time, assuming that the inductances of the X, Y and Z direction coils 303 a through 303 c measured in the X, Y and Z directions are L X , L Y , L Z , the expression of V X =f 1 (L X , L Z ), V Y =f 2 (L Y , L Z ), and V Z =f 3 (V Z ). Here, f 1 through f 3 are certain function.
FIG. 16 illustrates the fourth embodiment of the present invention.
In the fourth embodiment of the present invention, the vibrations in the washing machine are detected using only the water level sensor 111 without the support members 201 , 301 and 401 and the sliding members 202 , 302 and 402 .
FIG. 16 illustrates the water level and vibration detection method according to the fourth embodiment of the present invention based on FIGS. 2, 3 and 6 . FIG. 16A is a resonant frequence wave form measured based on the water level sensor at the time when the dehydration process is performed in the non-eccentric process, and FIG. 16B is a resonant frequence wave form measured based on the water level sensor at the time when the dehydration process is started in the eccentric process. As shown in FIG. 16A, in the case that there is not eccentricity in the laundry or in the case of the non-load dehydration process, the induction motor 103 is driven in the zero water level state, and even when the speed of the induction motor 104 is increased based on the time lapse, the washtub 101 is not eccentrically rotated. Therefore, the resonant frequency of the water level sensor 111 is not changed.
However, as shown in FIG. 16B, in the case that there is a great eccentricity at the laundry, as the speed of the induction motor 103 is increased, the eccentric rotation of the washtub 101 is increased. The thusly increased eccentric rotation operates as an impact force which is applied to the outer casing 102 , and the thusly applied impact force is detected by the water level sensor 111 . The core 13 of the water level sensor 111 is moved in the interior of the coil 14 in the vertical direction based on the impact degree of the outer casing 102 , so that the inductance of the coil 14 is changed. The thusly changed inductance is changed to a resonant frequency by the LC resonant circuit, so that it is possible to measure the vibration by measuring the thusly changed resonant frequency. Namely, as shown in FIG. 16B, in the case that there is a great eccentricity at the laundry, the variation ΔHz of the resonant frequency of the water level sensor 111 is increased. Therefore, it is possible to check the current dehydration vibration state by detecting the variation ΔHz of the resonant frequency.
In more detail, the changed water pressure based on the water level of the washtub 101 is changed to the resonant frequency variation. In the case that the water level of the washtub 101 is a zero level checked by the water level sensor 111 , and there is not water to be dehydrated, the resonant frequency H 1 is measured and is set in the microprocessor 114 as a reference resonant frequency.
Thereafter, it is confirmed whether the current washing operation is a dehydration process. If the current mode is the dehydration mode, the resonant frequency H 2 is measured in the case that the water level is a zero level measured by the water level sensor 111 , and there is water to be dehydrated for thereby obtaining deviations H 2 -H 1 based on the reference resonant frequency H 1 . The thusly obtained deviation is compared with the reference variation ΔH. If the deviation is smaller than the reference variation ΔH, the induction motor 103 is rotated at a high speed for thereby implementing a normal dehydration. However, if the thusly obtained deviation is larger than the reference variation ΔH, the driving operation of the induction motor 103 is stopped, and the dehydration process is temporarily stopped, so that the over vibration of the washtub 101 is prevented.
The reference variation ΔH is a value which is previously set with respect to the values which are obtained based on a characteristic such as a type, capacitance, standard, etc. of the washing machine. In the dehydration process of the fourth embodiment of the present invention, the case that the vibrations are detected was explained. In another embodiment of the present invention, in the case that the induction motor 103 is in the turned on mode, it is possible to detect an over vibration during the entire washing processes by measuring the frequency variation using the water level sensor 111 .
In the present invention, it is possible to detect the vibrations of the washing machine based on the water level of the washtub and the rotation of the washtub using the water level and vibration sensor in the washing and dehydration modes compared to the conventional art in which the water level of the washtub is detected using the water level sensor and LC resonant circuit in the washing process, and the vibration of the washing machine is detected using a mechanical vibration sensor such as a limit switch in the dehydration mode.
As a result, in the present invention, it is possible to accurately measure the vibration of the washing machine based on the water level of the washtub and the eccentric rotation of the washtub, so that the error of the vibration detection and the time for dehydration are decreased. In addition, the number of the mechanical elements is decreased.
As described above, in the present invention, the vibration of the washing machine due to the eccentricity of the laundary and the water level are more accurately measured for thereby preventing the energy increase due to the vibration detection error and the increased dehydration time in the conventional art.
In the present invention, the water level and vibrations are accurately detected based on a quick operational response of the sliding member and coils in accordance with the eccentric degree of the laundry, so that it is possible to implement a better washing and dehydration process compared to the conventional washing machine. In addition, the reliability of the product is enhanced by implementing a performance stabilization of the product.
In the water level and vibration detection apparatus for a washing machine according to the present invention, the water level of the washtub and the vibration of the washing machine are accurately detected by a unitary sensor or a water level sensor, so that the mechanical vibration detection limit switch is not used for thereby implementing a cost reduction and preventing a complicate structure.
In addition, in the present invention, it is possible to implement a three dimensional vibration measurement. If the vibration width of the washing machine is large, it is possible to implement a simple control for stopping the washing and dehydration processes, and an active operation which is directed to detecting the vibration state during the washing and dehydration processes.
Although the preferred embodiment of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as recited in the accompanying claims. | A method and apparatus for sensing the water level and vibration for a washing machine are disclosed. The method includes the steps of measuring a resonant frequency, when a water level of a washtub corresponds to the water level of zero and there is no wash within the washtub, in a water level sensor which converts the variation of water pressure according to the water level of the washtub into the resonant frequency and senses the water level as the converted resonant frequency, setting the measured resonant frequency as a reference resonant frequency, measuring the resonant frequency from the water level sensor, during a dehydration operation among washing operations, and obtaining a deviation of the measured resonant frequency from the reference resonant frequency, and comparing the deviation of the measured resonant frequency from a deviation of the reference resonant frequency to determine whether the dehydration operation is continued, for thereby achieving an optimal washing operation, wherein the method is comprised of the step of sensing the excessive vibration within the washing machine only with an output of existing water level sensor, without having a mechanical vibration sensor. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to compounding ingredients for basic cosmetics and basic cosmetics, and more specifically, to a compounding ingredients for basic cosmetics and basic cosmetics containing the compounding ingredients which contain enzymes or hydrolysis products of nucleoprotein and/or DNA or RNA, or deoxy oligonucleotide, deoxy mononucleotide, oligopeptide, oligonucleotide, mononucleotide separated from the hydrolysis products, or at least two kinds of mixtures selected from the hydrolysis products or compounds as active ingredients.
[0003] 2. Description of the Related Art
[0004] Chapping of the skin, blotches, freckles, wrinkles etc. are assumed to be caused by various matters, effects of female hormone resulting from aging, stimulation of ultraviolet rays from sunlight, adverse effect of increased peroxide concentration in the body on epidermis, oversecretion of sebum, drop of blood flow to epidermis, malnutrition, mental stress, and the like.
[0005] It is manifested that chapping of the face skin, blotches, freckles, wrinkles, etc. are of a matter of serious concern for cosmetic reasons by an increase in product lineups of basic cosmetics not only for women but also for men in recent years. Because the face serves as a large element to give a first impression to other people, there are many persons who yearn for having a lustrous supple skin (beautiful skin) and a fair and clear skin (whitening), and therefore, interests of the world in general in basic skin cosmetics that improve chapping of the face skin, blotches, freckles, wrinkles, etc. have been more and more growing.
[0006] In conventional cosmetics which are included in the category of “basic cosmetics,” many efforts have been made to increase skin moisturizing action and to achieve lustrous skin by adding a moisturizing agent and oil component such as glycerin and the like. Recently, to achieve whitening effects to the skin, cosmetics containing L-ascorbic acid and its derivatives which have the action of suppressing the production of melanin, or hydroquinone derivatives have made an appearance.
[0007] And now, in recent years, to reflect growing interest of the world in general in health, healthfoods using deoxyribonucleic acid (DNA), ribonucleic acid (RNA) or nucleoprotein for material or active ingredients have been provided. It is proposed to depolymerize nucleoprotein of high molecular weight in order to make it water-soluble and easily-digestive (patent literature 1).
[0008] It is known that deoxyribonucleic acid (DNA), ribonucleic acid (RNA), or nucleoprotein has antiaging effects, but attempts to apply them to basic cosmetics have not yet been thoroughly made.
[0009] [Patent Literature 1] JP-A-2004-16143
[0010] Chapping of the skin, blotches, freckles, wrinkles, and other skin troubles are caused by aged facial skin, poor circulation, influence of ultraviolet rays, stresses, and other various factors, but are directly caused by degraded metabolism of skin cells and decreased regenerative function of new cells.
[0011] Conventional basic cosmetics are not intended to work on the metabolism mechanism of skin cells and to exhibit their functions but are anything more than merely pursuing effects on the skin surface. Consequently, effects that can be said satisfactory have never been obtained for chapping of the skin, blotches, freckles, wrinkles, whitening and the like.
[0012] In addition, L-ascorbic acid and their derivatives which have functions to suppress melanin generation mentioned above are not stable and have insufficient ultraviolet ray inflammation prevention effects, and hydroquinone derivatives have a problem with safety. Consequently, it is difficult to directly expect the melanin biosynthesis prevention effects and melanin bleaching action which the above-mentioned compounds possess as active ingredients of cosmetics.
[0013] That is, products with high skin whitening effects which promote regeneration of new cells by cellular stimulation and blood flow facilitation and prevent chapping of the face skin, blotches, freckles, wrinkles, etc. are desired but conventional basic cosmetics have not yet achieved the effects that satisfy these requirements.
[0014] Consequently, it has been desired to develop new basic cosmetics which stimulate cells themselves and which produce lively skin.
SUMMARY OF THE INVENTION
[0015] The present inventors devoted themselves to studies to obtain new basic cosmetics which provide prevention effects of chapping of the face skin, blotches, freckles, wrinkles, etc. and skin whitening effects, and as a result, found that decomposition products containing deoxy oligonucleotide, deoxy mononucleotide or oligopeptide obtained by enzyme-degradation treating or hydrolysis treating nucleoprotein and/or DNA, or decomposition products containing oligonucleotide or mononucleotide obtained by enzyme-degradation treating or hydrolysis-treating RNA, or their mixtures provide outstanding prevention effects of chapping of the face skin, blotches, freckles, wrinkles, etc., and have completed the present invention.
[0016] That is, the compounding ingredients for basic cosmetics according to the present invention are characterized by containing as active ingredients,
[0017] decomposition products obtained by depolymerizing by enzyme degradation or hydrolysis of nucleoprotein and/or DNA and containing 20 to 50% fractions of molecular weight ranging from 1000 to 3000, or deoxyoligonucleotide, deoxymononucleotide or oligopeptide separated from the decomposition products; or
[0018] decomposition products obtained by depolymerizing by enzyme degradation or hydrolysis of RNA and containing 20 to 50% fractions of molecular weight ranging from 1000 to 3000, or oligonucleotide or mononucleotide separated from the decomposition products; or
[0019] at least two kinds of mixtures selected from the group consisting of the nucleoprotein and/or DNA decomposition products, the RNA decomposition products, deoxy oligonucleotide or mononucleotide, oligopeptide, oligonucleotide, and mononucleotide.
[0020] In a preferable embodiment of the compounding ingredients for basic cosmetics according to the present invention, it is preferable to obtain the nucleoproteins and DNA from soft roes of salmon, trout, herring, bonito, cod, and others.
[0021] In addition, the RNA is obtained from enzymes selected from the group consisting of beer yeast, torula yeast, milk yeast, and baker's yeast.
[0022] Furthermore, the basic cosmetics according to the present invention contain the above-mentioned compounding ingredients for basic cosmetics.
[0023] The basic cosmetics are preferably selected from the group consisting of lotions, milky lotions, creams, gels, jellies, extracts, lip creams, facial masks, or massage masks.
[0024] The compounding ingredients for basic cosmetics contain decomposition products obtained by depolymerizing by enzyme degradation or hydrolysis of nucleoprotein and/or DNA and containing 20 to 50% fractions of molecular weight ranging from 1000 to 3000, or deoxyoligonucleotide, deoxymononucleotide, oligopeptide, oligonucleotide, mononucleotide separated from the decomposition products, or at least two kinds of mixtures selected from the decomposition products or the compounds as active ingredients. Because the deoxy oligonucleotide, etc. have comparatively small molecular weight, they are easy to be absorbed percutaneously and they provide cellular stimulation action and blood flow facilitation action when absorbed percutaneously. Consequently, in the event that they are applied to the epidermis of facial surface, they beautifully prevent chapping of the skin, blotches, freckles, wrinkles, etc., and achieve skin whitening effects.
[0025] In addition, because the basic cosmetics according to the present invention contain the compounding ingredients for basic cosmetics, when they are applied to epidermis of a face, effects of preventing chapping of the skin, blotches, freckles, wrinkles, etc. which the compounding ingredients for basic cosmetics possess are exhibited and skin whitening effects are achieved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a diagram that shows an analysis example of deoxy oligonucleotide by HPLC of nuclease-treated DNA (decomposition product);
[0027] FIG. 2 is a diagram that shows an analysis example of deoxy oligonucleotide by HPLC of nuclease-treated nucleoprotein (decomposition product); and
[0028] FIG. 3 is a diagram that shows an analysis example of oligonucleotide by HPLC of nuclease-treated RNA (decomposition product).
DETAILED DESCRIPTION OF THE INVENTION
[0029] Deoxy oligonucleotide or deoxy mononucleotide used as an active ingredient of the compounding ingredients for basic cosmetics of the present invention as well as for purified preparations are able to be obtained by enzyme-degradation treating or hydrolysis-treating DNA, and oligonucleotide or mononucleotide by enzyme-degradation treating or hydrolysis-treating RNA, and oligopeptide by enzyme-degradation treating or hydrolysis-treating nucleoprotein, respectively.
[0030] DNA and nucleoprotein are able to be obtained by, for example, extracting and purifying soft roes of fish. Examples of the fish include salmon, trout, herring, bonito, and cod, and in particular, salmon is preferable.
[0031] Now, DNA will be described more in detail as follows.
[0032] DNA which is the manufacturing material of the compounding ingredients for basic cosmetics of the present invention may be of various modes, and for example, may be double-stranded, single-stranded, or circular DNA. The DNA supply sources are various living organisms, such as animals, plants, microorganisms and the like. Testes (soft roes) of fishes which are wastes in fish-processing, in particular, salmon, trout, herring, bonito, and cod contain, in particular, a large amount of DNA, but conventionally, they were not effectively utilized as resources and a lot of them were discarded. Consequently, from the viewpoint of recycling of wastes, it is desirable to utilize the testes-derived DNA. In addition, it is possible to use DNA obtained from thymus glands of mammals and birds, for example, pigs, chickens and the like. Furthermore, synthetic DNA, too, may be able to be used.
[0033] By the way, to obtain DNA from fish soft roes, the extraction and purification method stipulated in Japanese Patent Application Laid-open No. 2005-245394.
[0034] Specifically, first of all, fish soft roes are coarsely ground, protein decomposition enzyme (protease) treatment is performed on coarsely ground fish soft roes under the conditions in which DNA is not decomposed, and the enzyme-treated solution is filtered. And using a hollow fiber membrane whose molecular weight cutoff ranges from 2,000 to 1,000,000, the filtrate is dialyzed to remove decomposed protein and ions and at the same time to concentrate DNA. Furthermore, DNA salts are allowed to be precipitated from the dialyzed solution or the solution is concentrated and these precipitates or concentrates are recovered.
[0035] The DNA salt powder obtained by drying the DNA salts obtained by the above method may be used for manufacturing material of the compounding ingredients for basic cosmetics of the present invention.
[0036] To obtain DNA from fish soft roes, not only this method but also publicly known methods may be used.
[0037] RNA is obtained from yeasts, and preferably, is obtained by extracting from a yeast selected from the group consisting of beer yeast, torula yeast, milk yeast, and baker's yeast and refining it.
[0038] The enzyme which treats DNA and RNA is, for example, nuclease, and for example, Penicillium-derived nuclease is preferable.
[0039] Oligopeptide is obtained by hydrolyzing nucleoprotein (protein constituent of cell nuclei) contained in fish soft roes, etc. by protease.
[0040] The protease primarily consists of trypsin. Trypsin is serine protease which has high specificity, and selectively hydrolyzes the peptide bond on the carboxyl side of arginine and lysine, and therefore, this is suited for hydrolyzing protamine which contains arginine. In addition, the above-mentioned protease may contain other protease, for example, chymotrypsin, etc. in addition to trypsin, too. For favorable protease, protease commercially available from Novozymes Japan Ltd. (former Novo Nordisk Bioindustry Ltd.) can be mentioned.
[0041] For the nuclease, 3′, 5′-phosphodiester linkage of deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) is hydrolyzed to generate 5′-(deoxy) nucleotide of oligomer polymerization. There is no particular limitation to the character of the nuclease but it is preferable to have a certain level of thermostability. This kind of nuclease is able to be obtained as a commercially-available product from Amano Enzyme Inc. (former Amano Pharmaceutical Co., Ltd.), Sigma Genosys Japan and the like.
[0042] What is important in hydrolysis treatment of DNA, RNA and nucleoprotein using the nuclease is the temperature at which reactions are conducted. The reaction temperature must be within the range from 60 to 75° C., and 70° C. is most preferable. Allowing reactions to take place at temperatures lower than the relevant temperature range prevents depolymerization of DNA, RNA and nucleoprotein to satisfactorily take place, and the decomposition products do not acquire water solubility. On the other hand, allowing reactions to take place at temperatures higher than the relevant temperature range causes depolymerization to take place excessively, and there is a fear of losing the superb effects of nucleoprotein.
[0043] As described above, by treating DNA, RNA and nucleoprotein by hydrolysis conducted at 60 to 75° C. using nuclease, it is possible to depolymerize DNA, RNA and nucleoprotein to such an extent that they contain 20 to 50% fractions whose molecular weight is 1000 to 3000, as well as to contain, for example, 30 to 50% fractions whose molecular weight is 1000 or less in a quantity larger than the quantity of fractions of molecular weight of 1000 to 3000, and by this, DNA, RNA and nucleoprotein decomposition products with both water solubility and transdermal absorptivity equipped can be manufactured.
[0044] In the nucleoprotein decomposition products and DNA decomposition products obtained by the foregoing treatment, depolymerized deoxy oligonucleotide, deoxy mononucleotide and oligopeptide are contained as a principal part or a large part, and insufficiently depolymerized deoxy nucleotide, etc. are contained as a negligible-amount part.
[0045] In addition, in the RNA decomposition product obtained by the similar treatment, oligonucleotide and mononucleotide are contained as a principal part or a large part, and insufficiently depolymerized nucleotide, etc. are contained as a negligible-amount part.
[0046] Consequently, almost all or the majority of nucleotides (deoxyoligonucleotide, deoxymononucleotide, oligonucleotide, and mononucleotide) are composed with monomers which originally do not take any helical strand, oligomers of perfect single-strand, and oligomers which have double-strand structure only partly. In other words, even if a case in which the above-mentioned depolymerization did not take place successfully is assumed, the ratio of double-strand of nucleotides contained in the decomposition products never exceeds 20%.
[0047] By the way, in order to obtain oligopeptide by hydrolyzing nucleoprotein, protease treatment must be performed, while in order to obtain oligonucleotide, nuclease treatment must be performed, but preferably, it is desirable to first treat with protease and then, treat with nuclease as a matter of operational convenience as well as from the viewpoint of the quality of final products obtained.
[0048] It is possible to use the decomposition product obtained by enzyme-decomposing or hydrolyzing nucleoprotein and/or DNA or the decomposition product obtained by enzyme-decomposing or hydrolyzing RNA as they are (without refining) for active ingredients of the compounding ingredients for basic cosmetics of the present invention. In the decomposition products, for example, amino acid, etc. may be contained.
[0049] In addition, it is possible to use the following compounds: deoxy oligonucleotide, deoxy mononucleotide, oligopeptide, oligonucleotide and mononucleotide, separated from nucleoprotein and/or DNA or RNA decomposition products by commonly-used separation means and/or refining means as active ingredients of the compounding ingredients for basic cosmetics of the present invention.
[0050] In such event, the strand length of deoxy oligonucleotide and oligo nucleotide contained in the nucleoprotein, DNA and RNA decomposition products or separated and refined by the use of commonly-used separation means and/or refining means from the decomposition products is preferably 2 to 12.
[0051] The decomposition products and the compounds may be used independently, or may be used by mixing at least two kinds of these decomposition products or compounds. In the event that the decomposition products and the compounds are mixed, the mixture ratio may be suitably selected.
[0052] In such event, it is particularly preferable that as the decomposition products and the compounds, at least any one of deoxy oligonucleotide or the olygonucleotide of strands 2 to 12 long is contained, and at the same time, a total of the deoxy oligonucleotide and the oligonucleotide of strands 2 to 12 long is 20% or more with respect to the grand total of the decomposition products and the compounds.
[0053] In addition, the decomposition products and the compounds may be used by further combining with commonly-used additive ingredients of the compounding ingredients for basic cosmetics at a predetermined ratio.
[0054] The concentration of active ingredients (the decomposition products and/or the compounds) in the compounding ingredients for basic cosmetics of the present invention may be suitably selected.
[0055] In addition, the basic cosmetics of the present invention contain the compounding ingredients for basic cosmetics.
[0056] The dosage form which the basic cosmetics according to the present invention can be suitably selected if it is a dosage form applicable to the skin. Preferably, basic cosmetics are desirable to be skin lotions, milky lotions, creams, gels, jellies, extracts, lip creams, facial masks, or massage masks.
[0057] The compounding ingredients for basic cosmetics according to the present invention may have publicly known ingredients which can be compounded to existing basic cosmetics in addition to the compounding ingredient for basic cosmetics. For example, perfumes, moisturizing agents, etc. may be compounded independently or in combination.
[0058] To the basic cosmetics of the present invention, as medication ingredients, Vitamin E or its derivatives, for example, Vitamin E acetate; vasodilator such as derivative of acetylcholine, etc.; skin function accelerating agent such as cepharanthine, etc.; glycyrrhetinic acid and its derivatives; female hormones such as estradiol, estrone, etc.; amino acids such as serine, methionine, arginine, etc.; Vitamin A, Vitamin B 1 , Vitamin B 6 , biotin, pantothenic acid or its derivatives, and other Vitamins may be compounded independently or in combinations.
[0059] Furthermore, to the basic cosmetics of the present invention, additives generally used for skin external preparations such as cosmetics, medicinal products, etc., for example, oil contents, antiseptics, surfactants, dispersion stabilizers, thickeners, moistening agents, ultraviolet absorbers, antioxidants, pH adjusters, purified water, alcohols, etc. may be compounded independently or in combinations.
EXAMPLE
[0060] In examples and comparisons shown as follows, the present invention will be described specifically and further in detail. The following examples are for explanation of the present invention only but the technological scope shall not be restricted by these examples.
[0061] The compounding amount in the following examples and comparisons shall be the percent in mass with respect to the total amount. In addition, the amount of prototype 1 through prototype 3 (containing decomposition products obtained by enzyme-decomposing DNA, DNA and nucleoprotein, or RNA, respectively) used in examples is shown as the amount of solid content.
1. Manufacture of (Deoxy) Oligonucleotide
[0062] For the salmon soft roe derived DNA, limited decomposition was performed using nuclease [for example, enzyme preparation nuclease “Amano” [available from Amano Enzyme (former Amano Pharmaceutical)], which is licensed as food additives. The produced deoxy mononucleotide and deoxy oligonucleotide were analyzed by an electrophoresis unit and optimum conditions were determined.
[0063] Specifically, to warm water adjusted to around 65° C., as material, DNA-Na salt powder was charged and stirred; then, the mixture was further heated to 70° C., nuclease was added in a suitable amount to a range from 0.05 to 0.25% with respect to the material and the mixture was allowed to react for 3 hours. Then, the mixture was heated at 85° C. for 10 minutes to deactivate nuclease and then centrifuged, and to the supernatant, a spray dry method was applied, and dry powder (decomposition products) containing deoxy oligonucleotide was obtained.
2. Analysis of (Deoxy) Oligonucleotide
[0064] To warm water adjusted to around 65° C., as material, DNA-Na salt powder derived from salmon soft roes was charged and stirred; then, the mixture was further heated to 70° C., enzyme preparation nuclease “Amano” [available from Amano Enzyme (former Amano Pharmaceutical)] was added 0.05% with respect to the material and the mixture was allowed to react for 3 hours and the decomposition product was obtained. Then, the mixture was heated at 85° C. for 10 minutes to deactivate nuclease and then the decomposition product was analyzed by HPLC.
[0065] FIG. 1 shows an analysis example of decomposition product deoxy oligonucleotide by HPLC (high-performance liquid chromatography). In FIG. 1 , 5′-deoxy mononucleotide and 3′-deoxy mononucleotide were eluted to peak 20, and the subsequent comparatively large peaks, that is, peaks after peak 26 can be regarded as absorption of deoxy oligonucleotide. In addition, peaks after peak 41 can be regarded as absorption of decomposition products whose molecular weight exceeds 3000. Consequently, as a result of computation from peak strengths of peak 26 through peak 41, it was clarified that in the present example, fractions of 31% deoxy oligonucleotide (molecular weight: 1000-3000) were contained with respect to the whole decomposition product.
3. Manufacture of Basic Cosmetics Using (Deoxy) Oligonucleotide
[0066] As prototype 1 designated as dry powder (decomposition product) containing deoxy oligonucleotide obtained by the manufacturing method, using this prototype 1, the basic cosmetics of the present invention were manufactured as follows. For control, basic cosmetics which do not contain prototype 1 were manufactured. Table 1 summarizes these compositions.
Example 1
[0067] Purified water was added to 95% ethanol, and to this, polyoxy ethylene (25 mole), hardened castor oil ether, glycerin, and propylene glycol were added and stirred; then, prototype 1 was added and stirred to dissolve, and transparent liquid-form basic cosmetics of Example 1 was obtained.
[Comparison 1]
[0068] Using the same amount of glycerin in place of prototype 1, basic cosmetics of Comparison 1 was obtained by the manufacturing method same as that of Example 1.
4. Blood Flow Volume Measuring Test
[0069] The basic cosmetics of Example 1 and the basic cosmetics of Comparison 1 were applied to the human upper arm at a rate of 10 μL, respectively, and 1 hour after the application, the blood flow volume was measured by the laser Doppler blood flow meter. The judgment of test results was performed in accordance with the following judgment criteria:
++: The blood flow volume markedly increased as compared to Comparison (marked effect) +: The blood flow volume increased as compared to Comparison (effective) +/−: The blood flow volume slightly increased as compared to Comparison (slightly effective) −: The blood flow volume was equivalent to or less than
Comparison (Ineffective)
[0074] The results are summarized in Table 1 below.
5. Improvement Test on Chapping of the Skin
[0075] With 10 middle-aged and older women who had chapping of the skin in legs designated as subjects, basic cosmetics of Example 1 and basic cosmetics of Comparison 1 were applied at about 1 g/once/day after taking bath at different places of right and left legs, respectively.
[0076] Based on the skin condition of the applied portions before the test and after 1 month, using the following judgment criteria, the test results were judged from the viewpoints of the skin peeling condition and moisture condition.
5-1 Judgment Criteria of Skin Peeling and Judgment of Efficacy
[0077] The skin peeling conditions before and after the test were judged by the following judgment criteria:
[0078] 0: No peeling; 1: Minor peeling; 2: Medium peeling; 3: Major peeling.
[0079] By the above judgment, the skin condition judgment improved by one stage from the condition before the test was designated as “slightly effective,” and the skin condition judgment improved by two stages or more as “effective,” and the skin condition on the same level or aggravated as “ineffective.”
5-2 Judgment Criteria of the Moisture Condition
[0080] The moisture condition of the skin after one month (moisture retention capacity) was measured by a moisture meter and judgment was made in accordance with the following criteria:
<Judgment Criteria of Moisture Condition>
[0000]
++: The moisture retention capacity of the applied portion increased 5% or more before the test (marked effect)
+: The moisture retention capacity of the applied portion increased 2-5% before the test (effective)
+/−: The moisture retention capacity of the applied portion increased 0-2% before the test (slightly effective)
−: The moisture retention capacity of the applied portion was equivalent to or less than that before test (ineffective)
[0085] The results are summarized in Table 1 below.
6. Evaluation Test
[0086] With middle-aged and older women as subjects, by the single blind study, the evaluation test was conducted on the basic cosmetics of Example 1 and the basis cosmetics of Comparison 1. By the way, 10 subjects were selected for each cosmetics. The evaluation was made by delivering questionnaires to subjects and answers were received on 5 items of “smoothness,” “fine texture,” “whitening condition,” “elasticity of the skin,” and “improved blotches and freckles” before the use and one month after the use. Based on the answers obtained, the test results were judged in accordance with the following judgment criteria:
++: Improved as compared to the condition before use (marked effect) +: Slightly improved as compared to the condition before use (effective) +/−: The condition was equivalent to or less than that before test (ineffective)
[0090] The results are summarized in Table 1 below.
[0000]
TABLE 1
Composition and evaluation test results of basic
cosmetics of Example 1 and Comparison I
Compounded ingredients
Example 1
Comparison 1
Prototype 1 (DNA salt
2.0
—
decomposition products)
Concentrated glycerin
2.0
4.0
Polyoxyethylene (25 mol)
2.0
2.0
hardened castor oil ether
Propylene glycol
5.0
5.0
95% ethyl alcohol
1.0
1.0
Purified water
Remainder
Remainder
Blood flow volume measuring
++
(Criteria)
test
Improved
Skin peeling
Effective
9
persons
0
person
chapping
Slightly
1
person
3
persons
of the skin
effective
Ineffective
0
person
7
persons
Moisture retention
++
±~−
capacity
Evaluation
Smoothness
++
8
persons
0
person
test by
+
2
persons
3
persons
trial use
±
0
person
7
persons
Fine texture
++
7
persons
0
person
+
3
persons
2
persons
±
0
person
8
persons
Whitening
++
2
persons
0
person
condition
+
5
persons
0
person
±
3
persons
10
persons
Elasticity of
++
8
persons
0
person
the skin
+
2
persons
1
person
±
0
person
9
persons
Improved
++
1
person
0
person
blotches and
+
3
persons
0
person
freckles
±
6
persons
10
persons
7. Manufacture and Analysis of DNA and Nucleoprotein Decomposition Products (Prototype 2) or RNA Decomposition Products (Prototype 3)
[0091] Products which contain as active ingredients the decomposition products obtained by enzyme-decomposing DNA and nucleoprotein manufactured by Nissei Bio Co., Ltd. were designated as prototype 2 (those containing deoxy oligonucleotide, deoxy mononucleotide and oligopeptide) and products which contain as active ingredients the decomposition products obtained by enzyme-decomposing RNA manufactured by Nissei Bio Co., Ltd. were designated as prototype 3 (those containing oligonucleotide and mononucleotide).
[0092] The manufacturing method and analysis results of prototype 2 and prototype 3 are shown as follows:
7-1 Manufacturing Method and Analysis of Prototype 2 (DNA and Nucleoprotein Decomposition Products
[0093] Prototype 2 was obtained by mixing the decomposition product obtained by depolymerizing DNA by enzyme decomposition treatment with the decomposition product obtained by depolymerizing nucleoprotein by enzyme decomposition treatment in an equal amount. The detail of the manufacturing method of each decomposition product is shown as follows:
<DNA Decomposition Products>
[Manufacturing Method]
[0094] Manufacture was carried out by the method same as that of “1. Manufacture of (deoxy) olygonucleotide” mentioned above and DNA decomposition product was obtained.
[Construction and Composition]
[0095] Analysis was performed by the method same as that of “2. Analysis of (deoxy) olygonucleotide” mentioned above and it was found out that fractions of 31% deoxy olygonucleotide (molecular weight: 1000-3000) were contained with respect to the whole decomposition product.
<Nucleoprotein Decomposition Products>
[Manufacturing Method]
[0096] To water, the nucleoprotein derived salmon soft roes (available from Nissei Bio Co., Ltd.), was charged and heated and stirred at 50° C.; then, enzyme preparation protease “PTN” (available from Novozymes Japan) was added 0.065% and allowed to react for 4 hours; the mixture was further heated at 70° C. and stirred. Then, enzyme preparation nuclease “Amano” (available from Amano Enzyme) 0.1% and allowed to react for 3 hours. Then, the mixture was heated at 85° C. for 10 minutes to deactivate nuclease and then centrifuged, and by applying the spray dry method, dry powder (decomposition products) containing deoxy oligonucleotide was obtained.
[Construction and Composition]
[0097] The above-mentioned decomposition products obtained were analyzed by HPLC.
[0098] FIG. 2 shows an analysis example of deoxy olygonucleotide of decomposition products by HPLC (high-performance liquid chromatography). In FIG. 2 , peaks (peak 1 through peak 4) within holding time from 19 minutes to 24 minutes can be regarded as absorption of oligonucleotide. Consequently, as a result of computing from the peak strength of peak 1 through peak 4, in the present example, it was found out that fractions of 33.4% deoxy oligonucleotide (molecular weight: 1000-3000) were contained with respect to the whole decomposition products.
7-2. Manufacturing Method and Analysis of Prototype 3 (RNA Decomposition Products)
[0099] Prototype 3 is the decomposition products obtained by depolymerizing RNA in place of material DNA by enzyme decomposition treatment by the manufacturing method as is the case with prototype 1, and the detail is shown as follows.
<RNA Decomposition Products>
[Manufacturing Method]
[0100] To warm water adjusted to around 70° C., as material, RNA derived from enzyme (available from Nissei Bio Co., Ltd.) was charged and stirred; then, the mixture was further heated to 70° C., enzyme preparation nuclease “Amano” (available from Amano Enzyme) was added 0.05% with respect to the material and the mixture was allowed to react for 3 hours. Then, the mixture was heated at 85° C. for 10 minutes to deactivate nuclease and then centrifuged, and by applying the spray dry method, dry powder (decomposition products) containing oligonucleotide was obtained.
[Construction and Composition]
[0101] The above-mentioned decomposition products obtained were analyzed by HPLC.
[0102] FIG. 3 shows an analysis example of olygonucleotide of decomposition products by HPLC (high-performance liquid chromatography). In FIG. 3 , peaks (peak 2 through peak 5) within holding time from 13 minutes to 24 minutes can be regarded as absorption of oligonucleotide. Consequently, as a result of computing from the peak strength of peak 2 through peak 5, in the present example, it was found out that fractions of 41.1% oligonucleotide (molecular weight: 1000-3000) were contained with respect to the whole decomposition products.
8. Manufacture of Various Basic Cosmetics
[0103] Using prototype 2 (DNA and nucleoprotein decomposition products) and prototype 3 (RNA decomposition products) obtained by the above-mentioned methods, basic cosmetics of the present invention were manufactured as follows. In addition, as controls, basic cosmetics of Comparison which did not contain any prototype 2 and prototype 3 were manufactured. Tables 2 through 5 summarize the compositions of these cosmetics.
[0104] By the way, suppliers of the products used for the following basic cosmetics are shown in parentheses.
8-1 Gel-Form Basic Cosmetics
Example 2
Examples 2-1 Through 2-3
[0105] To purified water, Pemulen TR-1 (Nikko Chemicals Co., Ltd.) was gradually added with stirring and thoroughly dispersed, and then, Ultrez-10 (Nikko Chemicals) was stirred and dispersed, to which concentrated glycerin was added to obtain a gel base material. Separately, Lecinol WS-50 (Nikko Chemicals), jojoba oil, squalene, LIALCARB SR-1000 (Nikko Chemicals), AMITER MA-HD (Nihon-Emulsion Co., Ltd.) and rose hip oil were heated, dissolved, and mixed to have an oil-based ingredient. Furthermore, separately, Ceralipid W-2 (Nikko Chemicals), 1,3-butylene glycol (BG), dipropylene glycol (DpG) and 2-phenoxyethanol were added to superheat, stir, and mix (held at 300 rpm and 80° C. for 5 minutes), and purified water was added and thoroughly stirred; then, the oil-based ingredient was combined and thoroughly mixed to obtain a compounded ingredient stock solution.
[0106] The gel base material and the compounded ingredient stock solution were mixed, to which ethanol was added; then, 18% sodium hydroxide was added to neutralize, stir, and mix. To this, prototype 2 and prototype 3, and an equivalent mixture of prototype 2 and prototype 3 (prototype 4), each mixed with purified water, were dissolved, respectively, and basic cosmetics of Example 2-1, Example 2-2, and Example 2-3 were obtained.
Comparison 2:
[0107] Basic cosmetics of Comparison 2 was obtained in the method same as Example 2-1, Example 2-2, and Example 2-3 except for adding concentrated glycerin 2 mass % more to add a total of 7 mass % in place of prototype 2 and prototype 3.
8-2. Emulsified Basic Cosmetics
Example 3
Example 3-1 Through 3-3
[0108] To purified water, concentrated glycerin was added and the mixture was heated to 70° C. and adjusted. Separately, to cetyl alcohol, beeswax, Vaseline, squalene, and dimethylpolysiloxane, monooleic acid ester, and glycerol monostearic acid ester were added and heated to 70° C. This was added to the water phase prepared in advance and preliminary emulsification was performed. Further, quince seed extract solution and ethanol were added and stirred, and the emulsified particles were homogenized by homomixer.
[0109] When this emulsified liquid reached 40° C., prototype 2 and prototype 3, and equivalent mixture of prototype 2 and prototype 3 (prototype 4), each mixed with purified water, were dissolved, respectively, further stirred, deaerated, filtered, and cooled, and emulsified basic cosmetics of Example 3-1, Example 3-2, and Example 3-3 were obtained.
Comparison 3:
[0110] Basic cosmetics of Comparison 3 was obtained in the method same as Example 3-1, Example 3-2, and Example 3-3 except for adding concentrated glycerin 2 mass % more to add a total of 10 mass % in place of prototype 2 and prototype 3.
8-3. Lotion-Form Basic Cosmetics (Skin Lotions)
Example 4
Examples 4-1 Through 4-3
[0111] In purified water, 1, 3-butylene glycol, concentrated glycerin, buffering agent, and brown inhibitor were dissolved at room temperature. In addition, in ethanol, prototype 2 and prototype 3, and equivalent mixture of prototype 2 and prototype 3 (prototype 4), each mixed with oleyl alcohol, sorbitan monolaurate acid ester and purified water, were dissolved, respectively. These were mixed and stirred, and lotion-form basic cosmetics of Example 4-1, Example 4-2, and Example 4-3 were obtained.
Comparison 4:
[0112] Lotion-form basic cosmetics of Comparison 4 was obtained in the method same as Example 4-1, Example 4-2, and Example 4-3 except for adding concentrated glycerin 2 mass % more to add a total of 6 mass % in place of prototype 2 and prototype 3.
8-4. Cream-Form Basic Cosmetics
Example 5
Examples 5-1 Through 5-3
[0113] In purified water, 1, 3-butylene glycol, pentylene glycol, concentrated glycerin, and polyquaternium were successively dissolve, and heated to 80° C. to have a water phase. On the other hand, polyglyceryl stearate, stearyl alcohol, behenyl alcohol, batyl alcohol, cetyl palmitate, glyceryl stearate, Crodaran SWL (Croda Japan KK), isopropyl palmitate, squalene, octyldodecyl myristate, macadamia nut oil, Trioctanoin, and dimethicone were mixed, and heated and stirred at 85° C. to have an oil phase. To the water phase, the oil phase was injected and stirred (300 rpm), and was emulsified by homomixer for high viscosity (4000 rpm). When this emulsified substance reaches 40° C., to purified water, prototype 2, prototype 3, and equivalent mixture of prototype 2 and prototype 3 (prototype 4), each mixed with sodium hydroxide, sodium citrate, and purified water, were dissolved, mixed and stirred, and cream-form basic cosmetics of Example 5-1, Example 5-2, and Example 5-3 were obtained.
Comparison 5:
[0114] Cream-form basic cosmetics of Comparison 5 was obtained in the method same as Example 5-1, Example 5-2, and Example 5-3 except for adding concentrated glycerin 2 mass % more to add a total of 7 mass % in place of prototype 2 and prototype 3.
9. Performance Test of Basic Cosmetics (Gels, Milky Lotions, Skin Lotions, and Creams)
[0115] For basic cosmetics of Example 2 through Example 5 and Comparison 2 through Comparison 5, the above-mentioned blood flow volume measuring test, improvement test on chapping of the skin, and evaluation test by trial use were performed, respectively, under the same conditions of Example 1 and Comparison 1.
[0116] Table 2 through Table 5 summarize the results.
[0000]
TABLE 2
Composition and evaluation test results of gel-form
basic cosmetics of Example 2 and Comparison 2
Compounded ingredients
Example 2-1
Example 2-2
Example 2-3
Comparison 2
Prototype 2
2.0
None
1.0
None
Prototype 3
None
2.0
1.0
None
Concentrated glycerin
5.0
5.0
5.0
7.0
Ultrez-10
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Lecinol WS-50
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Pemulen TR-1
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
1,3-butylene glycol (BG)
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Dipropylene glycol (DpG)
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
18% sodium hydroxide
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Squalene
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
LIALCARB
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Jojoba oil
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Ceralipid W-2
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
AMITER MA-HD
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Rose hip oil
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Purified water
Remainder
Remainder
Remainder
Remainder
Blood flow volume measuring
++
++
++
(Standard)
test
Improved
Skin peeling
Effective
9
persons
5
persons
6
persons
0
person
chapping of
Slightly
1
person
3
persons
3
persons
2
persons
the skin
effective
Ineffective
0
person
2
persons
1
person
8
persons
Moisture retention
++
++
++
±~−
capacity
Evaluation
Smoothness
++
8
persons
6
persons
7
persons
0
person
test by
+
2
persons
2
persons
2
persons
2
persons
trial use
±
0
person
2
persons
1
person
8
persons
Fine
++
7
persons
3
persons
3
persons
0
person
texture
+
1
person
5
persons
5
persons
1
person
±
2
persons
2
persons
2
persons
9
persons
Whitening
++
2
persons
0
person
2
persons
0
person
condition
+
5
persons
1
person
5
persons
0
person
±
3
persons
9
persons
3
persons
10
persons
Elasticity
++
8
persons
6
persons
6
persons
0
person
of the skin
+
2
persons
2
persons
3
persons
1
person
±
0
person
2
persons
1
person
9
persons
Improved
++
1
person
0
person
1
person
0
person
blotches
+
4
persons
2
persons
3
persons
0
person
and
±
5
persons
8
persons
6
persons
10
persons
freckles
[0000]
TABLE 3
Composition and evaluation test results of emulsified
basic cosmetics of Example 3 and Comparison 3
Compounded ingredients
Example 3-1
Example 3-2
Example 3-3
Comparison 3
Prototype 2
2.0
None
1.0
None
Prototype 3
None
2.0
1.0
None
Concentrated glycerin
8.0
8.0
8.0
10.0
Cetyl alcohol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Beeswax
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Vaseline
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Dimethylpolysiloxane
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Ethanol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Squalene
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Monooleic ester
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Glycerol monostearic acid
Appropriate
Appropriate
Appropriate
Appropriate
ester
amount
amount
amount
amount
Quince seed extract solution
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Purified water
Remainder
Remainder
Remainder
Remainder
Blood flow volume measuring
++
++
++
(Standard)
test
Improved
Skin
Effective
9
persons
5
persons
6
persons
0
person
chapping of
peeling
Slightly
1
person
3
persons
2
persons
3
persons
the skin
effective
Ineffective
0
person
2
persons
2
persons
7
persons
Moisture retention
++
++
++
±~−
capacity
Evaluation
Smoothness
++
8
persons
6
persons
6
persons
0
person
test by
+
2
persons
3
persons
4
persons
3
persons
trial use
±
0
person
1
person
0
person
7
persons
Fine
++
7
persons
3
persons
4
persons
0
person
texture
+
3
persons
4
persons
4
persons
2
persons
±
0
person
3
persons
2
persons
8
persons
Whitening
++
2
persons
1
person
1
person
0
person
condition
+
5
persons
3
persons
6
persons
0
person
±
3
persons
6
persons
3
persons
10
persons
Elasticity
++
8
persons
5
persons
8
persons
0
person
of the skin
+
2
persons
3
persons
2
persons
1
person
±
0
person
2
persons
0
person
9
persons
Improved
++
1
person
0
person
0
person
0
person
blotches
+
3
persons
2
persons
3
persons
0
person
and
±
6
persons
8
persons
7
persons
10
persons
freckles
[0000]
TABLE 4
Composition and evaluation test results of lotion-form
basic cosmetics of Example 4 and Comparison 4
Compounded ingredients
Example 4-1
Example 4-2
Example 4-3
Comparison 4
Prototype 2
2.0
None
1.0
None
Prototype 3
None
2.0
1.0
None
Concentrated glycerin
4.0
4.0
4.0
6.0
1,3-butylene glycol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Buffering agent
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Brown inhibitor
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Ethanol
10.0
10.0
10.0
10.0
Oleyl alcohol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Sorbitan monolaurate acid
Appropriate
Appropriate
Appropriate
Appropriate
ester
amount
amount
amount
amount
Purified water
Remainder
Remainder
Remainder
Remainder
Blood flow volume measuring
++
++
++
(Standard)
test
Improved
Skin peeling
Effective
10
persons
6
persons
7
persons
0
persons
chapping of
Slightly
0
persons
3
persons
3
persons
4
persons
the skin
effective
Ineffective
0
persons
1
persons
0
persons
6
persons
Moisture retention
++
++
++
±~−
capacity
Evaluation
Smoothness
++
6
persons
4
persons
6
persons
0
person
test by
+
3
persons
4
persons
2
persons
2
persons
trial use
±
1
person
2
persons
2
persons
8
persons
Fine
++
8
persons
4
persons
7
persons
0
person
texture
+
2
persons
3
persons
2
persons
3
persons
±
0
person
3
persons
1
person
7
persons
Whitening
++
3
persons
1
person
2
persons
0
person
condition
+
5
persons
4
persons
6
persons
2
persons
±
2
persons
5
persons
2
persons
8
persons
Elasticity
++
6
persons
2
persons
6
persons
0
person
of the skin
+
3
persons
4
persons
1
person
0
person
±
1
person
4
persons
3
persons
10
persons
Improved
++
3
persons
1
person
3
persons
0
person
blotches
+
3
persons
1
person
3
persons
0
person
and
±
4
persons
8
persons
4
persons
10
persons
freckles
[0000]
TABLE 5
Composition and evaluation test results of cream-form
basic cosmetics of Example 5 and Comparison 5
Compounded ingredients
Example 5-1
Example 5-2
Example 5-3
Comparison 5
Prototype 2
2.0
None
1.0
None
Prototype 3
None
2.0
1.0
None
Concentrated glycerin
5.0
5.0
5.0
7.0
1,3-butylene glycol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Pentylene glycol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Polyquaternium
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Polyglyceryl stearate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Stearyl alcohol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Behenyl alcohol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Batyl alcohol
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Cetyl palmitate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Glyceryl stearate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Crodaran SWL
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Isopropyl palmitate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Squalene
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Octyldodecyl myristate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Macadamia nut oil
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Trioctanoin
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Dimethicone
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Sodium hydroxide
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Sodium citrate
Appropriate
Appropriate
Appropriate
Appropriate
amount
amount
amount
amount
Purified water
Remainder
Remainder
Remainder
Remainder
Blood flow volume measuring
++
++
++
(Standard)
test
Improved
Skin
Effective
10
persons
7
persons
8
persons
0
person
chapping of
peeling
Slightly
0
person
2
persons
2
persons
3
persons
the skin
effective
Ineffective
0
person
1
person
0
person
7
persons
Moisture retention
++
++
++
±~−
capacity
Evaluation
Smoothness
++
10
persons
6
persons
7
persons
5
persons
test by
+
0
person
4
persons
3
persons
3
persons
trial use
±
0
person
0
person
0
person
2
persons
Fine
++
9
persons
8
persons
8
persons
4
persons
texture
+
1
person
2
persons
2
persons
4
persons
±
0
person
0
person
0
person
2
persons
Whitening
++
5
persons
2
persons
4
persons
0
person
condition
+
3
persons
4
persons
4
persons
3
persons
±
2
persons
4
persons
2
persons
7
persons
Elasticity
++
10
persons
4
persons
6
persons
0
person
of the skin
+
0
person
4
persons
3
persons
0
person
±
0
person
2
persons
1
person
10
persons
Improved
++
5
persons
1
person
3
persons
0
person
blotches
+
5
persons
3
persons
2
persons
0
person
and
±
0
person
6
persons
5
persons
10
persons
freckles
[0117] Based on the results shown in Table 1 and Table 2 though Table 5, the following were found out.
[0118] (1) The evaluations of blood flow volume measuring tests of Example 1 or Example 2 through Example 5 were ++ [the blood flow volume markedly increased as compared to Comparison (marked effect)] and it is apparent that the active ingredients of cosmetics of Example 1 through Example 5 penetrate from human skin and markedly increase the blood flow volume.
[0119] (2) In the improvement test on chapping of the skin of cosmetics of Example 1 or Example 2 through Example 5, cosmetics which contain Prototype 1, Prototype 2 and Prototype 4 that contains Prototype 2 exhibited marked efficacy, and the efficacy was confirmed with cosmetics which contain Prototype 3, too. By the way, for the left legs to which no skin care product was applied as controls, improvement of chapping of the skin was scarcely recognized, proving the efficacy of cosmetics which contain Prototype 1 through Prototype 4.
[0120] (3) In the test results shown in Table 1, the evaluation test by trial use of cosmetics by the cosmetics which contain Prototype 1 (DNA decomposition products) produced evaluation results in which marked improvement effects were recognized particularly in “smoothness,” “fine texture,” and “skin elasticity.”
[0121] (4) In comparison of test results in the same cosmetics shown in Table 2 through Table 5, in the evaluation test by trial use of cosmetics containing Prototype 2 through Prototype 4 proved their superiority in any of skin care product forms in order of Prototype 2>Prototype 4>Prototype 3>Comparison. In the cosmetics which contain Prototype 2 trough Prototype 4, marked important effects were recognized particularly in “smoothness” “fine texture” and “skin elasticity”.
[0122] (5) On the other hand, in the evaluation test by trial use in Example 1 or Example 2 though Example 5, “whitening effects” and “improved blotches and freckles” were recognized with part of subjects, but with the skin metabolism, etc. taken into account, a slightly longer use would be required.
[0123] By the way, in Example 1 through Example 5, for active ingredients, prototype 1 (DNA salt decomposition products), prototype 2 (DNA and nucleoprotein decomposition products), prototype 3 (RNA decomposition products), and prototype 4 (mixture of prototype 2 and prototype 3) were used, but even when deoxy oligonucleotide, deoxy mononucleotide, oligopeptide, oligonucleotide, or mononucleotide separated from them and refined were used independently or in combination in place of prototype 1 through prototype 4, the effects were identified in the manner same as that in which prototype 1 through prototype 4 were used.
[0124] That is, based on the present embodiment, it has been determined that compounding ingredients for basic cosmetics which contain deoxy oligonucleotide, deoxy mononucleotide, oligopeptide, oligonucleotide or mononucleotide as well as basic cosmetics that contain the compounding ingredients of basic cosmetics have effects of increasing the blood flow volume, effects of improving chapping of the skin, as well as effects of improving smoothness of the skin, fine texture, and skin elasticity.
[0125] The formulation examples of basic cosmetics using Prototype 1 through Prototype 4 are shown as Example 6 through Example 8 as follows. By the way, the “prototype(s)” stipulated in these examples should mean any of the prototypes selected from Prototype 1 through Prototype 3, independently, respectively, and the equivalent mixture of Prototype 2 and Prototype 3 (Prototype 4).
[0126] In any of the examples, it was identified that the examples have effects of increased blood flow volume and effects of improving chapping of the skin, as well as effects of improving skin smoothness, fine texture, and skin elasticity.
Example 6
Lip Cream
[0127]
[0000]
TABLE 6
Formulation of lip cream
Blending quantity
Compounded ingredients
(mass %)
Solid paraffin
10.0
Caster oil
20.4
Lanolin
14.0
Beeswax
5.0
Candelilla wax
12.0
Carnauba wax
7.0
2-cetyl ethylhexanoate
18.0
Isopropyl myristate
12.0
Prototype(s)
1.5
Perfume
0.1
<Manufacturing Method>
[0128] Of the above-mentioned compounded ingredients, ingredients other than perfume were mixed and dissolved; then, perfume was added, stirred, and mixed. The mixture was injected in a mold and cooled to prepare lip cream.
Example 7
Cold Cream
[0129]
[0000]
TABLE 7
Formulation of cold cream
Blending quantity
Compounded ingredients
(mass %)
Solid paraffin
5.0
Beeswax
10.0
Vaseline
15.0
Liquid paraffin
41.0
Glyceryl monostearate
2.0
Polyoxyethylene (20 mol) sorbitan
2.0
monolaurate
Prototype(s)
1.0
Soap powder
0.1
Perfume
Appropriate
quantity
Antiseptics
Appropriate
quantity
Antioxidan
Appropriate
quantity
Purified water
Remainder
<Manufacturing Method>
[0130] To purified water, prototype(s) and soap powder were added, heated and dissolved, and kept to 70° C. (water phase). Other ingredients were mixed, heated, and dissolved, and kept to 70° C. (oil phase). Oil phase was gradually added to water phase with stirring, and after completing the addition, the mixture was homogeneously emulsified by homomixer, and after emulsification, the mixture was cooled to 30° C. with good stirring, and cold cream was prepared.
Example 8
Clay Facial Mask
[0131]
[0000]
TABLE 8
Formulation of clay facial mask
Blending quantity
Compounded ingredients
(mass %)
Prototype(s)
1.0
Kaolin
25.0
Ethanol
5.0
1,3-butylene glycol
10.0
Glycerin
5.0
PEG-20 methyl glucose sesquistearate
4.0
Xanthan gum
0.1
Antiseptics
Appropriate quantity
Purified water
Remainder
<Manufacturing Method>
[0132] 1,3-butylene glycol, glycerin, PEG-20 methyl glucose sesquistearate, xanthan gum, antiseptics, and purified water were added and stirred to homogenize the whole.
[0133] While this is being stirred by homomixer, prototype(s) and kaolin were added, and the whole was homogenized, and further ethanol was added, stirred, and mixed, and clay facial masks were prepared. | The present invention relates to a compounding ingredients for basic cosmetics and basic cosmetics containing the compounding ingredients which contain enzymes or hydrolysis products of nucleoprotein and/or DNA or RNA, or deoxy oligonucleotide, deoxy mononucleotide, oligopeptide, oligonucleotide mononucleotide separated from the hydrolysis products, or at least two kinds of mixtures selected from the hydrolysis products or compounds as active ingredients. Because the active ingredients such as deoxy oligonucleotide and others have comparatively small molecular weights, they are easy to be absorbed percutaneously, and when they are percutaneously absorbed, they exhibit cellular stimulating effects and blood circulation promoting effects, and therefore, in the event that they are applied to the facial skin, they marvelously prevent skin roughness, blotches, freckles, wrinkles, etc. and exhibit superb skin-lightening effects. | 0 |
CROSS-REFERENCES TO RELATED APPLICATIONS
none.
REFERENCE TO MICROFICHE APPENDIX
not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
not applicable.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates generally to apparatus for straightening coil stock, and then feeding the straightened coil stock to a using station.
More particularly, the invention relates to apparatus provided with both straightening and feed rolls that are adapted to simultaneously engage the coil stock during material demand by the using station, and to simultaneously release the coil stock in the absence of material demand from the using station, and which, while suitable for other uses, is particularly useful in intermittently feeding coil stock to a punch press for ease of final positioning of the stock in the press.
2. Description of Prior Art
A conventional punch press line adapted to punch parts from coiled strip stock includes a reel that holds the coiled stock, a stock straightening mechanism that straightens the stock as it is drawn off the reel, and a feed mechanism that draws the stock from the straightener and feeds the straightened stock to the punch press.
A conventional coil stock feed mechanism includes a set of power-rotated feed rollers between which the strip stock is gripped, to pull the stock from the straightener and feed the stock to the punch press. For use with a punch press, the feed rolls are operative to alternately advance the stock in a selected length increment to the press, and then release the stock during the each punch cycle of the press.
A conventional coil stock straightening mechanism includes two sets of rollers between which the stock travels in a wave such that the stock cyclically flexes in alternating directions as it travels therethrough.
Precision stamping of strip stock requires the stock to be precisely positioned in the punch press during each punch cycle. This precision positioning is typically accomplished by punching a pilot hole in the stock at a first station, and actuating a tapered pilot pin at a second station through a pilot hole that was punched at the first station during a preceding press cycle for final positioning of the stock at the second station prior to punching of the desired part. During each cycle, the stock is feed into the punch press approximately one to two thousandths (0.001-0.002) inch short of the desired position by the feed mechanism, the feed mechanism releases the stock, and the tapered pilot pin draws the stock the additional 0.001-0.002 inch into the desired final position. After the desired part has been punched, the pilot pin is withdrawn, and the feed mechanism re-engages the stock to feed stock for the next cycle. Thus, operation of the feed mechanism is controlled in cyclic synchronization with the pilot pin operation of the punch press, or some other type of position control associated with the cyclic operation of the press.
Traditionally, the straightener and feed mechanisms are provided in separate units, with a loop of the coil stock therebetween. This loop of stock accommodates the difference in feed characteristics of the continuously acting straightener and the intermittently pulling feed mechanism. One such conventional arrangement is generally shown in Waddington U.S. Pat. No. 5,150,022.
In certain instances, the straightener and feed mechanisms have been combined into a single unit. This provides advantages including the elimination of the loop of material and an associated reduction of floor space requirements. The combined unit also simplifies set-up and control of the entire straightening and feeding process because the straightened material moves directly from the straightening rolls into the feed rolls and then into the die area of the punch press.
However, prior combined roll-type straightener and feed mechanisms present certain difficulties as regards the final positioning of the stock in the punch press. With the elimination of the loop of material, the integrated straightening mechanism resists movement of the stock into its final position as a result of the continuous tension applied to the stock by the straightener rolls. As a result, the pilot mechanism in the punch press must be adapted to overcome this tension as it pulls the stock into final position. Consequently, presses set-up for use with a combined straightener and feed mechanism typically experience wear of the pilot pin at an increased rate distortion of the material being fed, and are subject to loss in final positioning accuracy at a faster rate as compared with presses that are fed by a conventional feed mechanism that is separated from the straightening mechanism. Another drawback of prior combined straightening and feed mechanisms is that they are subject to loss in roll position and overall feed length accuracy.
Thus, it is apparent that there is a need for a combined straightening and feed mechanism that provides the benefits, but eliminates the above-identified disadvantages associated with prior combined straightening and feed mechanisms.
SUMMARY OF THE INVENTION
The general aim of the present invention is to provide new and improved combined feed and straightening apparatus adapted to feed precisely controlled length increments of coiled strip stock to a punch press in synchronization with the final positioning control system of the press, and which eliminates the continuously acting straightening roller tension on the stock of prior apparatus of the same general type.
A detailed objective is to achieve the foregoing by providing feed rollers and straightening rollers that simultaneously engage the strip material for straightening and advancing a length of stock to the punch press during a material demand cycle, and that simultaneously release the material at the end of each material demand cycle for final positioning in the press.
These and other objectives and advantages of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
Briefly, a combined coil stock feed and straightening device includes a pair of feed rollers located on opposite sides of a feed path along which the strip stock is guided, and two sets of straightening rollers upstream of the feed rollers on opposite sides of the feed path.
Incremental movement of the coil stock through the device is accomplished by power rotating the feed rollers while the strip material is clamped therebetween, and stopping and separating the feed rollers to stop further powered movement of the strip material during operation of the punch press. The straightening rollers are adapted to separate from the coil stock simultaneously with the feed rollers for ease of final positioning of the stock in the press.
In preferred embodiments, one of the feed rollers is rotated on a fixed axis in relation to the feed path, and the other feed roller is moveable toward and away from the fixed feed roller between a material gripping position and a material release position. Similarly, one of the sets of straightening rollers rotate on fixed axes in relation to the feed path, and the other set is movable toward and away from the fixed set for movement between a material engaging-straightening position and a material release position.
A pair of operators, responsive to fluidic control signals, effect synchronized movement of the movable feed roller and the movable set of straightening rollers between said positions, and associated pilot release valves are operable to supply the fluidic control signals in response to material demand signals from the punch press.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a left side cross-sectional view taken substantially through the center of a combined coil stock straightening and feed apparatus incorporating the unique aspects of the present invention, the apparatus being shown in its material gripping condition, for straightening and feeding coil stock to a using station.
FIG. 2 is a view similar to FIG. 1, but with the apparatus shown in its material release condition.
FIG. 3 is a top view taken substantially along the line 3 — 3 of FIG. 6 .
FIG. 4 is a top view taken substantially along the line 4 — 4 of FIG. 6, with certain parts broken away and shown in cross-section, and with the apparatus shown in its material gripping condition.
FIG. 5 is a top view with certain parts broken away and shown in cross-section, and with the apparatus shown in its material release condition.
FIG. 6 is a left side view showing certain gear-drive and other internal components in dashed lines.
FIG. 7 is a right side view taken substantially along the line 7 — 7 of FIG. 3, with the apparatus shown in its material gripping condition.
FIG. 8 is a view similar to FIG. 7, but with the apparatus shown in its material release condition.
FIG. 9 is a view taken substantially along the line 9 — 9 of FIG. 3 .
FIG. 10 is a downstream end view, with certain parts broken away and shown in cross-section.
FIG. 11 is a schematic representation of certain fluidic and electrical components of the apparatus of FIG. 1 and showing said components in a material-feed condition.
FIG. 12 is a schematic representation similar to FIG. 11 but showing said components in a material-release condition.
While the invention is susceptible of various modifications and alternative constructions, a certain illustrated embodiment has been shown in the drawings and will be described below in detail. It should be understood, however, that there is no intention to limit the invention to the specific form disclosed, but on the contrary, the intention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention.
Reference numerals shown in the drawings correspond to the following items:
10 —combined straightening and feed device
12 —upstream end of device 10
14 —downstream end of device 10
16 —strip stock
18 —lower drive feed roller
18 a —bearings supporting lower drive feed roller
18 b —rotational axis of lower drive feed roller
20 —upper pinch feed roller
20 a —bearings supporting upper drive feed roller
20 b —rotational axis of upper drive feed roller in material gripping condition
20 b ′—rotational axis of upper drive feed roller in material release condition
22 —rotary drive unit
24 —output shaft of drive unit
26 —fixed straightening rollers
26 a —bearings supporting fixed straightening rollers
26 b —rotational axes of fixed straightening rollers
28 —movable straightening rollers
28 a —bearings supporting movable straightening rollers
28 b —rotational axes of movable straightening rollers
30 —casing/rigid frame structure
32 —fixed side supports
34 —drive belt
36 —pulley on lower drive unit
38 —pulley on drive unit output shaft
40 —bracket
40 a —bearings supporting bracket
40 b —rotational axes of bracket
42 —sidewalls of bracket
44 —connecting member
46 —tail section
46 a —hole in tail section
48 —gear of lower feed roll
50 —gear of upper feed roll
52 —idler gear
54 —idler gear
56 —spring assembly
56 a —adjustable spring retainer
56 b —lock nut
58 —actuator
60 —piston
62 —piston bore
64 —air chamber
66 —piston seal
68 —piston rod
70 —rod seal
72 —pin
74 —radius profile
76 —rubber stop
78 —actuator cap
80 —rubber stop
84 —gear
86 —gear
88 —gears
90 —gears
92 —platen
92 a —bearings supporting platen
92 b —pivoting axis of platen
92 c —bracket
94 —entrance guide roller
94 a —adjustable edge guides
96 —actuator
97 —actuator cap
98 —springs
98 a —counterbore
100 —cam
102 —wear plate
104 —piston
106 —piston bore
108 —piston seal
110 —piston rod
112 —rack
114 a —gear
114 b —gear
114 c —gear
116 —drive shaft
118 —air chamber
120 —rubber stop
122 —rubber stop
124 —air pilot valve
126 —air pilot valve
128 —control unit module
130 —air pressure supply
132 —control signals from punch press
A—A—feed path of strip stock 16
DETAILED DESCRIPTION OF THE INVENTION
For purposes of illustration, the present invention is shown in the drawings as a combined material feed and straightening device 10 (FIG. 1) adapted to incrementally feed precise lengths of straightened continuous strip material 16 along a feed path A—A from a supply coil to a punch press in synchronization with the final positioning arrangement of the press.
Briefly, the device 10 includes a casing or rigid frame structure generally indicated as 30 having fixed side supports generally indicated as 32 that extend lengthwise between upstream and downstream ends 12 and 14 on each side of the feed path A—A; a pair of feed rollers 18 and 20 operatively coupled to a rotary drive unit 22 for advancing the strip material 16 along the feed path; and two sets of straightening rollers 26 and 28 adapted to effect straightening of the material as it travels through the device.
The feed rollers 18 and 20 are located on opposite sides of the feed path A—A proximate the downstream end 14 , are mounted for rotation about parallel axes 18 b and 20 b extending transversely to the feed path, and comprise (i) a lower drive feed roller 18 mounted in fixed relation to the casing 30 , and (ii) an upper pinch feed roller 20 operably connected to a pneumatic operator 58 for movement between (a) a material gripping position (as shown in FIG. 1) cooperative with the lower drive feed roller for gripping the strip material 16 therebetween and advancing the material toward the punch press in response to a control or feedback signal from the press during a material demand cycle, and (b) a material release position (as shown in FIG. 2) spaced from the strip material in response to a second signal from the press indicating the end of the material demand cycle.
The straightening rollers 26 and 28 are located on opposite sides of the feed path A—A upstream of the feed rollers 18 and 20 , are mounted for rotation about axes 26 b and 28 b parallel to the feed rollers, and comprise (i) a lower set of straightening rollers 26 mounted in fixed relation to the casing 30 , and (ii) an upper set of straightening rollers 28 operably connected to a second pneumatic operator 96 for synchronized movement with the upper feed roller 20 between (a) a material engaging position (FIG. 1) cooperative with the lower straightening rollers for straightening the strip material 16 prior to reaching the feed rollers during the material demand cycles of the punch press, and (b) a material release position (FIG. 2) spaced from the strip material between the material demand cycles.
In the embodiment shown, the lower drive feed roller 18 is journaled between the side supports 32 of the casing 30 in bearings 18 a (FIG. 3) for rotation about axis 18 b below the feed path A—A. The output shaft 24 of drive unit 22 is coupled for rotation of the lower feed roller such as with gears or a chain, and in the embodiment shown through a drive belt 34 connected between pulleys 36 and 38 provided at the ends thereof (see FIGS. 5 and 7 ). Suitable drive units include, but are not limited to brushless AC servomotors and stepper motors, such as provided with a resolver adapted to provide a closed-loop roller position feedback signal for use by the system controller.
The upper pinch feed roller 20 is journaled in bearings 20 a (FIG. 3) between laterally spaced side walls 42 of a bracket 40 for rotation about axis 20 b above the feed path, and is journaled with respect to the casing 30 for limited pivoting toward and away from the lower feed roller. In this instance, the bracket is journal mounted between the side supports 32 about an axis 40 b above the feed path A—A and parallel to but spaced transversely of the axes 18 b and 20 b for swinging between (i) a lower position (FIG. 1 )in which the upper feed roller is in gripping engagement with the strip material 16 located in the feed path, and (ii) a raised position (FIG. 2) in which the upper feed roller is spaced from the strip material in the feed path. The bracket shown includes a generally horizontal upper section 44 connecting the side walls 42 , and a generally vertical tail section 46 depending therebetween at a position below the lower drive feed roller 18 .
The upper feed roller 20 is rotationally coupled to the lower feed roller 18 by gears 48 and 50 connected through idler gears 52 and 54 that are rotatably supported on idler shafts carried by the casing 30 (see FIGS. 3, 4 and 6 ). The gears 48 , 50 , 52 and 54 are provided with the same pitch diameter so that the feed rollers rotate at the same speed but in opposite angular directions as indicated. Thus, when the upper feed roller is in its material gripping position (FIG. 1 ), the drive unit 22 power rotates both feed rollers for advancing a length of the strip material 16 passing therebetween toward the punch press. Advantageously, idler gear 54 rotates about the journal mounting axis 40 b such that, as the bracket pivots about the same axis 40 b , the gear 50 connected to upper feed roller rotates about the center of, and rolls along the idler gear 54 to maintain full engagement therebetween.
As shown in FIG. 1, the upper feed roller 20 is spring biased into its material gripping position by spring 56 , and pneumatically actuated to the material release position (FIG. 2) by pneumatic actuator 58 . To that end, spring 56 is grounded to the casing 30 and positioned to engage the bracket 40 oppositely of the journal mounting axis 40 b with respect to the pinch roller axis 20 b to continuously bias the bracket toward its lower position, and the actuator 58 is connected to the tail section 46 of the bracket oppositely of the journal mounting axis 40 b with respect to the feed path A—A for rotation of the bracket from its lower position to its upper position in contravention to the resilient biasing force of the spring. An adjustable spring retainer 56 a threaded through the casing 30 and locked into position with a threaded nut 56 b , permits manual adjustment of the spring-bias gripping force between the feed rollers.
The linear pneumatic actuator 58 includes a piston 60 slidably located in a piston bore 62 defined within the casing 30 and pneumatically responsive for linear movement therein to pressure in air chamber 64 defined in the piston bore; a piston seal 66 positioned to establish a sliding, sealing engagement between the piston and the piston bore; and a piston rod 68 that extends through a rod seal 70 and that is operatively connected at its free end to the tail section 46 of the bracket 40 . In this instance, the piston rod extends slidably through a hole 46 a in the tail section of the bracket, and a pin 72 located in a cross-hole in the piston rod maintains the piston rod in position therein. A radius-profile 74 formed in the tail section provides a relatively low-friction, automatically centering interface with the outer cylindrical profile of the pin. For actuation stability, the actuator is aligned with the lateral center of the bracket for connection to the center of the tail section (see FIG. 3 ).
With this arrangement, as air pressure is supplied to chamber 64 , the piston 60 strokes in a direction away from the tail section 46 (to the left as shown in FIGS. 1 and 2 ), and the pin 72 engages and draws the tail section 46 with the piston, pivoting the bracket 40 toward its raised position (clockwise as shown in FIGS. 1 and 2) and the upper feed roller 20 toward its material release position, until a rubber stop 76 engages against the actuator cap 78 (FIG. 2 ).
As air pressure is relieved from the chamber 64 , the bias force of spring 56 rotates the bracket 40 towards it lower position (counter-clockwise as shown) and the upper feed roller 20 toward the lower feed roller 18 and into gripping engagement with the strip material 16 therebetween. As the bracket rotates, the tail section acts against the pin 72 to return the piston to its extended position (FIG. 1 ). A second rubber stop 80 is optionally provided in the actuator chamber 64 to cushion the return stroke of the piston, and to reduce the volume of the chamber without affecting the pressure responsive area of the piston for relatively short actuator response time characteristics.
The lower straightening rollers 26 are journaled between the side supports 32 of the casing 30 in bearings 26 a (FIG. 3) for rotation about axes 26 b below the feed path A—A. The lower straightening rollers are rotated by the drive unit 22 through a gear train comprising a gear 84 that is connected for rotation with the lower feed roller 18 and that drives gears 86 a and 86 b , the latter of which is connected via a common shaft to gear 86 c which, in turn, drives idler gears 88 journaled in the side supports 32 on idler shafts and gears 90 connected to ends of the lower straightening rollers engaging the idler gears (see FIGS. 3, 6 and 8 ).
The upper straightening rollers 28 are journaled in a platen 92 for free rotation about axes 28 b (see FIGS. 1 and 9 ), and are journaled for limited pivoting with respect to the casing 30 toward and away from the lower straightening rollers. In this instance, the straightening rollers 28 are journaled on pins 28 a connected to the sides of a bracket 92 c carried by the platen, and the platen is pivotally mounted between the side supports 32 for pivoting about an axis 92 b parallel to the feed path A—A proximate the upstream end thereof for swinging between (i) a lower position (FIG. 1 )in which the upper straightening rollers are in straightening engagement with the strip material 16 located in the feed path, and (ii) a raised position (FIG. 2 )in which the upper rollers are spaced from the strip material in the feed path. The axes 28 b of the upper straightening rollers may be fixed in the platen 92 , or the bracket 92 c may be adapted for adjustment of the axes 28 b such as disclosed in further detail in patent, U.S. Pat. No. 4,594,872 which is incorporated herein by reference. An entrance guide roller 94 provided upstream of the straightening rollers includes adjustable edge guides 94 a (FIG. 3) to position the strip material 16 laterally between the side supports 32 as it feeds into the device 10 .
The upper straightening rollers 28 are spring biased into their material release position, and pneumatically actuated to their material engaging-straightening position by a second pneumatic actuator 96 . In this instance, a pair of laterally spaced springs 98 (see FIGS. 1 and 4) are positioned for acting between the casing 30 and the downstream end of the platen 92 to continuously bias the platen upwardly toward its raised position against a cam 100 , and the actuator 96 is connected for actuation of the cam 100 (i) to effect movement of the platen from its raised position to its lower position in contravention to the resilient biasing force of the springs 98 , and (ii) to permit rotation of the platen from its lower position to its raised position from the biasing action of the springs 98 .
The cam 100 is carried by a drive shaft 116 that is journal mounted for pivoting about axis 116 b above the downstream end of the platen 92 between first and second positions associated with the raised and lowered positions of the platen. The cam includes an operative surface portion that is off-set below axis 116 b and that is positioned to slidably act against a hardened wear-plate 102 carried at the downstream end of the platen 92 such that pivoting of the cam about axis 116 b causes the contact between the cam and the wear plate to lower and raise as shown in FIGS. 1 and 2, respectively. In the embodiment shown, the opposite end of the cam is threaded into a spacer 100 a that is connected to the end of the shaft 116 with a pin 100 b extending therethrough.
The second pneumatic actuator 96 is constructed similar to actuator 58 , and includes a pneumatically actuated piston 104 slidably located in a piston bore 106 defined within the casing 30 for linear movement between retracted and extended positions as shown in FIGS. 4 and 5, respectively, a low friction piston seal 108 positioned to establish a sliding, sealing engagement between the piston and the piston bore, and a piston rod 110 extending from the piston for linear movement therewith.
In this instance, the piston rod 110 is coupled to a gear-toothed rack 112 for linear reciprocating movement as shown in FIGS. 7 and 8, and the rack drivingly engages a set of gears 114 a-c to translate the linear piston motion into rotary motion. The upper gear 114 c rotates about axis 116 b and is connected to the cam 100 through the drive shaft 116 .
With this arrangement, as air pressure is supplied to the chamber 118 , the piston 104 strokes in the direction away from the rack 112 (to the left as shown in FIGS. 7 and 8 ), the rack moves with the piston and rotates the gears 114 a-c , rotating the cam 100 toward its lowered position, until the rubber stop 120 engages against the actuator cap 97 as shown in FIG. 7 . As the cam pivots downwardly, it acts against the upwardly biased wear plate 102 to drive the platen 92 downwardly to its lower position and the upper straightening rollers 28 to their material engaging-straightening position (FIG. 1 ).
As air pressure is relieved from the chamber 118 , the bias force of springs 98 simultaneously raises the platen 92 , and acting through the wear plate 102 , rotate the cam 100 to their raised position (FIG. 2 ), and returns the piston 104 to its extended position (FIG. 8 ). A second rubber stop 122 is optionally provided to cushion the return stroke of the piston, and to reduce the volume of the chamber without affecting the pressure responsive area of the piston for relatively short actuator response time characteristics.
Synchronized pneumatic signals are provided to the actuators 58 and 96 , to effect synchronized operation of the feed roller 20 and the straightening rollers 28 , via synchronized operation of solenoid operated air pilot valves 124 and 126 that are pneumatically coupled to the actuators and electrically connected to receive control signals from a control unit 128 .
As shown in the schematic in FIG. 11, the pilot valve 124 is spring biased to a normally open position to vent chamber 64 of actuator 58 to atmosphere, and the pilot valve 126 is spring-biased to a normally closed position to establish fluid communication between chamber 118 of actuator 96 and a fluid pressure supply 130 . Thus, absent an energizing control signal to the pilot valves 124 and 126 , the spring 56 biases the feed roller 20 to its material gripping position, and the actuator 96 drives the cam 100 to its lower position and the upper straightening rollers 28 to their material straightening position, such that the device 10 is operative to simultaneously straighten the coil stock 16 and feed the straightened material to the punch press.
When the pilot valves 124 and 126 are energized, the valve 124 closes to establish communication between the chamber 64 and the pressure source 130 , and the valve 126 opens to vent the chamber 118 to atmosphere. As discussed above, pressure to the chamber 64 causes the upper feed roller 20 to swing to its material release position, and the absence of pressure in chamber 118 allows the platen springs 98 to bias the upper straightening rollers 28 upwardly to their material release position.
Thus, simultaneously energizing and de-energizing the solenoid operated pilot valves 124 and 126 results in synchronized actuation of the feed rollers and the straightening rollers between their material engaging-gripping positions and material release positions.
An automatic control system operatively coupled between the combined material feed and straightening device 10 and the punch press is adapted to synchronize the feed and straightener operations of the device 10 with the material demand cycles of the punch press. Preferably, the control system includes a closed-loop, electronic control module 128 that is adapted to control the feed and straightening functions of a conventional material feed device, but modified to accomplish the feed and straightening synchronization functions of the present invention. Thus, the controller can be programmed with an integral or remote data entry keypad and associated programmable control module. The controller will be typically adapted for manual, single cycle, and automatic operating modes. And the controller can be provided with adjustable ramping speed and suitable fault diagnostics, as well as job memory, full batch and cumulative/cyclic counting functions.
To accomplish synchronized operation between the device 10 and the punch press, the controller receives signals 132 from the punch press indicating the start and end of the material demand cycles, and provides appropriate control signals to the pilot valves 124 and 126 in accordance herewith. In the embodiment described, when the controller receives a signal from the punch press indicating the start of a material demand cycle, the controller provides signals to simultaneously de-energize the solenoids of the pilot air valves such that the feed roller 20 and straightening rollers 28 simultaneously move to their material gripping-feeding and straightening positions, whereupon the power-rotated feed rollers draw the strip material through the straightening rollers, and advance the straightened stock toward the punch press. When the controller receives a signal from the press indicating a sufficient length of material has been provided and thus the demand for material has ended, the controller initiates signals to energize the pilot valves, whereupon the upper feed roller and the upper straightening rollers actuate to their material release positions and free the strip for final position in the press. Upon receiving the next material demand signal from the press, the controller simultaneously de-energized the pilot valves, and the upper feed roller and straightening rollers return to their material gripping-feeding and straightening positions without any loss in material roll position. This activity cycle is repeated for each operating cycle of the punch press.
Those skilled in the art will recognize that alternate arrangements are suitable for use in the invention hereof. For example, but without limitation, alternate arrangements will include the use of hydraulics to actuate the operators, dual-acting actuators rather than spring-biased actuators, and alternate biasing arrangements such as air springs. These and additional equivalents and alternate arrangements will fall within the scope of the present invention.
From the foregoing, it will be apparent that the present invention brings to the art a new and improved apparatus adapted to simultaneously straightening and feed strip material to a punch press or other using station. More particularly, the device is uniquely adapted to simultaneously release both the feed pressure and the straightening pressure on the strip material during a portion of each press cycle for ease of final positioning in the press, or for other using station purposes, and to simultaneously reset and regrip the strip material, to reapply the feed pressure and straightening pressure to the material for advancing and simultaneously straightening the next length of stock to the press. | A roll-type straightening and feed mechanism includes opposing sets of straightening rolls adapted to straighten coil stock as it travels therebetween, opposing feed rolls adapted to grip the coil stock therebetween to advance the straightened coil stock to a using station, and operators connected to simultaneously separate the straightening rolls and the feed rolls and release the coil stock therebetween, and to simultaneously reset the straightening rolls and the feed roll and re-grip the coil stock for advancing straightened stock. | 1 |
This is a continuation-in-part of U.S. patent application Ser. No. 07,381,062 filed 07/17/89, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a hand-truck and more particularly to a hand-truck that when empty can be folded into a compact unit flat enough to be stored beneath the seat of an aircraft or train.
2. Description of the Prior Art
U.S. Pat. No. 3,947,054 Hall, describes a folding luggage carrier, with a folding handle and small wheels, that easily folds for storage beneath an aircraft passenger seat.
U.S. Pat. No. 4,299,403 Brewer et al describes a wheeled baggage carrier with foldable handle and foldable platform of truss-like configuration. U.S. Pat. No. 4,062,565 Holtz, describes a collapsible baggage cart as tubular configuration with a foldable handle and a foldable platform. The U.S. Pat. No. 3,043,603 Major, Sr., describes a hand-truck with pivoted wheel supports.
SUMMARY OF THE INVENTION
The principal objectives of the instant invention is to provide a luggage carrier foldable into a flat configuration that will fit beneath the seat of a passenger aircraft. The luggage carrier capable of being opened for use and locked in the open position by folding down the luggage platform. The limiting factor in obtaining a flat package for many luggage carriers is the diameter of the wheels, thus necessitating the use of impractical small wheels. The instant invention provides pivoted wheel support, allowing the wheels to swing inwardly parallel to the luggage carrier frame. This arrangement permits the use of a larger wheel diameter, for traversing uneven surfaces.
A second limiting factor in obtaining a flat package in the configuration of the handle hinge assembly. The instant invention describes a hinge assembly of the same outside dimensions as the carrier frame member.
Luggage carriers currently available having pivoted wheel supports and foldable platforms require the use of two hands in order to swing each wheel outwardly and to fold down the platform. The instant invention utilizes a motion conversion device coupled between the platform hinge and the pivoted wheel support that simultaneously rotates the wheels as the platform is lowered into position by one hand.
The instant invention describes a luggage carrier with a tubular substantially rectangular basic frame with a pair of wheels rotatable around the vertical axis attached to two adjacent corners. A second frame of similar construction is hinged to the top of the basic frame so as to be capable of extending the basic frame into a coplanar position. A rectangular tubular frame attached to the basic frame near the wheels supports luggage stacked onto the carrier. The rotatable wheel supports which are angularly movable from an extended position to a folded position are mounted on the lower end of the main support structure. The wheel supports are rotatable around the tubular support structure by means of a vertical slot engaging an extended section extending upwardly from the platform hinge which rotates around a diametric pin extending from the tubular support.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front view of the foldable luggage carrier;
FIG. 2 is a right side view of the foldable luggage carrier;
FIG. 3 is a back view of the foldable luggage carrier;
FIG. 4 is a front view of the foldable luggage carrier in the folded configuration;
FIG. 5 is a left side view of the foldable luggage carrier in the folded configuration
FIG. 6 is a detailed side view of the rotary motion conversion bracket in the folded configuration;
FIG. 7 is a detailed side view of the rotary motion conversion bracket in the open configuration;
FIG. 8 is a detailed view of the motion conversion rotary hub;
FIG. 9 is a bottom view of the rotary motion conversion bracket;
FIG. 10 is a detailed front view of the handle hinge;
FIG. 11 is a detailed side view of the handle hinge;
FIG. 12 is an end view of the rotary motion conversion bracket.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 the foldable luggage carrier 10 is shown in a front view with the second or upper frame structure 12 with horizontal brace 19 hinged to the lower basic frame structure 13 with horizontal braces 20 and 11. The slidable hinge lock tube 18 is shown in the locked position. Rotatable around the tubular structure 13 are the wheel support brackets 14 with luggage support frame 16 hinged vertically to the tubular structure 13 by rotary motion conversion bracket 17.
The side view of FIG. 2 shows the luggage carrier 10 with upper frame 12, the hinge lock tube 18, lower basic frame 13 with rotatable wheel support bracket 14 supporting the wheel 15. The rotary motion conversion bracket 17 is shown with attached luggage support frame 16.
The rear view of FIG. 3 shows the luggage carrier 10 with the upper frame structure 12, with horizontal brace 19, hinged to the lower tubular vertical support structure 13 with horizontal braces 20 and 11. The hinge covered by slidable lock tube 18 is shown in the locked position. Rotatable around the tubular structure 13 are the wheel support brackets 14 with the wheels 15, the rotary motion conversion bracket 17 and the luggage arm 16.
A front view of the foldable luggage carrier 10 is shown in FIG. 4 with the carrier in the folded configuration. The wheels 15 and support brackets 14 are rotated inwardly and the luggage support arm 16 folded upwards into the vertical position. The upper frame structure 12, with horizontal brace 19, is folded downwards by means of hinges 28 coupling the upper frame to the lower frame and horizontal braces 10 and 11. The rotary motion conversion bracket 17 is shown in the folded position:
FIG. 5 is a left side view of FIG. 4 showing the upper frame structure 12 and the lower frames structure 13 with coupling hinges 28 and hinge locking tube 18 raised to permit hinge operation. The luggage support frame 16 is shown in the upward position, the wheel support bracket 14 is shown with the rotary motion converter bracket 17.
FIG. 6 is a detailed view of the rotary motion conversion bracket 17 in the folded position. The bracket 17 rotatable around the hinge pin 27 has a cam slot 31 which engages the radial pin 26 extending from the hub 24 and which serves to fasten the hub 24 to the rotatable tube frame member 34. The hinge pin 27 extends through orifices in the bracket 23 which is rotatable around the rotatable tube frame member 34. The wheel support bracket 14 is fastened to the rotatable tube frame member 34 by rivets 33 or other fastened to the rotatable tube frame member 34 by rivets 33 or other suitable means. The luggage support bracket 16 is shown extending from the bracket 17 with the position locking protrusion 30.
FIG. 7 is a detailed view of the rotary motion conversion apparatus 17 rotated around the hinge pin 27 with the cam slot 31 engaging the radial pin 26 to rotate the hub 24, the rotatable tube frame member 34 and the wheel support bracket 14 to extend the wheels into the open position and engaging the protrusion 30 between the side walls of the bracket 14.
FIG. 8 is a detailed view if the pin support orifice 32 in the bracket 23, the hub 24 with radial pin 26 and rotatable tube frame member 34.
FIG. 9 is a bottom view of the rotary motion conversion bracket showing the wheel support bracket 14, the hub 24, the rotatable tube frame member 34, the radial pin 26 and the luggage support frame 16 with fastening rivets 29.
FIG. 10 shows a side view of the hinge 28 with clevis 21 in the top structure 12 and the bottom basic frame member 13 with the clevis 22. The slidable lock tube 18 is shown in the upper or unlocked position.
FIG. 11 is a front view of the hinge 28 with upper portion 25 in the clevis 21 and the lower portion 25 in the clevis 22 in the basic frame member 12.
FIG. 12 is a left end view of FIG. 7 showing the bracket 17 with protrusion 30 engaging the side walls of the wheel support bracket 14 with radial pin 26 engaging the cam slot 31, the rotatable tube frame member 34 with flange 35 supported by circular slot 35 and ring 36.
In use, rotating the luggage frame and bracket clockwise, or downwardly, around the hinge pin 27 rotates cam slot 31 to rotate radial pin 26 with the hub 24 and the rotatable tube member 34 clockwise around the vertical axis of the basic frame member 13. The wheel support bracket fastened to the rotatable tube member 34 is rotated clockwise with the hub 24 rotating the wheel support bracket 90 degrees to engage the protrusion 30 in the space between the side walls of the wheel support bracket 14. | A light weight, foldable, luggage carrier capable of being folded to a flat package storable beneath the seat of an airplane or a train. The carrier having larger than normal diameter wheels whose axis rotates inwardly between the frame members when the luggage support frame is raised to the closed or stored position. This conversion of the carrier from the open to the closed position can be accomplished by the use of one hand. | 8 |
BACKGROUND OF INVENTION AND PRIOR ART
1. Field of Invention
Gastric antisecretory and antiulcer compounds, compositions, and treatment; novel thioformamidines useful for such purpose.
2. Prior Art
Cimetidine [(N-Cyano-N'-methyl-N''-[2-[[(5-methyl-1H-imidazol-4-yl)methyl]thio]ethyl]guanidin e; Tagamet (TM)] is a renowned antagonist to histamine H 2 receptors, especially in the treatment of duodenal and gastric ulcers, and therefore is a compound which may advantageously be employed as a standard when testing the effectiveness of another compound against excessive gastric secretion and ensuing ulcers.
The compounds of the present invention, which are novel formamidines, are superior to cimetidine in their gastric antisecretory effect and approximately equal thereto in the inhibition of ulcer lesions.
OBJECTS OF THE INVENTION
An object of the invention is to provide novel formamidines which are effective gastric antisecretory agents, pharmaceutical compositions thereof, and a method of treating excessive gastric secretions and inhibiting ulcer formation therewith. Other objects of the invention will become apparent hereinafter, and still others will be obvious to one skilled in the art.
SUMMARY OF THE INVENTION
The present invention, inter alia, comprises novel formamidine compounds, pharmaceutical compositions thereof, a method of reducing excess gastric secretion and inhibiting the formation of ulcer lesions therewith, all as set forth in more detail hereinafter and as claimed in the claims appended hereto.
THE INVENTION
The present invention, developed at the Pierre Fabre Research Center, has as its object new chemical compounds, their method of preparation, pharmaceutical compositions thereof, and their use as drugs. The new chemical compounds are selected from those having the general Formula I: ##STR2## in which: R 1 represents hydrogen or lower-alkyl containing one to four carbon atoms, inclusive,
R 2 is benzoyl, benzyl, or alpha-hydroxybenzyl, the aromatic ring being optionally substituted by a halogen atom,
R 3 and R 4 , which are identical or different, represent hydrogen, lower C 1-4 alkyl, or lower C 1-4 alkenyl, or, together with the formamidine function, form a heterocycle, such as, for instance, imidazole, imidazoline, benzimidazole, triazole, pyrimidine, or tetrahydropyrimidine,
R 5 represents hydrogen, or lower-alkyl containing 1 to 4 carbon atoms, inclusive, or forms with R 4 a double bond (--N=R 4 ) in the case of pseudoaromatic heterocycles,
n equals 0 or 1,
A represents a linear or branched alkylene group having 1 to 4 carbon atoms, inclusive, and
X represents hydrogen, halogen, lower C 1-4 alkyl, lower C 1-4 alkoxy, or nitro,
and pharmaceutically-acceptable organic and inorganic salts thereof.
The present invention also concerns a method of preparing compounds of Formula I by reaction of a thioformamidine with a halogenated reagent: ##STR3## wherein Y represents chlorine or bromine,
and R 1 , R 2 , R 3 , R 4 , R 5 , A, n and X have the same meaning as given in the foregoing.
The reaction is preferably carried out in an organic solvent such as methanol or ethanol and under reflux.
The present invention moreover also concerns the use of compounds of Formula I as drugs as well as pharmaceutical compositions containing these compounds.
The pharmaceutical compositions of the present invention may contain one or more compounds of Formula I, possibly in association with other active principles. Among the compounds of Formula I, mention may be made more particularly of the following specific compounds, all of which are produced in accord with the following Examples:
N-methyl 2-[2-(Δ2-imidazolinyl)thio]2'-orthochlorobenzoyl-4'-chloroacetanilide hydrochloride. (1) ##STR4##
N-methyl 2-2-(Δ2-imidazolinyl)thio] 2'-benzoyl-4'-chloroacetanilide hydrochloride. (2) ##STR5##
2-[2-(Δ2-imidazolinyl)thio] 2'-orthochlorobenzoyl-4'-chloroacetanilide hydrochloride. (3) ##STR6##
N-methyl 2-[2-(1-methylimidazolyl)thio] 2'-orthochlorobenzoyl-4'-chloroacetanilide hydrochloride. (4) ##STR7##
2-(2-imidazolylthio) 2'-benzoyl-4'-chloroacetanilide hydrochloride. (5) ##STR8##
2-(2-imidazolylthio) 2'-orthochlorobenzoyl-4'-chloroacetanilide hydrochloride. (6) ##STR9##
N-methyl 2-orthochlorobenzoyl-4'-chloro 2-[(2-imidazolyl)thio]acetanilide hydrochloride. (7) ##STR10##
1-(2-imidazolylthio) 2-[(2-benzoyl-4-chloro)anilino]ethane. (8) ##STR11##
1-[2-(Δ2-imidazolinyl)thio] 2-(2-benzoyl-4-chloro)anilinoethane. (9) ##STR12##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-[2-(1-methyl-Δ2-imidazolinyl)thio]acetanilide hydrochloride. (10) ##STR13##
N-methyl 2'-(orthochloro-α-hydroxybenzyl)-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide. (11) ##STR14##
N-methyl 2'-benzyl-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide hydrochloride. (12) ##STR15##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]propionanilide citrate. (13) ##STR16##
N-methyl 2'-benzoyl 2-[2-imidazolylthio]acetanilide. (14) ##STR17##
N-methyl 2'-benzoyl-4'-chloro 2-(2-imidazolylthio)acetanilide hydrochloride. (15) ##STR18##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-isothioureidoacetanilide hydrochloride. (16) ##STR19##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-(2-pyrimidinyl)thioacetanilide. (17) ##STR20##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-(1-ethyl-2-imidazolyl)thioacetanilide hydrochloride. (18) ##STR21##
N-methyl 2'-orthochlorobenzoyl-4'-chloro 3-(2-imidazolyl)thiopropionanilide. (19) ##STR22##
N-methyl 2'-benzoyl-4'-nitro 2-[(2-imidazolyl)thio]acetanilide hydrochloride. (20) ##STR23##
N-methyl 2'-orthofluorobenzoyl-4'-chloro 2-[(2-imidazolyl)thio]acetanilide hydrochloride. (21) ##STR24##
N-methyl 2'-benzoyl-4'-methoxy 2-[(2-imidazolyl)thio]acetanilide hydrobromide. (22) ##STR25##
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described in further detail by the following non-limitative examples: EXAMPLE 1
Preparation of N-methyl 2-[2-(Δ2-imidazolinyl)thio]2'-benzoyl-4'-chloroacetanilide hydrochloride. (2)
22.55 grams of N-methyl 2'-benzoyl-2,4'-dichloroacetanilide and 6.13 grams of ethylene thiourea are refluxed for 6 hours in 150 ml of absolute ethanol. The solution is evaporated under vacuum and taken up in a minimum amount of chloroform and then diluted with ethyl ether. Upon crystallization, 23.6 grams are obtained of N-methyl 2-[2-(Δ2-imidazolinyl)thio]2'-benzoyl-4'-chloroacetanilide hydrochloride (yield =92%).
MP=202° C.
C.C.M.=silica gel Merck 60 F 254; solvent: CHCl 3 --MeOH :
85-15 - Rf=0.27.
EXAMPLE 2
N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-[(2-imidazolyl)thio]acetanilide hydrochloride. (7)
A suspension of 10.68 grams of N-methyl 2'-orthochlorobenzoyl-2,4'-dichloroacetanilide and 2.4 grams of 2-mercaptoimidazole are treated for 8 hours under reflux with methanol. After cooling, evaporation under vacuum, and taking up by an acetone-ether mixture, there is obtained by crystallization the hydrochloride of N-methyl 2'-orthochlorobenzoyl-4'-chloro 2-[(2-imidazolyl)thioacetanilide (9.12 g).
MP=165° C.
Rf=0.22 (ethyl acetate)
EXAMPLE 3
1-[2-(Δ2-imidazolinyl)thio] 2-(2-benzoyl-4-chloro)anilinoethane. (9)
A suspension of 16.9 grams of β -bromo-2-ethylamino-5-chlorobenzophenone and 5 grams of ethylene thiourea is refluxed for 3 hours with a solution containing 100 ml of 95° ethanol, 10 ml of 10N sodium hydroxide and 15 ml of water. After evaporation in vacuum, taking up by absorption in 6N hydrochloric acid, and washing with ethyl acetate, the aqueous phase is neutralized with sodium bicarbonate and extracted with ethyl acetate. The concentrated organic phase is purified over a silica column by elution with MeOH--NHCl 3 --NH 4 OH / 9-90-1 and the 1-[2-(Δ2-imidazolinyl)thio]2-(2-benzoyl-4-chloro)anilinoethane is isolated by crystallization;
MP=146° C.
Rf=0.13 (CHCl 3 --MeOH : 85-15)
EXAMPLE 4
N-methyl 2'-(orthochloro-alpha-hydroxybenzyl)-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide. (11)
750 mg of sodium borohydride are added in individual portions to a suspension of 2.8 grams of 2-methylamino-2',5-dichlorobenzophenone in 20 ml of methanol. After reaction for about ten minutes, the solvent is evaporated in a vacuum. After absorption in ether, washing with water, and then drying, 2-methylamino-2',5-dichlorobenzhydrol is isolated by crystallization (2.52 g).
MP=110° C.
The compound obtained (2.26 g) in solution in ethyl acetate is treated at a temperature of 0° C. with 0.8 ml of bromoacetyl chloride in solution in ethyl acetate (10 ml). After washing with water and drying, 2-(N-methylbromacetamido)-2',5-dichlorobenzhydrol is obtained (2.83 g). MP=196° C.
This product (6.5 g) in suspension in absolute ethanol (30 ml) is treated with ethylene thiourea (1.63 g) under reflux for three hours. After cooling, crystals are obtained which are filtered out and washed with ether. Upon absorption in 1N sodium hydroxide, extraction by THF-ethyl acetate and then drying and recrystallizing from ethyl acetate, N-methyl 2'-(orthochloro-alpha-hydroxybenzyl)-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide is obtained.
MP=170° C.
Rf=0.2 (CHCl 3 --MeOH : 85-15)
EXAMPLE 5
N-methyl 2'-benzyl-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide hydrochloride. (12)
a) 2'-benzyl-4'-chlorotosanilide
8.31 g of tosyl chloride are added to a solution of 2-benzyl-4-chloroaniline (7.9 g) in pyridine (35 ml). After 1 hour at 100° C. followed by cooling, it is poured onto 100 ml of 6N hydrochloric acid and 200 g of ice. A gum forms which is extracted with ethyl acetate. After washing with water, drying and concentrating, 2'-benzyl-4'-chlorotosanilide is obtained by precipitation with petroleum ether (10.85 g).
MP=115° C.
b) N-methyl 2'-benzyl-4'-chlorotosanilide
The above compound (8.82 g) in solution in toluene is treated with benzyltriethylammonium chloride (522 mg), 10N sodium hydroxide solution (23.6 ml), and methyl sulfate (5 ml). After agitation for 30 minutes and being set aside overnight, the mixture is decanted, washed with water and then dried over Na 2 SO 4 ; N-methyl 2'-benzyl-4'-chlorotosanilide is obtained by crystallization (8.37 g).
MP=114° C.
c) N-methyl 2-benzyl-4-chloroaniline
The preceding product (24.49 g), suspended in acetic acid (50 ml), and 70% sulfuric acid (50 ml), is heated for 11 hours at 100° C. and then poured into 100 ml of ice water. After neutralization with 10N sodium hydroxide, extraction with ether, washing with water and drying, an orange oil (13.16 g) hydrochloride is obtained upon evaporation.
MP=125° C.
d) N-methyl 2'-benzyl-4'-chlorobromoacetanilide
The N-methyl 2-benzyl-4-chloroaniline (10.8 g) in solution in ethyl acetate is treated at 5° C. with 4.9 ml of bromoacetyl bromide. After 1 hour at room temperature, decantation and washing with water, the solution is concentrated. Upon crystallization, N-methyl 2'-benzyl-4'-chloro-bromoacetanilide is obtained (12.21 g). MP=78° C.
e) N-methyl 2'-benzyl-4'-chloro 2-[2-(Δ2-imidazolinyl)thio]acetanilide hydrochloride
The product obtained above (1.76 g) is treated under reflux with ethanol (20 ml) for 2 hours in the presence of ethylene thiourea. After cooling and filtration, 2.19 grams of crude product are obtained. It is taken up in 1N sodium hydroxide, extracted with ethyl acetate, washed with water and then evaporated under vacuum. The residue, when treated with an ethanolic solution of hydrochloric acid, gives, upon crystallization from ethyl ether, N-methyl 2'-benzyl-4'-chloro 2-[2-( Δ2-imidazolinyl)thio]acetanilide (1.7 g).
MP=217° C.
Rf=0.7 (CHCl 3 --MeOH : 50--50).
EXPERIMENTAL
Various toxicological and pharmacological tests were carried out on the compounds of the present invention.
A - TOXICOLOGY
The compounds of the invention were subjected to examination as to their toxicity. This was determined by the 50% lethal dose (LD 50 ). It was determined on lots of ten (10) mice orally and calculated in accordance with the method of Thomson and Weil (Biometrics 1952, 8, 249). The LD 50 of the compounds tested is greater than 500 mg/kg orally.
B - PHARMACOLOGICAL PROPERTIES
In pharmacological experiments, the compounds of the invention exhibited excellent antiulcer and gastric antisecretory properties. The results obtained with certain products of the present invention are reported below by way of example as compared with cimetidine.
1. Test study of gastric secretion by ligature of the pylorus using Shay's technique (Gastroenterology 5, 53, 1945 and 26, 906, 1954) on male Sprague-Dawley rats. Acute treatment by intraduodenal route in a dose of 50 mg/kg.
______________________________________ % Variation decrease of the increase of theProduct volume secreted intragastric pH______________________________________Cimetidine 47 901 76 1587 70 1184 76 26716 79 15315 50 181______________________________________
2. Activity toward ulcers with acetyl salicylic acid quantified in accordance with the Pfeiffer scale (Arch. Int. Pharmacodyn. 190, 5, 13, 1971) on male rats. Treatment orally, acute.
______________________________________ % Inhibition Dose of theProduct (mg/kg) ulcer lesions______________________________________Cimetidine 40 46 1 40 34 7 40 4612 40 4015 50 3516 50 32______________________________________
C - THERAPEUTIC APPLICATIONS
Based on their pharmacological properties, the compounds of the invention can be used in the treatment of digestive pathology and more particularly of ulcer pathology. The pharmaceutical preparations containing these active principles can be administered orally. It is also possible to combine therewith other pharmaceutically and therapeutically-acceptable active principles.
Those compounds of the present invention comprising a salt-forming group can be administered to man or animal orally or parenterally in the form either of the free base or in the form of a therapeutically-acceptable salt. The new derivatives which are bases can be converted into acid addition salts with acids, which acid addition salts form part of the invention. These acid addition salts can be obtained by reaction of the new basic derivatives with an acid in a suitable solvent, such as for example, in the mineral acid series, hydrochloric, hydrobromic, methanesulphonic, sulphuric, and phosphoric, and in the organic series, acetic, propionic, maleic, fumaric, tartaric, citric, oxalic, and benzoic acid, to name only a few. The selection of the free base or acid addition salt thereof in preparation of the desired acid addition salt in any particular case will be apparent and fully within the capability of one skilled in the art. Such novel compounds of the invention are frequently used in the form of their pharmaceutically-acceptable acid addition salts, such as the hydrochloride, hydrobromide, or the like, since the salt form is usually the best form for pharmaceutical formulations. Innumerable other pharmaceutically-acceptable acid addition salts can be prepared from the hydrochloride or other acid addition salt via the free base in conventional manner.
Based on their pharmacological properties, the compounds of the invention, and more especially the compounds of the Examples, can be used in therapy in the treatment of excessive gastric secretion and ulcers. Pharmaceutical preparations containing these active principles can be administered orally or parenterally. It is also possible to combine them with other pharmaceutically- and therapeutically-acceptable active principles.
On a basis of their pharmacological properties and their relatively low toxicity, the compounds of the invention can be employed for gastric antisecretory effect in a subject in need of the same, as well as for their antiulcer effect in a subject in need of the same, and accordingly may be employed in the form of pharmaceutical preparations which facilitate bioavailability and/or in the form of pharmaceutical compositions thereof containing an effective amount of the active ingredient together with a pharmaceuticallyacceptable carrier, diluent, or adjuvant. The preparations may as usual be provided in solid form, for example, in the form of tablets, pills, capsules, or the like, or in liquid form, for example, in the form of solutions, suspensions, or emulsions. Alternatively, the pharmaceutical preparations may be made available in a form suitable for injection by subjecting the same to conventional pharmaceutical operations such as sterilization, and in any event may contain adjuvants, for instance, preservatives, stabilizers, wetting or emulsifying agents, buffers, and the usual carriers or inert pharmaceutically-acceptable diluents such as sugar, starch, water, or the like. The doses in which the active compounds and the pharmaceutical compositions thereof may be administered vary widely depending upon the subject, but daily doses of from about 0.1 g to 1 mg/kg of body weight and which approximate or are somewhat lower than those usual for Cimetidine may be employed. The pharmaceutical compositions of the invention can be used in human or veterinary medicine where indicated, for instance, in gastric antisecretory and antiulcer therapy and prevention in a subject in need of the same. Other active principles may of course be associated with the compounds of the invention, in order to supplement or reinforce their therapeutic activity within a given pharmaceutical composition or for a given pharmaceutical indication, as is conventional in the art. The exact individual and daily dosages, as well as dosage regimens, will as usual be determined by the physician or veterinarian in charge.
In conclusion, from the foregoing, it is apparent that the present invention provides novel compounds which are useful for their gastric antisecretory and antiulcer properties, a process for the production thereof, pharmaceutical compositions comprising the same, and a method of treating a subject in need of such gastric antisecretory and antiulcer therapy by treating the said subject with an amount of a compound of the invention which is effective for such purpose, all of the foregoing compounds, process, compositions, and method of treating having the foregoing enumerated characteristics and advantages.
It is to be understood that the invention is not to be limited to the exact details of operation or to the exact compounds, compositions, methods, procedures, formulations, or embodiments shown and described, as obvious modifications and equivalents will be apparent to one skilled in the art, and the invention is therefore to be limited only by the full scope which can be legally accorded to the appended claims. | Formamidine compounds of general formula I ##STR1## in which: R 1 represents H or C 1-4 alkyl,
R 2 represents benzoyl, benzyl, or alphahydroxybenzyl, the aromatic ring being optionally substituted by a halogen atom,
R 3 and R 4 , which are identical or different, represent hydrogen, lower-alkyl, or lower-alkenyl, or form between them with the formamidine function a heterocycle,
R 5 represents hydrogen or C 1-4 lower-alkyl or forms with R 4 a double bond (--N═R 4 ) in the case of pseudoaromatic heterocycles,
n equals 0 or 1,
A represents a linear or branched C 1-4 alkylene chain,
X represents hydrogen, halogen, C 1-4 lower-alkyl, C 1-4 lower-alkoxy, or nitro, and pharmaceutically-acceptable salts thereof, are disclosed.
The compounds and pharmaceutical compositions thereof are used, optionally in combination with other active principles, as drugs for the treatment of gastrointestinal ailments, especially as gastric antisecretory and antiulcer agents. | 2 |
FIELD OF THE INVENTION AND RELATED ART STATEMENT
The present invention relates to a single facer for use in a corrugating machine comprising an apparatus for correcting a distance between the centers of shafts which is adapted to adjust (correct) a contacting condition between a lower roll and other rolls such as a top roll, a press roll and a gluing roll etc., which are in contact with said lower roll.
FIG. 1 conceptionally illustrates a typical single facer which has been used in a traditional corrugating machine. The major components of the single facer are a top roll 1 having teeth 1a formed around the circumferential surface thereof and arranged for free rotary movement, a lower roll 2 having teeth 2a formed around the circumferential surface thereof and arranged for free rotary movement with teeth 2a being engaged with teeth of the top roll 1 so that a corrugating medium 5 may be shaped into a corrugated configuration by urging the medium to enter into a gap formed between teeth 1a and 2a. A gluing roll 3 is arranged closely adjacent to the teeth 2a of the lower roll 2 for rotary movement and is adapted to apply a predetermined quantity of glue over the corrugated top portion of the corrugating medium 5 which has been formed by the rolls 1 and 2, and a press roll 4 etc., arranged to be closely adjacent to or in contact with the teeth 2a of the lower roll 2 for rotary movement and is adapted to produce a single faced corrugated board by allowing the corrugating medium 5 with glue applied and a liner board 6 to pass between it and the lower roll 2 under pressure for lamination. Gaps formed between the top roll 1 and the lower roll 2, between the lower roll 2 and the gluing roll 3 and between the lower roll 2 and the press roll 4 are all made to be variable in dimension by means of an apparatus for adjusting the roll contacting pressure (clearance), i.e., an apparatus for adjusting a distance between the centers of roll shafts supporting the rolls.
In such a single facer, suitable pressing forces and heating means for heating of the glue must be provided to laminate the corrugating medium 5 with the liner board 6 by applying glues, and consequently an apparatus for circulating steam to supply heating energy is incorporated in said rolls 1, 2 and 3.
There is a problem as described below in the traditional single facer illustrated in FIG. 1. That is, when a glue is used to laminate the liner board 6 to the corrugating medium 5 which has been formed in a corrugated configuration, a certain heating means is required to heat the starch glue to a flowable state, and hot rolls which have been heated act to elevate the temperature and expand the opposite sides of frame 8 on which the rolls are supported. This results, for example, in the increase of the distance P between the centers of shafts of the lower and press rolls 2 and 4 which are journaled, and consequently a gap amount S also tends to increase with time. Because of these shortcomings, pressing forces of the press roll 4 are gradually reduced, and such reduced pressing forces may result in the production of a single faced corrugated fiberboard 7 with inconsistent thickness and also an imperfectly formed lamination between corrugating medium 5 and the liner board 6 from which the single faced corrugated fiberboard sheet is made, and thus a poor quality corrugated sheet has frequently been made having substantially reduced strength and quality. The problem in the prior art has been described with reference to the lower roll 2 and the press roll 4, but a similar problem of varying distance between the centers of roll shafts may also occur between the top roll 1 and the lower roll 2, or between the lower roll 2 and the gluing roll 3, as the temperature of the frame 8 is elevated, and this has been a significant factor to hinder the improvement of the apparatus toward automation. Therefore, it has been a common practice to check the corrugated fiberboard 7 which is being produced for any abnormality through a visual inspection, and then to manually remove any defect if any. This procedure, however, needs a high level of skills and experience, which hinders automation.
OBJECT AND SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a single facer which can maintain a constant gap between rolls by automatically correcting a distance between the centers of roll shafts.
To achieve the above object, the present invention provides a single facer, wherein a top roll, a lower roll, a press roll and a gluing roll are supported on a frame, heating means are provided to heat the top, lower and press rolls, a corrugating medium is passed between the lower roll and the top roll so that it may be shaped to a corrugated configuration, while rolls are being heated, then the corrugating medium is guided to pass between the lower roll and the gluing roll to apply glue over the corrugated top portion of the corrugating medium, and then the corrugating medium is caused to pass between the lower roll together and the press roll with a liner board to bond the corrugating medium with the liner board, said single facer being characterized in that at least one of the top roll, gluing roll and press roll is arranged so as to be movable toward and away from the lower roll, an apparatus for adjusting a distance between the centers of roll shafts is provided between said at least one roll and said lower roll which are arranged for movement toward and away from said lower roll, said apparatus being operable to move the roll which is arranged for movement toward and away from said lower roll by actuating driving means, said frame is provided either with a temperature sensor which senses the temperature of the frame or a sensor which senses the start of the heating operation of the heating means, and furthermore a controller is provided which can actuate said apparatus for correcting the distance between centers of roll shafts in response to detection signals from the sensor.
Thus, the inventors of the present invention have found that the temperature of the frame is increased with time as steams is caused to circulate within each of the rolls, and that there is a certain interrelationship between the temperature of the frame and the gap amount of the lower roll. When the steam valve is opened, the temperature of the frame may increase in a curved fashion with time, and the gap amount between said rolls may also increase proportionally. It is also found that the temperature of the frame may cease increasing further at a predetermined time and therefore the temperature is kept at a constant level, and the gap amount will become steady after the passage of the predetermined time. Such tendency has been substantially common to the same single facer.
Taking the above phenomenon into account, the present invention has been made such that a temperature sensor is utilized to measure the temperature variation of the frame, and an apparatus is driven via a controller for correcting the distance between centers of roll shafts so as to maintain a gap amount at a constant level. Furthermore, because the temperature increase of the frame may be taken as a function of time, a timer is preset so that the apparatus for correcting the distance between the centers of roll shafts may be actuated in response to the clapsing of the preset time, instead of the variation in the frame temperature, and thereby maintaining the gap amount between rolls constant.
As described above, the present invention is constituted such that the variation in the distance between the centers of roll shafts may be detected either as a function of time or by directly measuring the frame temperature, and the apparatus for correcting the distance between the centers of the roll shafts may be controlled in response to such temperature variation or passage of time and thus a precise correction is achievable for the expansion (increase in the gap amount between the lower roll and the press roll and the like). As a result, it is possible to eliminate inconsistent lamination between single faced corrugated fiberboard sheets and the like, providing a remarkable effect in the improvement of the product quality such as thickness, strength and aesthetical appearance etc., moreover, the single facer does not need to be stopped to adjust the contact pressure between rolls, and besides numerous other merits are derived such as an automatic operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view showing a typical single facer in the prior art;
FIG. 2 is a lateral cross-sectional view showing a single facer embodying the concept of the present invention;
FIG. 3 is a partial cross-sectional view showing a press roll section of the single facer in accordance with the present invention;
FIG. 4 is a front elevation view showing essential parts of the apparatus for adjusting a distance between the centers of the shafts of the press roll and the lower roll according to the invention;
FIG. 5 is a diagrammatic view showing a relationship between the passage of time after steam is caused to circulate in each of the rolls, the gap amount between rolls and the frame temperature; and
FIG. 6 is a view showing an alternative mode of operation of the apparatus for adjusting the distance between the centers of the roll shafts.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A single facer is constituted as shown in FIG. 2 by a top roll 11 having teeth 11a formed around the circumfernetial surface, a lower roll 12 having teeth 12a formed around the circumferential surface with said teeth 12a engaged with teeth 11a of the top roll 11, a gluing roll 13 arranged to be closely adjacent to teeth 12a of said lower roll 12, and a press roll 14 arranged to be closely adjacent to or in contact with teeth 12a of the lower roll 12. The lower roll 12 has its bearings pinched and fastened in place between the frame 15 and the bracket 16. The top roll 11 is supported via bearings (not shown) on an arm 17 one end of which is attached to the frame via a pivot pin 18 for free pivotable movement and an opposite end of which is coupled with the piston rod tip end of a pressure cylinder 19 via a pin 20. The pressure cylinder 19 is supported on the bracket 16 which is in turn fastened to the frame 15. A positioning stop (not shown) is used in conjunction with the cylinder 19 to adjust a contacting pressure (gap) between the two rolls 11 and 12.
As shown in FIG. 3, the shaft 14a of the press roll 14 is journaled on bearings 22 opposite ends of which are embraced by an eccentric disc or cam 21 which is held on the frame 15 via a bushing 23 for pivotal movement. A press lever 25 is secured via a tapered pin 24 on the eccentric disc 21. An eccentricity adjustment rod 26 is provided to be closely adjacent to one end of the press lever 25. As shown in FIG. 4, the eccentricity adjustment rod 26 has its opposite ends journaled on the frame via a slide bushing 27 for axial slidable movement. Furthermore, a female thread 26a is formed on an outside end of the rod 26 and is threadably engaged with a thread rod 28. A portion of the thread rod 28 is journaled on the bracket 30 through bearings 29 and the top end of the rod 28 is directly coupled through a coupling 32 with the shaft 31a of the motor 31 which is secured on the bracket 30. The motor 31 is controlled as described below in response to the temperature sensor 33 provided on the frame 15, and is connected with the temperature sensor 33 through the controller 34. An inclined slider 35 is secured in place on the rod 26 at a position corresponding with the bearing section of the press roll 14, and as the rod 26 slides in an axial direction indicated by the double arrow line in FIG. 4, the press lever 25 and the eccentric disc 21 are caused to pivot by means of the slider 36 which is in sliding contact with the inclined surface 35a of the slider 35, thereby shifting the position of the center c of the press roll shaft 14a. A cylinder 37 for securing the eccentric disc is arranged between an opposite end of the press lever 25 and the frame 15 as shown in FIG. 3. The cylinder 37 biases the press lever 25 towards a counterclockwise direction in FIG. 3. Thus, the slider 36 which is arranged on one end of the press lever 25 is constantly in abutment with the slider 35. The shaft 13a of the gluing roll 13 is supported on the frame 15 or an arm and the like via bearings. The gluing roll 13 has its lower portion oriented toward and immersed in a glue 39 in a glue container 38. An adjustment roll 40 is arranged above the glue container 38. The adjustment roll 40 functions to suitably adjust the quantity of glue 39 adhered on the gluing roll 13 surface, and has its shaft 40a supported for movement on the frame 15 or an arm and the like via bearings and its circumferential surface in abutment with the gluing roll 13 to scrape away an excess glue 39 adhered on the roll 13.
In such single facer, a single faced corrugated fiberboard sheet is manufactured in accordance with a process wherein the corrugating medium 41 is urged to enter into a gap between rolls 11 and 12, and formed into a corrugated shape under cooperation between two rolls 11 and 12, then the corrugated medium 41 is guided to pass between rolls 12 and 13, the glue 39 is applied over the top portion of the corrugated medium 41 by means of the roll 13, the corrugated medium 41 and the liner board 42 are overlapped on each other between rolls 12 and 14, and finally the liner board 42 is urged against the corrugated medium 41 by means of the roll 14.
During the course of this process, steam is supplied to rolls 11, 12 and 14 though the valve 44 with the actuation of the single facer, and the steam acts to heat rolls 11, 12 and 14. As these rolls 11, 12 and 14 are elevated in temperature, the heat is transmitted to the frame 15 through the bearings and the like. In this manner, as the temperature of the frame 15 increases, the frame 15 is expanded in response to such heat, and as a result distances P between rolls 11 and 12 and between rolls 12 and 14 increase.
FIG. 5 shows an interrelationship between the frame temperature T which is variable with the passage of time after steam is caused to circulate in rolls 11, 12 and 14 and the gap amount S between the lower roll 12 and the press roll 14. In this graphical illustration, it is indicated that when the steam valve is opened at the time Ha, the temperature of the frame 15 is increased from Ta to Tb after a predetermined period is expired as shown with a solid line, and proportionally the gap amount between said rolls is increased from Sa to Sb. In the meantime, the temperature increase of the frame 15 reaches its peak value after the predetermined time H b and then the temperature stops elevating further and thereafter a constant temperature T b is maintained and the gap amount S between rolls is also maintained constant after the expiration of the predetermined time H b . This tendency is substantially common to the same single facer.
In this above embodiment, the phenomenon is taken into account, and the temperature sensor 33 is used to measure the temperature variation of the frame 15 and then the controller 34 is actuated to drive the motor 31 in accordance with the temperature thus measured, thereby maintaining the gap amount S between rolls 12 and 14 constant. From the graphical illustration in FIG. 5, it is also possible to take the temperature increase of the frame 15 as a function of time from Ha to Hb. Thus, as shown in FIG. 6, the gap amount S between the lower roll 12 and the press roll 14 can be maintained constant by providing the valve 44 with the sensor 33' adapted to verify the opening of the valve 44, and the output from the sensor 33' is supplied to the controller 34' in which the motor 31 is actuated to operate in accordance with the amount which corresponds with the passage of time in FIG. 5.
Meanwhile, the broken line in FIG. 5 is a curve indicating one example of how variations in the gap may be corrected, and such correcting amount may be freely preset through controllers 34 and 34'.
In the embodiment described above, apparatus for correcting the distance between the centers of the roll shafts in accordance with the present invention is provided between the lower roll 12 and the press roll 14, but it is also possible to arrange the same apparatus between the lower roll 12 and the top roll 11 and between the lower roll 12 and the gluing roll 13. | A single facer comprises an apparatus for automatically adjusting a gap between rolls, i.e., an apparatus for maintaining a roll gap constant. The apparatus for adjusting the distance between the centers of the roll shafts is operable to move one roll toward the other by actuating driving means. The driving means is controlled in response to the variation in the temperature of the frame which supports the driving means of the roll in place, or to the passage of time after a heating mechanism for heating the rolls has started operation. | 1 |
INCORPORATION BY REFERENCE
[0001] U.S. Pat. No. 6,139,913, “Kinetic Spray Coating Method and Apparatus,” is incorporated by reference herein.
TECHNICAL FIELD
[0002] The present invention is directed to electrical contacts that comprise spaced particles embedded into the surface of conductors in which the particles have been kinetically sprayed onto the conductors with sufficient energy to form direct mechanical bonds between the particles and the conductors in a pre-selected location and particle number density that promotes high surface-to-surface contact and reduced contact resistance between the conductors. The method of making such electrical contacts is also provided.
BACKGROUND OF THE INVENTION
[0003] Most electrical contacts are copper or copper alloy conductors with a tin-plated surface layer. The tin surface layer is a single continuous layer directly bonded to a clean non-oxidized copper substrate in order to promote maximum conductance between conductors while limiting resistance from the tin-copper metallic bond. Tin is used as a surface layer since it is substantially softer than copper and may be recurrently wiped to provide a fresh de-oxidized surface for metal-to-metal connection between conductors.
[0004] Electrical contacts have been traditionally made by electroplating a layer of tin to copper substrates followed by stamping out individual conductors. The copper substrates must be cleaned prior to placement in the electroplating bath to remove any oxidized surface layers that may otherwise create additional electrical resistance. The substrates are coated to a thickness of about 3 to 5 microns of tin.
[0005] Because most electrical contacts undergo repeated connections and reconnections, increasing the thickness of the tin surface layer correlates well with the longevity and durability of the contact. However, due to processing limitations and increased frictional properties, the threshold thickness for electroplating tin onto copper is about 5 microns.
[0006] While it may be possible to use other available coating methods to increase coating thickness, methods that rely on melting and/or depositing the tin in a molten state are undesirable because, unless conducted in the absence of oxygen, they will introduce significant oxidation into the tin surface layer. Also, due to the increased costs of use, such methods are not practical.
[0007] One of the main problems with present electrical contacts is debris build-up due to fretting on the contact surface. With relative movement of mated electrical contacts, a small portion of the oxidized surface layer is rubbed away to expose a fresh electrical connection surface. The portion rubbed away usually does not flake off, but instead remains adjacent to the contact point and begins to create a build-up of oxidized debris. It is well known that this oxidized debris becomes a source for additional resistance and degradation of the contact's conductance.
[0008] Prior to the present invention, removal of this debris has been impractical. In the prior art, the solution has been to provide continuous layer coatings that have been believed to result in maximum surface area for conductance.
[0009] A new technique for producing coatings by kinetic spray, or cold gas dynamic spray, was recently reported in an article by T. H. Van Steenkiste et al., entitled “Kinetic Spray Coatings,” published in Surface and Coatings Technology, vol. 111, pages 62-71, Jan. 10, 1999. The article discusses producing continuous layer coatings having low porosity, high adhesion, low oxide content and low thermal stress. The article describes coatings being produced by entraining metal powders in an accelerated air stream and projecting them against a target substrate. It was found that the particles that formed the coating did not melt or thermally soften prior to impingement onto the substrate.
[0010] This work improved upon earlier work by Alkimov et al. as disclosed in U.S. Pat. No. 5,302,414, issued Apr. 12, 1994. Alkimov et al. disclosed producing dense continuous layer coatings with powder particles having a particle size of from 1 to 50 microns using a supersonic spray.
[0011] The Van Steenkiste article reported on work conducted by the National Center for Manufacturing Sciences (NCMS) to improve on the earlier Alkimov process and apparatus. Van Steenkiste et al. demonstrated that Alkimov's apparatus and process could be modified to produce kinetic spray coatings using particle sizes of greater than 50 microns and up to about 106 microns.
[0012] This modified process and apparatus for producing such larger particle size kinetic spray continuous layer coatings is disclosed in U.S. Pat. No. 6,139,913, Van Steenkiste et al., that issued on Oct. 31, 2000. The process and apparatus provide for heating a high pressure air flow up to about 650° C. and accelerating it with entrained particles through a de Laval-type nozzle to an exit velocity of between about 300 m/s (meters per second) to about 1000 m/s. The thus accelerated particles are directed toward and impact upon a target substrate with sufficient kinetic energy to impinge the particles to the surface of the substrate. The temperatures and pressures used are sufficiently lower than that necessary to cause particle melting or thermal softening of the selected particle. Therefore, no phase transition occurs in the particles prior to impingement.
SUMMARY OF THE INVENTION
[0013] The present invention is directed to kinetic spraying electrically conductive materials onto conductive substrates. More particularly, the present invention is directed to electrical contacts that comprise spaced electrically conductive particles embedded into the surface of conductors in which the particles have been kinetically sprayed onto the conductors with sufficient energy to form direct mechanical bonds between the particles and the conductors in a pre-selected location and particle number density that promotes high surface-to-surface contact and reduced contact resistance between the conductors. The particle number density, as used herein, defines the quantity of spaced particles deposited within a selected location.
[0014] Utilizing the apparatus disclosed in U.S. Pat. No. 6,139,913, the teachings of which are incorporated herein by reference, it was recognized that thick continuous layer coatings could be produced on conductive substrates in the production of electrical contacts. Such thick coatings are practical due to the mechanical bonds that are formed by impact impingement of the particles onto the substrate. These thicker continuous layer coatings are beneficial in producing electrical contacts since they provide low porosity, low oxide, low residual stress coatings that result in electrical contacts having greater longevity and durability.
[0015] When the feed rate of the particles into the gas stream is reduced, it is difficult to maintain a uniform output of particles necessary to form a continuous layer. The production of a continuous layer of particles is even more problematic if the substrate is moved across the nozzle or vice versa.
[0016] The present inventors used this process to embed a large number of spaced apart particles in the surface of conductors to provide multiple contact points that are particularly useful for electrical contacts. A large number of spaced particles embedded in the surface of the conductors provide a structure having a surface layer with a plurality of particles forming ridges and valleys. Each embedded particle defines a ridge, and the space in between particles defines a valley. The ridges provide multiple contact points for conductance while the spaces provide multiple avenues for the removal of debris produced from repeated fretting. Thus the discontinuous nature of the particle coating caused by the method of application leads to an electrically conductive contact that can with stand repeated fretting, as discussed further below.
[0017] In addition, the present invention provides the means for controlling the location of deposition of kinetic sprayed particles and the particle number density deposited in that location on the conductive substrate by simply controlling the feed rate of particles into the gas stream and the traverse speed of the substrate across the apparatus and/or nozzle. By doing so, the spray of conductive materials is controlled so that particles are only deposited on those portions that are to be stamped out as conductors.
[0018] This provides a tremendous advantage in processing. It substantially reduces waste of the conductive particles and aids in the reuse of substrate materials. Furthermore, there are no plating bath waste products or associated disposal costs.
[0019] In a typical coating procedure it is necessary to pre-clean the surface that is to be coated to remove the oxide layer, the present process eliminates this step. The impact of the initial kinetic sprayed particles on the surface is sufficiently forceful to fracture any oxide layer on the surface. The subsequent particles striking the now cleaned surface stick. As a result, electrical contacts produced by kinetic spraying spaced electrically conductive particles are particularly useful.
[0020] The present invention provides that particles can be kinetic sprayed onto conductors with sufficient energy to form direct mechanical bonds between the particles and the conductors in a pre-selected location and particle number density that promotes high surface-to-surface contact between the conductors with reduced contact resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] [0021]FIG. 1 is a scanning electron micrograph of an electrical contact of the present invention comprising a copper conductor with kinetic sprayed tin particles, having an original particle diameter of about 50 to 65 microns, embedded on its surface;
[0022] [0022]FIG. 2 is a chart that shows the contact resistance as a function of fretting cycles of a prior art electroplated tin electrical contact; and
[0023] [0023]FIG. 3 is a chart that shows the contact resistance as a function of fretting cycles of a tin-copper electrical contact made according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0024] An electrical contact of the present invention preferably has a contact resistance of less than about 10 milli-ohms and more preferably less than about 2 milli-ohms (when measured with a 1 Newton load and a 1.6 mm radius gold probe per ASTM B667). However, it is well recognized that electrical contacts of any contact resistance fall within the scope of the invention. The electrical contact comprises first and second mated conductors. While more than two conductors may be used to form an electrical contact, two are preferred. The conductors are stamped out of conductive substrates made of any suitable conductive material including, but not limited, to copper, copper alloys, aluminum, brass, stainless steel and tungsten. It is preferred, however, that the substrate be made of copper.
[0025] In each contact of the present invention, at least one of the conductors comprises a plurality of spaced particles that have been embedded into the surface of the conductor in a pre-selected location and particle number density. As contemplated, the spaced particles are embedded and bonded into the surface using the kinetic spray process as described herein and as further generally described in U.S. Pat. No. 6,139,913 and the Van Steenkiste et al article (“Kinetic Spray Coatings,” published in Surface and Coatings Technology, Vol. III, pages 62-71, Jan. 10, 1999), both of which are incorporated herein by reference.
[0026] The particles may be selected from any electrically conductive particle. Due to the impact of the particle on the substrate, it has been found that it is no longer necessary to select the particle from a material that is softer than the material being selected for the conductors. Any electrically conductive particle, including mixtures thereof, may be used in the present invention, including for example, particles comprising monoliths, composites and alloys. Suitable monolithic conductive particles include, for example, tin, silver, gold, and platinum; suitable composite particles include, for example, metal/metal composites of metals that do not easily form alloys; and suitable alloys include, for example, alloys of tin, such as tin-copper, tin-silver, tin-lead and the like. In the present invention, tin or mixtures with tin are preferred. It has been found that particles having a nominal diameter of about 25 microns to about 106 microns are suitable, but the preferred range has a nominal diameter of greater than about 50 microns and more preferably have a nominal diameter of about 75 microns.
[0027] Each embedded particle, due to the kinetic impact force, flattens into a nub-like structure with an aspect ratio of about 5 to 1, reducing in height to about one third of its original diameter. The nubs are discontinuous and define ridges for conductance when mating the conductors and the spaces in between the nubs define valleys for removal of debris produced from the rubbing, or “fretting,” that occurs from relative movement between mated contacts.
[0028] A scanning electron micrograph of the surface of an electrical contact of the present invention is shown in FIG. 1. The lumps (or nubs) are the tin particles and the substrate is copper. The original particle size was about 50 to 65 microns.
[0029] Electrical contacts of the present invention are preferably made using the apparatus disclosed in U.S. Pat. No. 6,139,913. However, the process used is modified from that disclosed in the prior patent in order to achieve the discontinuous layer of particles contemplated in the present invention. The operational parameters are modified to obtain an exit velocity of the particles from the de Laval-type nozzle of between about 300 m/s (meters per second) to less than about 1000 m/s. The substrate is also moved in relation to the apparatus and/or the nozzle to provide movement along the surface of the substrate at a traverse speed of about 1 m/s to about 10 m/s, and preferably about 2 m/s, adjusted as necessary to obtain the discontinuous particle layer of the present invention. The particle feed rate may also be adjusted to obtain the desired particle number density. The temperature of the gas stream is also modified to be in the range of about 100° C. to about 550° C., ie. lower than in a typical kinetic spray process. More preferably, the temperature range is from 100° C. to 300° C., with about 200° C being the most preferred operating temperature especially for kinetic spraying tin onto copper.
[0030] It will be recognized by those of skill in the art that the temperature of the particles in the gas stream will vary depending on the particle size being kinetic sprayed and the main gas stream temperature. Since these temperatures are substantially less than the melting point of the original particles, even upon impact, there is no change of the solid phase of the original particles due to transfer of kinetic and thermal energy, and therefore no change in their original physical properties.
[0031] In a preferred embodiment of the present invention, the electrical contact has a contact resistance of about 1 to 2 milli-ohms and comprises first and second mating copper conductors. Each of these copper conductors further comprises a plurality of spaced tin particles kinetic sprayed onto the surface of the conductors in a pre-selected location and particle number density. The kinetic sprayed particles have an original nominal particle diameter of about 75 microns and are embedded into the surface of each conductor forming a direct metallic bond between the tin and copper. The direct bond is formed when the kinetic sprayed particle impacts the copper surface and fractures the oxidized surface layer and subsequently forms a direct metal-to-metal bond between the tin particle and the copper substrate. Each embedded tin particle has a nub-like shape with the average height of each particle being about 25 microns from the surface of the copper substrate.
[0032] In the preferred process for making electrical contacts of the invention using the apparatus disclosed in U.S. Pat. No. 6,139,913, tin particles are introduced into a focused air stream, pre-heated to about 200° C., and accelerated through a de Laval-type nozzle to produce an exit velocity of about 300 m/s (meters per second) to less than about 1000 m/s. The entrained particles gain kinetic and thermal energy during transfer. The particles are accelerated through the nozzle as the surface of a copper substrate begins to move across the apparatus and/or nozzle at a traverse speed of about 2 m/s within a pre-selected location on the substrate that approximates the shape of the copper conductor contemplated to be stamped out of the copper substrate. While the pattern of particle deposition is random, the location and particle number density are controlled. Upon exiting the nozzle, the tin particles are directed and impacted continuously onto the copper substrate forming a plurality of spaced electrically conductive particles. Upon impact the kinetic sprayed particles transfer substantially all of their kinetic and thermal energy to the copper substrate, fracturing any oxidation layer on the surface of the copper substrate while simultaneously mechanically deforming the tin particle onto the surface. Immediately following fracture, the particles become embedded and mechanically bond the tin to the copper via a metallic bond.
[0033] The resulting deformed particles have a nub-like shape with an aspect ratio of about 5 to 1.
[0034] Performance results of an electrical contact produced according to the present invention and a standard electroplated contact are depicted in FIGS. 2 and 3. FIG. 2 shows the contact resistance as a function of fretting cycles of a prior art electrical contact having two copper conductors electroplated with tin. The electroplating forms a continuous layer as opposed to the discontinuous layer formed by the present process. The results show that the contact initially maintained a resistance of less than about 1 milli-ohm for the first 50 cycles, but then resistance began increasing to reach about 10 milli-ohms at about 120 cycles and over 100 milli-ohms at about 1000 cycles. FIG. 3 shows the contact resistance as a function of fretting cycles of a tin-copper electrical contact made according to the present invention in which two copper conductors were kinetic sprayed with tin particles. The results show that the contact initially maintained a resistance of less than about 1 milli-ohm for about 5000 cycles before resistance began increasing. As demonstrated by FIGS. 2 and 3, the present invention can produce improved electrical contacts that maintain a low resistance over time.
[0035] The table that follows shows other representative results of electrical contacts produced according to the present invention. Contact resistance was tested according to the industry standard. The spots were randomly selected and the contact resistance in mili Ohms is shown for each spot (NT=not tested). The temperature indicated was the temperature of the pre-heated air stream.
CONTACT RESISTANCE Spot Spot Spot Spot Spot Aver- Load 1 2 3 4 5 age Standard Sample (g) (mΩ) (mΩ) (mΩ) (mΩ) (mΩ) (mΩ) Deviation 801 a 100 1.43 0.85 1.62 1.17 0.88 1.19 0.34 (150° C.) 200 0.76 0.52 1.15 0.80 0.57 0.78 0.23 801 b 100 0.92 0.91 0.86 0.99 1.17 0.97 0.12 (200° C.) 200 0.62 0.60 0.64 0.55 0.82 0.67 0.09 901 a 100 1.14 1.00 1.30 1.20 1.75 1.28 0.29 (150° C.) 200 NT NT 0.85 0.90 1.20 0.98 0.19 901 b 100 2.19 0.89 0.89 0.95 1.36 1.26 0.56 (100° C.) 200 NT NT NT NT NT NT
[0036] While the preferred embodiment of the present invention has been described so as to enable one skilled in the art to practice the electrical contacts of the present invention, it is to be understood that variations and modifications may be employed without departing from the concept and intent of the present invention as defined in the following claims. The preceding description is intended to be exemplary and should not be used to limit the scope of the invention. The scope of the invention should be determined only by reference to the following claims. | The present invention is directed to electrical contacts that comprise spaced electrically conductive particles embedded and bonded into the surface of conductors in which the particles have been kinetically sprayed onto the conductors with sufficient energy to form direct mechanical bonds between the particles and the conductors in a pre-selected location and particle number density that promotes high surface-to-surface contact and reduced contact resistance between the conductors. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to vehicle customization and more specifically to customizing vehicle sounds.
[0003] 2. Description of Related Art
[0004] Vehicles typically have a multitude of interior notification sounds associated with vehicle accessories or systems. For example, notification sounds such as chimes, bells, rings, beeps and other audible tones are associated with such things as the vehicle message center, seatbelt warning, door ajar, lights on, low fuel, and other informational notification systems. Typically, these sounds are preset during manufacture of the vehicle and are unable to be changed by the consumer. For example, a chime sound made when leaving the vehicle door in an open position, the audible clicking sound occurring upon actuation of the vehicle turn signal and a chime or bell sound made when the vehicle lights are left on or the vehicle keys are left in the ignition. Each of the sounds designed to notify the vehicle operator or occupants of a particular condition of or the vehicle.
[0005] In addition, there are a plurality of vehicle components and systems that may be associated with some type of notification sound to call attention to or notify the vehicle operator or occupants of a particular vehicle condition or status. Current systems require a plurality of time or sound generators to generate the various sound signals emitted to notify a vehicle operator or onto the end of a particular vehicle condition or status. In addition, even given a plurality of various tones or sounds, it is often difficult for the vehicle operator or occupants to associate the particular sound with a particular event. For example, the chime tone associated with leaving the vehicle lights on may be similar to and thus not easily distinguishable or discernible from the chime tone or sound associated with leaving the vehicle keys in the ignition. Further, even if the chime tones are suitably distinct, it may be difficult for the operator to remember the particular shot event associated with the particular notification sound.
[0006] Increasingly, customers are viewing their vehicle as an extension of their personality and now demand the option of customization, that is, the ability to change these sounds to create a unique individualized vehicle interior. Therefore, what is needed is a system and method that enables a vehicle operator to customize the sound and level thereof emitted in association with a particular vehicle component or event.
SUMMARY OF THE INVENTION
[0007] Accordingly, the present invention provides a user with a method and system for customizing vehicle interior sounds associated with the vehicle accessories and events. In addition, the invention further provides the user with a means and mechanism to customize other aspects of the vehicle interior including lighting, driver information graphics and other instrument and interior schemes. The invention contemplates associating this concept with multiple driver memory settings such as those relating to the seat, steering column, steering wheel, and rearview mirror positions. It should be understood that these customizable features may be changed individually or as a group or theme.
[0008] In one embodiment of the invention, the user can select from a plurality of predefined or pre-selected sounds stored in a database by activating a selection mechanism whereby the operator associates a predetermined sound with a selected event. The invention further contemplates the user creating customized sound data and uploading the customized sound data into the system whereby the customized sound data is associated with a particular event. Accordingly, each user can customize the vehicle profile for their own needs and preferences.
[0009] Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
[0011] FIG. 1 is a combination flowchart/block diagram illustrating one aspect of the present invention.
[0012] FIG. 2 is a flowchart for event/sound mapping.
[0013] FIG. 3 is a graphical depiction of a sound/event table.
[0014] FIG. 4 is a schematic diagram illustrating a system according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
[0016] Referring to FIG. 1 there is shown a combination flowchart/block diagram illustrating the present invention, including disclosing various methods for implementation of the sounds selected by the owner/vehicle operator. The methods include but are not limited to, the vehicle message center if so equipped; pattern activation of certain instrument cluster control switches, i.e., ignition key activation, cruise control buttons; wireless interfaces for example Bluetooth®, 802.11, IRDA infrared technology; and dealer diagnostic interface tools operating in conjunction with onboard circuitry. While the present disclosure sets forth sound customization, it should be understood that it also enables a customer to customize other vehicle features such as interior lighting, driver information and other interior display schemes.
[0017] As illustrated in FIG. 1 block 10 shows the user wishing to change these sounds associated with a particular interior notification sound, for example the sound associated with and occurring when the vehicle door is left ajar. Accordingly, block 12 illustrates the path taken when the user selects a predefined sound, that is, a sound previously stored in associated memory. If the sound is predefined, the user has several options as shown by blocks 14 , 16 , 18 and 20 . Block 14 illustrates use of the message center to select the desired sound. In block 14 , the message center is activated and placed in the sound selection mode. Block 22 illustrates in the next step wherein the user scrolls through a list of available predefined or predetermined sounds. Block 24 shows the next step wherein when the selected sound is located, the user presses an enter button or toggle switch to activate a pointer to associate the selected sound with the associated event, in this case the event is the door being left ajar. Block 26 illustrates the next step of storing the selected sound and associated event in memory.
[0018] If the vehicle does not have a message center or the message center is not suited or programmed for sound selection the sound may be associated with the particular event at the vehicle dealership or service center. Block 16 illustrates a step whereby the dealer selects the input by connecting a computer or other input device to access the software and input a particular sound. Block 24 illustrates the step wherein the dealer activates the pointer to associate the selected sound with the particular event. Once again, block 26 illustrates storing the selected sound and event in memory. In addition, the dealership may have additional sounds for input into the vehicle thereby enabling the vehicle operator to download certain proprietary sounds and themes associated with the particular vehicle.
[0019] Block 18 shows an additional input method utilizing a key or input cycle. Block 28 illustrates the step of the user, through a pattern of actuating the ignition key or some other control button, selecting the various sounds associated with a particular event. Block 20 illustrates a further input method using the key fob to select from various sounds and associate them with predetermined events. Block 30 shows the step wherein the user presses a button or buttons of the key fob to select certain sounds and other parameters. Once the user has selected the desired sound, block 24 illustrates the next step of using the pointer to associate the selected sound with a particular event. All of the methods illustrated in blocks 14 - 20 are suitable for addressing the pointer whereby it associates the selected sound stored in the memory with the particular event.
[0020] While the memory contains a number of pre-selected sounds and predetermined sound themes additional sounds may also be downloaded from a manufacturer's web site. In addition, a controller or other vehicle software may contain a receiver that receives a signal from a manufacturer that sends new sounds directly to the vehicle where they are stored in the memory 26 .
[0021] In some instances a user may wish to select and associate with a particular event a sound that is not stored in memory or is unavailable as a predefined sound, for example a particular piece of music or spoken words. Block 30 illustrates the step of the user selecting a desired sound. The method further includes the step of block 34 wherein a computer-based compression software translates and compresses the sound to an appropriate sound file or byte sequence that can be stored and utilized by the system. Blocks 36 and 38 illustrates two steps by which the sound file or byte sequence is uploaded and stored as illustrated by block 40 . For example, in block 36 a wireless interface is used to perform the step of block 40 that shows storing the byte sequence or sound file in the memory 26 . Block 38 illustrates the step of the dealer performing the step of block 40 and storing the byte sequence or sound file in the memory 26 . Other methods may be used to input the particular sound byte sequence or sound file representing the sounds selected by the user into the memory 26 whereby it can be associated with a particular event.
[0022] FIG. 1 further illustrates a sound synthesizer 42 connected to the memory 26 and a system sound request 46 . Upon receiving notification of a triggering event, for example the vehicle door being left ajar, the systems on request 46 sends a signal to the sound synthesizer 42 to generate the appropriate sound associated with the door being left ajar. Accordingly, the sound synthesizer 42 retrieves from the memory 26 the appropriate sound and through a speaker 44 outputs the selected sound.
[0023] FIG. 2 illustrates a flowchart for event/sound mapping. Block 50 illustrates that the user wishes to map particular or desired sounds to particular events. Block 52 illustrates the next step, which is to select the particular event using the increment/decrement event step shown in block 54 . Once the desired event is selected, block 56 illustrates selecting the desired sound, once again using an increment/decrement sound pointer shown in block 58 . After the event and particular sound are selected, block 60 shows the step of mapping the particular sound with the selected event to create a mapping table. Block 62 shows storing the mapping table in some type of memory or other electronic storage mechanism or media. While FIG. 2 illustrates one method of mapping sounds to events, as set forth above there is a plurality of ways, including use of the message center, to accomplish the association a particular sound with a selected event.
[0024] FIG. 3 illustrates the graphical depiction of a sound/event table. As shown therein a plurality of themes can be programmed for individual users whereby there are multitudes of variations. As indicated in FIG. 3 , block 64 discloses a theme for a first user wherein different sounds are associated with different events. For instance, sound one is associated with the lights being left on, sound two is associated with the message center and sound three is associated with the door being open or ajar. As illustrated, the theme may include a plurality of sounds associated with a plurality events. Block 66 illustrates a theme for a second user wherein both the door open or ajar and lights left on sounds are initially the same. However, the lights left on event also generates a second sound. The second sound may be programmed to come on after a preset time. For example, upon leaving the vehicle lights on, the operator would first hear sound one for a predetermined time and then hear sound two. Sound two presumably being a more intense sound designed to attract the operator's attention to the particular event, in this case the lights being left on. In addition, the intensity of the sound may vary with the length of time. For example, the longer the vehicle door is left ajar, the louder the sound notifying the operator of the event becomes. In addition, a delay or other time limitation may be included. For example, the vehicle operator may delay operation of the door ajar sound for a suitable predetermined period. Thus, the present invention provides a method and apparatus to vary both the sound and characteristics thereof associated with a particular event. Finally, block 68 illustrates a further theme for a third user. Accordingly, the present invention provides for a plurality of various sounds that can be associated with various events. In addition, the particular sounds can be combined or customized to a particular user or be preset in a particular theme.
[0025] FIG. 4 is a schematic illustration of one mechanism for associating a plurality of variable various sounds with a plurality of events. As set forth above, the system seen generally at 70 includes an instrument cluster 72 . A sound module and speaker, shown herein as a chime synthesis module 74 and chime speaker 76 connected to the instrument cluster 72 , generate the selected sounds. The instrument cluster 72 further includes instrument cluster buttons 78 and an instrument cluster display 80 . An ignition switch 82 is also connected to the instrument cluster. A system bus 84 connects various components of the system and transfers data and power between them. The system bus 84 can be a Controller Area Network bus, that is, a differential serial type bus typically used in the automotive industry. Attached to the bus is a plurality of components including an electronic control unit or ECU 86 , an electronic storage mechanism or media shown herein as a memory module 88 , a wireless interface module 90 , a wired interface module 92 , a lighting module 94 and an onboard or other diagnostic link 96 . The system 70 may also include a key fob 98 and key fob receiver 100 . The key fob receiver 100 attached to the system bus 84 and receiving and input signal from the key fob 98 .
[0026] Both the that wireless interface module 90 and the wired interface module 92 can be used to upload information pertaining to sound data, sound files or sound byte sequences to the system. Specifically, the wired interface module 92 may include a USB port, a secure digital multi-media card or a custom flash memory all of which can be used to input information into the system. In addition, while the system 70 shows a separate memory 88 , the wired interface module 92 or wireless interface module 90 may each include a separate memory component. The wireless interface module 90 may include a satellite information receiver, a Bluetooth® receiver, or an IrDA port all of which can be used to upload information.
[0027] The system 70 further includes the lighting module 94 that controls the lighting system in the vehicle. Accordingly, it is contemplated that the system can also control the operation of the vehicle interior lighting system.
[0028] Finally, the ECU 86 operates to control the various sounds emitted from the chime speaker 76 based on input from the chime module 74 , which results from a signal received from the various vehicle systems and components. Accordingly, the ECU 86 upon receiving a signal that the vehicle door is left ajar transmits a corresponding signal to the instrument cluster 72 which correspondingly actuates the chime module 74 and chime speaker 76 to produce an audible sound notifying the vehicle operator that the vehicle door is ajar. In addition, the present invention contemplates controlling the vehicle lighting based upon certain inputs. Thus, should the vehicle operator to leave the keys in the vehicle and ignition, the ECU 86 upon receiving a signal indicating the keys are still in the ignition and a signal that no occupant is in the driver's seat initiates, through the chime module, a custom sound byte notifying the vehicle operator that the keys are still in the ignition. If after a suitable period of time the keys are not removed, the ECU 86 may act through the lighting module 94 to actuate or flash the vehicle interior lights to provide further notification that the vehicle keys are still in the ignition.
[0029] Accordingly, the present invention provides a method and system for modifying vehicle notifications sounds associated with particular events. In particular, the method and apparatus allows the customization of many of the sounds, including sound themes and styles associated with various automobiles. Further it would allow for various sounds including music, entertainment, spoken words, song lyrics, movie quotes, and other sound bytes, including the user's own voice to be used in place of the current chimes and bells associated with many vehicle events, such as leaving the vehicle keys in the ignition. In addition, the present system would allow the vehicle to audibly notify the vehicle user of certain conditions in addition to using the standard warning lights or indicators used in many vehicles.
[0030] Further, while shown herein using a chime module and chime speaker, it is contemplated that the present invention can use the vehicle sound system or other speakers located in the vehicle interior. Thus, audible notification of various events can be emitted through the vehicle sound system or other independent speakers rather than using the chime speaker. Further, it is contemplated that certain events or notification signals could override the radio/stereo output; for example, a low oil pressure signal may initially disable the radio output while the notification signal or sound byte is broadcast through the radio speakers.
[0031] Thus, the present invention provides a vehicle operator with a means of selecting a vehicle interior sound theme or profile using a plurality of selected sounds or a predefined group of sounds. The theme may include a set of warning or alert sounds, instrument cluster backlighting color and intensity, customize driver information graphics, interior lighting schemes, radio presets including station selections and other driver settings such as seat, steering column, steering wheel and rearview mirror positions. In addition to selectable customization by the vehicle operator, the invention further contemplates a predefined group of three to six themes for each vehicle the theme selected based on the intended market segment and desired vehicle/brand image. All themes designed to meet required criteria for audibility, visibility and luminance. The invention contemplates providing customers with the ability to update the entire theme package or portions thereof as new themes and sounds become available.
[0032] The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention. | A method and system for customizing vehicle interior sounds and other indicia associated with vehicle accessories and events. The method enables a vehicle operator to selectively associate a particular sound with a particular event by selecting a desired sound and associating it with a particular event whereby emission of the desired sound occurs upon occurrence of the particular event to notify the vehicle operator of the occurrence of the particular event. Accordingly, the present invention enables a vehicle operator to configure and associate specific vehicle notification with particular events. In addition, the present invention provides a method and system whereby the vehicle operator uploads into the system customized sounds and sound bytes. | 1 |
BACKGROUND AND PRIOR ART
The arylalkyl amines, in particular benzylamine and dibenzylamine are important industrial organic compounds. Benzylamine is a primary amine which is useful as a corrosion inhibitor. Dibenzylamine is a secondary amine which finds use in the production of synthetic penicillins and in the vulcanization of rubber.
Numerous procedures for the production of these amines are described in the literature and include: the reductive amination of benzaldehyde by hydrogen and ammonia in the presence of a catalyst; the catalytic reduction of benzonitrile or benzylhydroxylamine; or the condensation of benzaldehyde and benzylamine followed by catalytic hydrogenation of the intermediate Schiff's base. Generally, benzylamine and dibenzylamine are obtained in poor yield and each amine must be carefully separated from mixtures containing primary, secondary or tertiary amines, imines, aldehydes, alcohols or amides to obtain a high purity product.
For example, it is known that nitriles can be catalytically reduced to the primary amine through the intermediate imine by a wide variety of catalysts as follows:
RC.tbd.N+H.sub.2 →RCH═NH+H.sub.2 →RCH.sub.2 NH.sub.2
the intermediate imine further reacts with the primary amine to produce a Schiff's base with the liberation of ammonia,
RCH═NH+RCH.sub.2 NH.sub.2 ⃡RCH═NCH.sub.2 R+NH.sub.3 ↑
In the presence of a catalyst and hydrogen, the Schiff's base is further reduced to the secondary amine,
RCH═NCH.sub.2 R+H.sub.2 →(RCH.sub.2).sub.2 NH
in a batch process, the above reactions compete for reactants and a variety of reaction products are formed. Many means have been employed to minimize the extent of these reactions including reduction in very dilute organic solvent solutions, solvent selection and catalyst selection. Rylander et al. disclose, in U.S. Pat. No. 3,117,162 and Annals N.Y. Acad. Sci. 214:100-109(1973), a batch process for the reduction of benzonitrile in dilute organic solvent solutions such as hexane, octane, ethanol and benzene by hydrogenation over rhodium, palladium, platinum, or ruthenium catalysts (all 5% on carbon). At best, Rylander et al. obtain benzylamine at 63% yield from a mixed reaction product containing 34% of the secondary amine. The production of dibenzylamine is favored in this process by the selective use of rhodium on carbon or platinum on carbon catalysts, but in all other cases it is obtained as a mixture containing large amounts of the primary amine. In addition, long reaction times, 2 to 21 hours, are required to reduce the benzonitrile and the reaction products must be further separated from very dilute organic solvent solutions. Similarly, Takagi et al. in Sci. Papers Inst. Phys. Chem. Res. 61(3), 114-117(1967), disclose a batch process for the reduction of benzonitrile in ethanol over 3:1 iridium platinum oxide catalyst. This reaction produces about 42% benzylamine and 50% dibenzylamine. In each case long reaction times are required and the reaction products must be separated from very dilute solutions. As a result, these prior art techniques are time consuming and costly.
SUMMARY OF THE INVENTION
In accordance with the present invention, a novel process is provided for the preparation of a reaction product selected from the class consisting of benzylamine and dibenzylamine, which comprises passing benzonitrile and hydrogen countercurrently through a catalyst bed under suitable conditions of temperature and pressure to thereby hydrogenate the benzonitrile and produce the desired reaction product.
DESCRIPTION OF THE INVENTION
In the practice of this invention in the preferred manner, the catalyst is charged into any suitable vertical trickle bed reactor column capable of being heated under moderate pressures, to form a catalyst bed. Examples of such useful catalysts include Raney nickel pellets, zirconium promoted reduced nickel on Kieselguhr tablets, platinum on alumina tablets and the like. It is preferred to use Raney nickel pellets. It will be understood by those skilled in the art that reactor columns will vary in overall length and diameter and the catalyst bed depth may be varied accordingly without affecting the yield or purity of the desired reaction product obtained.
Benzonitrile is fed into the top of the reactor column through a suitable feeding device. At the same time hydrogen is introduced at the bottom of the reactor column at a pressure sufficient to produce the desired reaction product. The benzonitrile and the hydrogen thus flow countercurrently within the reactor bed, the downwardly flowing liquid being thoroughly contacted by the upwardly flowing hydrogen within the catalyst bed. The reactor column and contents are heated by any suitable means up to a temperature sufficient to promote hydrogenation of the benzonitrile in the presence of the catalyst and hydrogen. Usually a temperature between about 50° and 175° C. is sufficient. Higher temperatures tend to produce an undesirable colored product of lower than desired purity. The ratio of the input stream of hydrogen flow (measured at S.T.P.) to the input stream of benzonitrile flow based upon the volumes passed per unit of time can be varied depending upon the desired reaction product to be produced. When benzonitrile and hydrogen are continuously fed into the reactor column, the desired reaction product is produced in the reactor column and is continuously removed from the bottom thereof. Suitable controls and mechanical devices as will be understood by those skilled in the art are provided to permit control of flow rates, temperatures and pressures and thereby maintenance of steady state operation.
The production of the desired reaction product, as stated above, is dependent upon the pressures and the ratios of hydrogen stream flow to benzonitrile stream flow selected. When benzylamine is the desired reaction product to be produced, pressures of greater than about 115 p.s.i.a. and flow ratios of hydrogen to benzonitrile of less than about 600 based upon the relative volumes passed per unit of time are usually found to be sufficient. Flow ratios of hydrogen to benzonitrile of about 420 to 460 based upon the relative volumes passed per unit of time are preferred. Under these conditions, ammonia which is liberated during the course of the reaction accumulates in the column and as a result at equilibrium the reaction is shifted toward the production of primary amine and benzylamine is the principal reaction product. When dibenzylamine is the desired reaction product to be produced, pressures of less than about 115 p.s.i.a. and flow ratios of hydrogen to benzonitrile of greater than about 600 based upon the relative volumes passed per unit of time are usually found to be sufficient. The upper limit of flow ratios of hydrogen to benzonitrile is only limited by the cost of raw materials and recovery of excess hydrogen. Under these conditions, ammonia which is liberated during the course of the reaction is swept from the reactor column by the excess hydrogen flowing therethrough and as a result at equilibrium the reaction is shifted toward the production of secondary amine and dibenzylamine is the principal reaction product.
The following examples are given to further illustrate the method of preparing benzylamine and dibenzylamine and are not intended to limit the invention.
EXAMPLE 1
This example demonstrates the operation of a continuous countercurrent reactor system employing a small scale trickle bed reactor column, approximately 42 inches in length by 1 inch in diameter.
Raney nickel pellets, Grade 5842- crushed, granular nickel-aluminum alloy having the dimensions of about 1/4 in.×1/8 in., supplied by the Davison Chemical Division of W. R. Grace Co., were activated in the conventional manner by leaching about 10 to 12% of the original aluminum content from the surface of the pellets with an aqueous solution of about 7 to 25% by weight, of sodium hydroxide. The pellets were washed with water, followed by further washing with methanol and benzonitrile. About 925 grams of the thus-activated Raney nickel pellets were then charged into the reactor column to a bed depth of about 37 inches.
A. Preparation of Benzylamine
Undiluted, high purity benzonitrile was introduced at the top of the reactor column, prepared in manner described above, at a constant feed rate of 24 ml. per hour, and hydrogen was introduced at the bottom of the reactor column at a constant flow rate of 10.6 liters (S.T.P.) per hour at a pressure of 165 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen-to-benzonitrile of about 440 based upon the volumes passed per unit of time. The column and contents were heated to 100° C. After a steady state condition was achieved, samples of the effluent stream were taken from the bottom of the reactor and analyzed by gas chromatography. The percentages of reaction products as determined by gas chromatography in the following examples express the percent by weight. The effluent stream was composed of 93.2% benzylamine, 5.2% dibenzylamine, and about 1.6% unknown.
The above procedure was repeated at a pressure of 215 p.s.i.a. After a steady state condition was achieved, samples of the effluent stream were taken from the bottom of the reactor and analyzed by gas chromatography. The effluent stream was composed of 94.6% benzylamine and 5.4% dibenzylamine.
B. Preparation of Dibenzylamine
Unidiluted, high purity benzonitrile was introduced at the top of the reactor column, prepared in the same manner as described above, at a constant feed rate of 30 ml. per hour, and hydrogen was introduced at the bottom of the reactor column at a constant flow rate of 73.7 liters (S.T.P.) per hour at a pressure of 75 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen-to-benzonitrile of about 2450, based upon the volumes passed per unit of time. The column and contents were heated to 100° C. After a steady state condition was achieved, samples of the effluent stream were taken from the bottom of the reactor and analyzed by gas chromatography. The effluent stream was composed of 95.3% dibenzylamine, 1.0% benzylamine, 1.0% tribenzylamine, 1.9% cyclohexanemethylbenzylamine, and 0.8% Schiff's base.
The above procedure was repeated at a constant benzonitrile flow rate of 15 ml. per hour and a constant hydrogen flow rate of 121 liters (S.T.P.) per hour at a pressure of 60 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen-to-benzonitrile of about 8070 based upon the volumes passed per unit of time. The column and contents were heated to 100° C. After a steady state condition was achieved, samples of the effluent stream were taken and analyzed by gas chromatography. The effluent stream was composed of 94.6% dibenzylamine, 0.9% benzylamine, 1.1% tribenzylamine, 2.8% cyclohexanemethylbenzylamine and 0.4% Schiff's base.
EXAMPLE 2
This example demonstrates the operation of a continuous countercurrent reactor system employing a pilot scale trickle bed reactor column, approximately 72 inches in length by 4 inches in diameter.
About 26 kg. of Raney nickel pellets activated in the conventional manner described in Example 1 were charged into the reactor column to a bed depth of about 66 inches. Undiluted, high purity benzonitrile was then introduced at the top of the reactor column at a constant feed rate of 1080 ml. per hour, and hydrogen was introduced at the bottom of the reactor at a constant flow rate of 1152 liters (S.T.P.) per hour at a pressure of 55 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen-to-benzonitrile of about 1067, based upon the volumes passed per unit of time. The column and contents were heated to 100° C. After a steady state condition was achieved, samples of the effluent stream were taken from the bottom of the reactor and analyzed by gas chromatography. The effluent stream was composed of 92.8% dibenzylamine, 1.8% benzylamine, 2.0% tribenzylamine and 1.7% cyclohexanemethylbenzylamine. No benzonitrile and only 1.5% of Schiff's base were found.
EXAMPLE 3
A small scale trickle bed reactor column, approximately 42 inches in length by 1 inch in diameter, was prepared in the following manner. About 1000 grams of Girdler G-69, zirconium promoted reduced nickel on kieselguhr tablets, having the dimensions of about 3/16 in.×1/8 in., supplied by Chemetron Chemicals Division of Chemetron Corporation, were charged into the reactor column to a bed depth of about 40 inches.
Undiluted, high purity benzonitrile was introduced at the top of the reactor column at a constant feed rate of 18 ml. per hour and hydrogen was introduced at a constant flow rate of about 8.0 liters (S.T.P.) per hour at a pressure of 265 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen to benzonitrile of about 440, based upon the volumes passed per unit of time. The column and contents were heated to about 100° C. After a steady state condition was achieved, samples of the effluent stream were taken and analyzed by gas chromatography. The effluent stream was composed of 92.7% benzylamine, 5.5% dibenzylamine, 0.1% tribenzylamine, 0.8% benzonitrile, and 0.8% unknown.
EXAMPLE 4
About 875 grams of 1% platinum on alumina tablets, 3/16 in.×1/8 in., supplied by Englehard Industries Division, were charged into a small trickle bed reactor column to a bed depth of about 35 inches. Undiluted high purity benzonitrile was then introduced at the top of the reactor column at a constant feed rate of 42 ml. per hour, and hydrogen was introduced at the bottom of the reactor column at a constant flow rate of 108 liters (S.T.P.) per hour at a pressure of 95 p.s.i.a. This corresponds to a countercurrent flow ratio of hydrogen to benzonitrile of about 2570, based upon the volumes passed per unit of time. The column and contents were heated to 100° C. After a steady state condition was achieved, samples of the effluent stream were taken from the bottom of the reactor and analyzed by gas chromatography. The effluent stream was composed of 89.2% dibenzylamine, 0.1% benzylamine, 0.8% benzonitrile and 8.6% of a mixture of cyclohexanemethylbenzylamine and dicyclohexanemethylamine. | A process is provided for preparing benzylamine and dibenzylamine by passing benzonitrile and hydrogen counter-currently through a catalyst bed under suitable conditions of temperature and pressure to hydrogenate the benzonitrile and thereby produce the desired reaction product. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
Provisional Patent Application Ser. No. 60/384,978, filed Jun. 3, 2002, for “Multi-Bit Patricia Trees” and Utility Patent Application based thereon, Ser. No. 10/448,528, filled May 30, 2003, entitled “Multi-Bit Patricia Trees”, which are incorporated herein by reference, describe the operational parts and operation of a Patricia tree. This invention describes an algorithm required to maintain information and tree state to support continuous tree searches, leaf inserts, leaf updates, leaf reads, and leaf deletes.
FIELD OF THE INVENTION
The invention describes how to maintain a consistent and correct Patricia tree while doing leaf operations, i.e. insertion and deletions of leaves, including how to manage a prefix of a prefix (sometimes referred to as “nested prefix” or “bird”).
BACKGROUND INFORMATION
A conventional technique for forwarding computer messages to any one of a number of final destinations is to use a pattern of bits to identify the destination of a particular message, and then walk the pattern bits through a Patricia tree structure of a direct table and, if necessary, through one or more Pattern Search Control Blocks (PSCB's). One such technique is shown and claimed in application Ser. No. 10/448,528 filed May 30, 2003, entitled “Multi-Bit Patricia Tress”. In this application, the PSCB's are multibit, thus reducing the latency time. However, this problems in updating the Patricia tree. The present invention describes a technique for updating the Patricia tree by inserting and deleting leaves without interrupting the functioning of the Patricia tree.
SUMMARY OF THE INVENTION
According to the present invention, a technique is provided to either insert or delete a leaf in a Patricia tree while maintaining tree integrity without shutting down the functioning of the tree. A pattern of bits is identified as either a leaf to be inserted or deleted. Using the pattern, the tree is walked once to identify the location of the leaf to be deleted or the location where the leaf is to be inserted. If it is a delete operation, the leaf to be deleted is identified and deleted and any relevant PSCB modified, if necessary. If it is an insert operation, the tree is walked a second time to insert the leaf and reform or create any PSCB in the chain that needs to be reformed or created. The technique also is applicable to inserting or deleting a prefix of a prefix, also known as a nested prefix.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an example of a tree with two patterns and its associated prefix of a prefix PSCB.
FIG. 2 shows how 4 bits can be decoded to a 30 bit prefix of a prefix table.
FIG. 3 shows inserting at an existing PSCB, before key is inserted.
FIG. 4 shows inserting at an existing PSCB, after key is inserted.
FIG. 5 shows inserting a new PSCB before an existing PSCB, before key is inserted.
FIG. 6 shows inserting a new PSCB before an exiting PSCB, after key is inserted.
FIG. 7 shows inserting a new PSCB after an existing PSCB, before key is inserted.
FIG. 8 shows inserting a new PSCB after still existing PSCB, after key is inserted.
FIG. 9 shows a pattern that not the full length but ends on a 4 bit boundary is treated as a leaf pattern and makes the not full length pattern a prefix.
FIG. 10 shows that after the key (2020380) is inserted, this makes the not full length pattern 202018 a prefix.
FIG. 11 shows inserting a pattern whose length is not on a 4 bit boundary.
FIG. 12 shows after the pattern whose length is not a 4 bit boundary is inserted in the History Prefix of a prefix and Search Prefix of a prefix PSCB. Its LCBA address is copied in the real PSCB 12 .
FIG. 13 shows deleting a leaf causes a PSCB 12 to be collapsed.
FIG. 14 shows the PSCB 12 after leaf has been deleted.
FIG. 15 shows that deleting a prefix of a prefix causes 2 PSCB 12 's to be removed.
FIG. 16 shows after prefix of a prefix is deleted.
FIG. 17 shows deleting a prefix while the next longest prefix exists.
FIG. 18 shows after the prefix delete for deleting a prefix while the next longest prefix exists, and
FIG. 19 is an illustration of a computer disc medium on which the program may be stored.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In this application, different terms, including abbreviations and acronyms, are used. Table I listed below gives a definition of certain of the terms:
TABLE I
Terms (includinig abbreviations and acronyms)
Term
Definition
NPA
Next PSCB address
NBT
Next bit to test
LCBA
Leaf control block address
Bird
Prefix of a prefix or nested prefix
Trail End Flag
End of search - entry points to a leaf
SRAM
Static random access memory
DRAM
Dynamic random access memory
DT
Direct table
D. . .
DRAM identifier
Mem
Memory
LPM
Longest prefix match
PSCB
Pattern Search Control Block
Distpos
Distinct position
This invention describes elements and algorithms required to maintain a consistent and correct Patricia tree while search operations may be in progress. The entries in the tree structure are search keys or patterns of X bits in length. In addition, the management of the prefix of a prefix requires only 16 of 30 possible entries to be placed in the operational prefix of a prefix table. The remaining history prefix of a prefix must be maintained to allow for updating of the operational table during insertions and deletions. A prefix of a prefix is a bit pattern that has a length less than another bit pattern, but all the bits of the shorter pattern exactly match the equivalent bits in the longer pattern. For example, two patterns, pattern (A) and pattern (B):
(A) 20 20 39 48
length 29 (decimal) prefix of a prefix
(B) 20 20 39 4A
length 32 (decimal) prefix
In this example, pattern (A) is a prefix of the prefix (B). It has a shorter length (29<32) and all the 29 bits of (A) match the equivalent 29 bits of (B).
(It should be noted that, unless otherwise specified, the coding is in hexadecimal notation.)
This process is necessary to make use of the algorithms described in Provisional Application Ser. No. 60/384,978. The Multibit LPM algorithm uses 4 bit Patricia Tree nodes Pattern Search Control Blocks (PSCB) 12 . Each PSCB 12 node holds 2 m possible combinations of bits where “m” is commonly 4 or 1. Grouping bits together (in this case 4) minimizes the number of nodes to walk during a search, which increases the search performance. Each PSCB 12 entry contains either a leaf (end of trail) or pointer to another PSCB 12 . Prefixes of prefixes are stored in a corresponding slower memory to each PSCB 12 . A pattern is broken into groups of 4 bits after the Direct Table (DT) bit size is factored out. Each group of 4 bits has an associated index. The Next Bit to Test (NBT) field in the PSCB 12 or NBT is the index for the next PSCB 12 . Each PSCB 12 entry (one of 16) can either point to a next node or the end of the pattern or leaf, i.e. end of trail.
The Next PSCB 12 Address (NPA) 14 in the PSCB points to another node. The end bit in each entry indicates whether the entry contains a leaf or another node. The mode bit indicates whether the next PSCB 12 is a 4 bit PSCB or 1 bit PSCB 12 . In the following description, only 4 bit PSCB 12 is discussed. The prefix of a prefix bit indicates whether a prefix whose length ends at this index exists in the corresponding PSCB 12 . A prefix of a prefix length can be 1, 2, 3 or 4 bits long at an index. There are 30 possible combinations of a prefix of a prefix associated with one PSCB 12 (see FIG. 2 ). The hardware looks in the operational prefix of prefix table during searches to find the longest prefix match. The software needs to keep a history prefix of a prefix table to keep track of what prefixes have been inserted and deleted in order to store the longest prefix match in the operational prefix of prefix table. A 4 bit prefix of a prefix will be stored in the operational prefix of prefix table when a longer pattern exists in the tree. If no longer pattern exists, then the 4 bit prefix of prefix is the end of the trail in the main PSCB 12 . For example, pattern 20 20 39 48 length 32 will be stored in the operational prefix of prefix table when a longer pattern 20 20 39 48 40 length 40 exists in the corresponding main PSCB 12 . Any prefix of a prefix less than 4 will be stored always in the history prefix of a prefix. If a 4 bit prefix of a prefix does not exist, then the longest prefix is stored additionally in the operational prefix of prefix table as well as the corresponding main PSCB 12 at multiple entries (2 entries for 3 bits, 4 entries for 2 bits and 8 entries for 1 bit). The prefix of a prefix map is a word that represents the 30 possible prefix of a prefix combinations. When a prefix of a prefix is inserted, the corresponding prefix of a prefix number gets turned on and off when deleted. FIG. 1 shows an example of a tree with two patterns and its associated history prefix of a prefix NPA 14 .
Multibit Insert (in this Case 4 Bits)
This section describes the Multibit Insert Algorithm.
One of the fundamental principles is that an attempt is made to define the tree by only using enough information to distinguish the unique characteristics of each pattern being maintained within the free. Each PSCB 12 represents a set of 4 bits (y bits) which contain distinguishing information between different patterns. The number of PSCB's 12 will be minimized to the number of PSCB's 12 required to represent a set of patterns whenever possible. PSCB's will only exist for bit positions that contain distinguishing information (bits that do not match or length not the same) and that are required to uniquely identify a pattern from any other patent. When searching, one does not look at all the bits of the key, only the bits required to uniquely identify the leaf being searched. By looking at these unique bits 4 bits at a time, one can significantly decrease the search time to find the specific information related to the search key. The tree is walked twice based on the insert key's pattern. The first time through is to find the insert point or the index where the pattern of the new key first differs from the patterns in the tree starting from the left most bit (Distinguishing Position or Distpos). The second time is to modify the closest nodes to change the chaining of the tree.
Walk the Tree Based on the Insert Key
Starting with the Direct Table Entry, skip the number of bits specified in the Direct Table Bit Size starting from the most significant bit of the insert key. The first entry or DT entry will either indicate a leaf address (LCBA) or a next pointer address NPA 14 , along with a next bit to test (NPA 14 or NBT). If it is an NPA 14 and NBT entry, take the next four bits of the insert key starting as indicated by the NBT and use the 4 bits as an index to the next PSCB 12 or NPA 14 , continue to follow the chain until the entry is at the end of tail bit is set, a leaf address. If the end is an empty entry, find the nearest leaf address by looping through 16 entries of the current PSCB 12 . If none of the 16 entries is a leaf address, take the first next pointer address and loop through that PSCB's 16 entries until a leaf is found. A valid tree must have a leaf at the end of the chain. Determine the most significant bit distinguishing position between the found leaf address's pattern in the tree and the insert key.
Find the Insertion Point
The Distpos value indicates where the insert key should be inserted. The Distpos value indicates where two patterns differ. Subtract the DT size from the Distpos value, and then round that value down to a multiple of 4 bits grouping, and that is the insertion point. However, if two patterns are prefixes of each other, then the shorter length becomes the value to be rounded down.
Second Walk to Insert
Walk the tree the second time based on the next bit to test in the tree and the extracted bits from the insert key. If the rounded down insert value is equal to the NBT, then insert the new key at an existing PSCB 12 . If the rounded down insert value is less than the NBT, then insert the new key before the next PSCB 12 . If the rounded down insert value is greater than the NBT, continue to the next PSCB 12 until there's no more PSCB's. If the rounded down insert value is greater than the last NBT, then there is a need to insert after that PSCB 12 .
FIG. 3 shows an insert a key at an existing PSCB 12 , before key is inserted.
FIG. 4 shows inserting at an existing PSCB 12 , after key is inserted.
FIG. 5 shows inserting a new PSCB 12 before an existing PSCB 12 , before key is inserted.
FIG. 6 shows inserting a new PSCB 12 before an exiting PSCB 12 , after key is inserted.
FIG. 7 shows inserting a new PSCB 12 after an existing PSCB 12 , before key is inserted.
FIG. 8 shows inserting a new PSCB 12 after still existing PSCB 12 , after key is inserted.
Prefix of Prefix Insert
Table II below shows in the right two columns the operational prefix of prefix table, and in the left two columns the history prefix of prefix table:
TABLE II
History NP PSCB and Search NP PSCB Associated with Real PSCB
History NP PSCB
History NP PSCB
Search NP PSCB
Search NP PSCB
NP#17 and 18 LCBAs
NP#19 and 20 LCBAs
0000's LCBA 0001's LCBA
0010's LCBA 0011's LCBA
NP#21 and 22 LCBAs
NP#23 and 24 LCBAs
0100's LCBA 0101's LCBA
0110's LCBA 0111's LCBA
NP#25 and 26 LCBAs
NP#27 and 28 LCBAs
1000's LCBA 1001's LCBA
1010's LCBA 1011's LCBA
NP#29 and 30 LCBAs
NP Map in Bottom Word
1100's LCBA 1101's LCBA
1110's LCBA 1111's LCBA
Layout of NP Bit Map, each number is associated with an NP number
x
30
29
28
27
26
25
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
X
Prefixes of prefixes are handled separately. Length of Keys that end on a 4 bit boundary, even if it is not a full pattern, will be treated as a full bit pattern as long as the 4 bit pattern is not a prefix of some other pattern. When another key is inserted and the 4 bit pattern becomes a prefix, it will be treated as any other prefix of prefix. When a prefix of prefix length is less than 4 bits at an index, the prefix of prefix Address or LCBA gets stored in the history prefix of prefix table 16 (also in FIG. 1 ) and the corresponding prefix of prefix Number is turned on. If this prefix of a prefix is the longest prefix in the PSCB 12 , it gets stored in the corresponding operational prefix of a prefix table 16 entries. For example, if prefix of a prefix Number 26 is the only prefix of a prefix received, its LCBA gets copied into the operational prefix of a prefix table entries 4 , 5 , 6 , and 7 . Also, the LCBA gets copied into the real PSCB 12 with the prefix of a prefix bit on if those entries are empty or the leaf in the real PSCB 12 entry has a shorter length than the prefix of a prefix length. If the real PSCB 12 entries have a leaf that has a longer length or a Next Pointer Address, it will not get copied with the prefix of a prefix Address.
FIG. 9 shows a pattern that not the full length but ends on a 4 bit boundary is treated as a leaf pattern and makes the not full length pattern a prefix.
FIG. 10 shows that after the key (2020380) is inserted, this makes the not full length pattern 202018 a prefix
FIG. 11 shows inserting a pattern whose length is not on a 4 bit boundary.
FIG. 12 shows after the pattern whose length is not a 4 bit boundary is inserted in the history prefix of a prefix and operational prefix of a prefix table. Its LCBA address is copied in the real PSCB 12 .
Multibit Delete
When deleting a key, first one searches the key in the tree. If the key is not in the main tree, one makes sure it is not a prefix of a prefix. If it is a prefix of a prefix, search in the prefix of a prefix memory. If a key is not found, then a positive response is returned to confirm that the key is deleted anyway. When a key is found, it gets taken out of the PSCB 12 first. The second step is to try to collapse the PSCB's. One needs to update the PSCB 12 at the earliest point of the tree (left most PSCB 12 as one walks the tree) so not to break the tree search that may be occurring on a different thread or branch.
Walk Tree Based on Delete Key
Starting with the Direct Table Entry, skip the number of bits specified in the Direct Table Bit Size starting from the most significant bit of the delete key. Based on the NBT at each node in the tree, extract the 4 bits from the delete key to find the correct index into the next PSCB 12 . If the delete key is a full length key, then by following the tree, the last leaf in the tree should be the leaf to be deleted if the key is in the tree. If the delete key is not a match, then return a positive acknowledgement anyway. If the delete key is a prefix, then it could be encountered in one of two ways: If the length of the delete key is less than or equal to the Next Bit to Test, or if the length of the delete key is less than the last leaf in the tree.
Key to Delete is a Leaf
When the key to be deleted is a found leaf, then the most number of PSCB's to collapse is one. If the prefix of a prefix indicator is on, then need to go to the corresponding history prefix of a prefix table to determine if a prefix length of 4 has been received. If so, it needs to be moved to the real PSCB 12 and removed from the operational prefix of a prefix table. If no other shorter prefix exists, then the prefix of a prefix indicator in the real PSCB 12 can be turned off. If a shorter prefix exists at that PSCB 12 , it will be updated in the operational prefix of a prefix table, and the prefix of a prefix indicator in the corresponding real PSCB 12 is left on. If no prefix length of 4, then obtain the next longest prefix and copy it in the real PSCB 12 entry with its address. If the prefix of a prefix indicator is off, then zero the PSCB 12 entry. Loop through all the entries of that PSCB 12 , if there is only one entry that is not empty, then move that entry to the previous PSCB 12 's entry. Write the previous PSCB 12 and free the old PSCB 12 and leaf found. If there are more than one non-empty PSCB 12 entries, just write the PSCB 12 and free the leaf found.
FIG. 13 shows deleting a leaf causes a PSCB 12 to be collapsed.
FIG. 14 shows the PSCB 12 after Leaf has been deleted.
Key to Delete is a Prefix of a Prefix
When the key to be deleted is a prefix of a prefix, then the most number of PSCB's to collapse is two. The reason is a prefix of a prefix length that is not on a multiple of 4 must be stored at the PSCB's index that is rounded down for that prefix length. So when the last prefix is deleted in a PSCB 12 with no other entries, the previous PSCB 12 may contain the only non-zero entry which is the pointer to the PSCB 12 that contained the deleted prefix.
FIG. 15 shows that deleting a prefix of a prefix causes 2 PSCB's to be removed.
FIG. 16 shows a leaf 18 after prefix of a prefix is deleted.
When deleting a prefix of a prefix, one must first check the prefix of a prefix Map in history prefix of a prefix table 16 to see if the prefix of a prefix exists in the tree. If not found, return a positive acknowledgment. If found, search for the next longest prefix of a prefix that is a prefix of a prefix to be deleted within that PSCB 12 . If one exists, then replace the next longest prefix in the entries that the deleted prefix exists in the operational prefix of a prefix table entries and the real PSCB 12 entries. If no next longest prefix match is found, replace with zeros. Once the prefix has been removed from the history prefix of a prefix table, operational prefix of a prefix table and real PSCB 12 , then try to collapse the PSCB 12 's if possible to a leaf 18 .
FIG. 17 shows deleting a prefix while the next longest prefix exists.
FIG. 18 shows after the prefix delete for deleting a prefix while the next longest prefix exists.
FIG. 19 depicts a computer disc medium 20 having the computer program to perform the method described herein embedded in the medium 20 , which program when executed by a computer will perform the method described herein.
While preferred embodiments of the invention have been described herein, variations in the design may be made, and such variations may be apparent to those skilled in the art of computer architecture, systems and methods, as well as to those skilled in other arts. The present invention is by no means limited to the specific programming language and exemplary programming commands illustrated above, and other software and hardware implementations will be readily apparent to one skilled in the art. The scope of the invention, therefore, is only to be limited by the following claims. | A technique is provided to either insert or delete a leaf in a Patricia tree having a direct table and a plurality of PSCB's which decode portions of the pattern of a leaf in the tree without shutting down the functioning of the tree. A leaf having a pattern is identified as either a leaf to be inserted or deleted. Using the pattern, the tree is walked once to identify the location of the leaf to be deleted or the location where the leaf is to be inserted. If it is a delete operation, the leaf to be deleted is identified and deleted, and any relevant PSCB modified, if necessary. If it is an insert operation, the tree is walked a second time to insert the leaf and reform or create any PSCB in the chain that needs to be reformed or created. The technique also is applicable to inserting or deleting a prefix of a prefix. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority of Korean Patent Application No. 98-1854, filed Jan. 22, 1998.
FIELD OF THE INVENTION
The present invention relates to a shadow mask for a cathode ray tube (CRT) and a method of manufacturing the same. More particularly, the present invention relates to a shadow mask for a CRT and a method of manufacturing the same in which a carburization process is used to produce the shadow mask, thereby realizing improvements in tensional strength and the elongation rate.
BACKGROUND OF THE INVENTION
A conventional shadow-mask-type CRT comprises an evacuated envelope having therein a viewing screen comprising an array of phosphor elements of three different emission colors arranged in a cyclic order, means for producing three convergent electron beams directed towards the screen, and a color selection structure or shadow mask comprising a thin multi-apertured sheet of metal precisely disposed between the screen and the beam-producing means. The shadow mask shadows the screen, and the differences in convergence angles permit the transmitted portions of each beam to selectively excite phosphor elements of the desired emission color.
The conventional CRT shadow mask is typically manufactured by first coating a photoresist on a thin metal plate made of Invar or aluminum-killed (AK) steel. The plate is then exposed to light, developed and etched to form a plurality of holes therein. Thereafter, the plate formed with the holes is annealed using a heat-treating process in a hydrogen atmosphere at a high temperature, thereby removing residual stress and providing malleability to the plate. The plate is then formed into a predetermined mask shape by the use of a press, after which the plate is cleaned to remove all contaminants from the surface thereof including fingerprints, dust and other foreign substances. Finally, a blackening process is performed on the shaped plate to prevent doming of the same, thereby completing the manufacture of the shadow mask.
The shadow mask acts as a bridge between electron beams emitted from three electron guns (means for producing three convergent electron beams) and red, green and blue phosphor pixels formed on the panel, ensuring that the electron beams land on the correct phosphor pixels. Accordingly, any deviation of the shadow mask from its original position acts to mis-direct the electron beams to excite the unintended phosphor pixels.
The shadow mask can be repositioned in the CRT if the same receives external shock or vibrations, or as a result of the impact from speakers mounted in the system to which the CRT is applied. That is, if the CRT receives a substantial degree of such forces, the shadow mask moves in the CRT such that electron beams passing therethrough land on the wrong phosphor pixel, thereby deteriorating color purity. This will be described in more detail hereinbelow.
FIG. 1 shows a partial sectional view of a conventional CRT used to describe the shifting of a shadow mask caused by an external shock. As shown in the drawing, the CRT includes a panel 1 , a phosphor screen 2 formed on an inner surface of the panel 1 , and a shadow mask 6 fixedly suspended a predetermined distance from the phosphor screen 2 and having a plurality of apertures (not shown) formed therein. The shadow mask 6 is mounted to a side wall of the panel 1 . That is, a mask frame 5 joined to a periphery of the shadow mask 6 is coupled to a spring 4 , and the spring 4 is connected to a stud pin 3 protruding from the side wall of the panel 1 . An electron gun 11 is mounted in a funnel (not shown) of the CRT and emits electron beams 10 in a direction toward the shadow mask 6 .
When the CRT receives a substantial external shock or vibrations, the shadow mask 6 is shaken and moves from its initial position to a deviated position 7 . As a result, the electron beams 10 emitted from the electron gun 11 pass through an incorrect aperture of the shadow mask 6 . That is, an electron beam that is intended to pass through a predetermined aperture 8 of the shadow mask 6 , comes to pass through an incorrect aperture 9 as a result of the shadow mask 6 moving to the deviated position 7 . Accordingly, a position P 1 on the phosphor screen 2 on which the electron beam 10 lands is altered to deviated position P 2 , resulting in the excitation of the wrong phosphor pixel. This causes shaking of the displayed picture, a reduction in color purity and other picture quality problems.
Furthermore, in the case where the CRT receives an extreme shock, for example if the system in which the CRT is installed is dropped, it is possible for the shadow mask 6 to become deformed. An example of this is shown in FIG. 2 in which a deformed area 12 is illustrated. When electron beams 10 pass through the deformed area 12 , the above problems of shaking of the displayed picture and a reduction in color purity occur, in addition to the generation of spurious colors.
To remedy the above described problems, Japanese Patent Laid-Open No. Sho 62-223950 discloses a technique of improving tensional strength of the shadow mask by forming a plating layer thereon. However, aperture size is decreased when using this technique.
Also, Japanese Laid-Open Nos. Sho 56-121257 and Hei 1-276542 each disclose a technique of improving tensional strength of the shadow mask by heat treating the same in a gaseous atmosphere. However, in these conventional methods, the shadow mask is thermally deformed as a result of heat treating the same for long periods during the manufacturing process.
SUMMARY OF THE INVENTION
The present invention has been made in an effort to solve the above problems.
It is an object of the present invention to provide a shadow mask for a cathode ray tube (CRT) in which improvements in tensional strength and the elongation rate of the shadow mask are realized such that deformation of the shadow mask caused by external shock is prevented.
It is another object of the present invention to provide a shadow mask for a cathode ray tube (CRT) in which an improvement in the modulus of elasticity for the shadow mask is attained so that the same is not negatively influenced by external vibrations and vibrations caused by the operation of speakers in a system to which the CRT is used.
It is still another object of the present invention to provide a method of manufacturing a shadow mask for a CRT in which no thermal deformation of the shadow mask occurs during the manufacture of the same.
To achieve the above objects, the present invention provides a shadow mask for a CRT and a method manufacturing the same, the shadow mask includes a solid solution hardening material and a precipitation hardening material. The method includes the steps of heat-treating a metallic plate having a plurality of apertures formed therein using a carburizing gas, and press-forming the metallic plate into a shadow mask shape.
According to a feature of the present invention, the solid solution hardening material and the precipitation hardening material comprise carbon.
According to another feature of the present invention, the amount of carbon contained in the shadow mask is 0.01 to2.0 parts by weight based on the weight of the shadow mask.
According to yet another feature of the present invention, the shadow mask is made of a low thermal expansion material.
According to still yet another feature of the present invention, the shadow mask is made of AK steel or Invar.
According to still yet another feature of the present invention, the carburizing gas comprises an RX gas and a propane gas.
According to still yet another feature of the present invention, the temperature of the heat-treating step ranges from 600 to 1000° C.
According to still yet another feature of the present invention, the heat-treating step is conducted for a period of 0.1 to 5 hours.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of the specification and, together with the description, serve to explain the principles of the invention:
FIG. 1 is a partial sectional view of a conventional CRT used to describe shifting of a shadow mask caused by an external shock;
FIG. 2 is a partial sectional view of a conventional CRT used to describe damage to a shadow mask caused by an extreme external shock; and
FIG. 3 is a graph illustrating the tensional strength and the elongation rate of a shadow mask manufactured without having undergone a conventional annealing process;
FIG. 4 is a graph illustrating the tensional strength and the elongation rate of a shadow mask manufactured after having undergone a conventional annealing process; and
FIG. 5 is a graph illustrating the tensional strength and the elongation rate of a shadow mask manufactured using a carburization process according to a preferred embodiment of the present invention.
FIG. 6 depicts a shadow mask according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
A CRT shadow mask of the present invention is made of a low thermal expansion material, such as AK steel or Invar, including a solid solution hardening material and a precipitation hardening material. A shadow mask 6 according to the invention having a solid-solution and precipitation surface hardening layer 13 is shown in FIG. 6 .
An inventive method of manufacturing a shadow mask for CRTs is described hereinafter.
A predetermined number of metallic plates made of a low thermal expansion material such as aluminum-killed (AK) steel or Invar, and having a plurality of apertures formed in a predetermined area to form aperture portions, is stacked and loaded on a tray. After setting a pre-heating furnace to a temperature ranging from 500 to 700° C., the tray having the stacked metallic plates thereon is placed in the pre-heating furnace.
Next, a reacting furnace is set to a temperature over 150° C., and a carburizing gas comprising an RX gas and a propane gas is fed into the reacting furnace. Here, the RX gas comprises 40% H 2 , 40% N 2 and 20% CO. The carburizing gas is injected into the reacting furnace at a rate of 5 to 25 liters per minute, and the propane gas is injected therein at a rate of 1 to 10 liters per minute. Subsequently, the temperature in the reacting furnace is increased to between 600 and 1000° C., and the gaseous atmosphere therein is suitably maintained, after which the metallic plates in the pre-heating furnace are transferred to the reacting furnace.
If the temperature in the reacting furnace is maintained within the range described above, the RX gas and the propane gas decompose, thereby generating free carbons and a minute quantity of nitrogen. The free carbon atoms and nitrogen atoms effectively permeate the shadow mask. At this time, since mainly a source of free carbon is generated, the resulting effects are almost wholly those resulting from the permeation of the free carbon, rather than that of free nitrogen.
The metallic plates are heat-treated in the carburizing gas atmosphere inside the reacting furnace for between 0.1 and 5 hours. A heat treating time of less than 0.1 hours results in the insufficient reaction between the metallic plates and the gases, while it is needless to surpass 5 hours since the effects of heat-treating the metallic plates are fully realized before this time.
If the temperature of the reacting furnace is not increased to reach the lower limit of 600° C., the separation of the gases does not occur, and the heat-treating process is not effective. If the temperature exceeds 1000° C., deformation of the shadow mask may occur. Moreover, it is possible to directly place the metallic plates in the reacting furnace without first heating the same in the pre-heating furnace. However, placing the metallic plates first in the pre-heating furnace enables a more gradual increase in the temperature of the metallic plates, in addition to preventing an abrupt temperature decrease of the same after the heat-treating process.
After the carburization process is completed, the temperature in the reacting furnace is reduced to 150° C. while the atmosphere in the same is maintained in the present state. When this temperature is reached, the injection of gas into the reacting furnace is discontinued. Next, the metallic plates are removed from the reacting furnace and then press formed into the desired shadow mask shape.
Because of the limited thickness of the metallic plates used to form the shadow masks, a rolling process must be undertaken a number of times during manufacture. Therefore, following the formation of the apertures in the metallic plates using an etching process, an annealing process is required before press-forming the metallic plates into the desired shape. As shown in FIG. 3, if the annealing process is not performed, although the tensional strength of the shadow mask is high, the elongation rate is low, thereby making it impossible to press-form the metallic plates into the shadow mask shape. Accordingly, it is necessary to conduct the annealing process. However, as shown in FIG. 4, annealing the metallic plates increases the elongation rate.
Therefore, in the present invention, rather than using the conventional annealing process, a carburization process is used, thereby increasing both the elongation rate and the tensional strength of the metallic plates used to manufacture the shadow masks. With regard to the carburization process, carbon monoxide (CO) is generated using RX gas and propane gas in a reaction furnace maintained at a high temperature. The carbon monoxide is permeated or diffused in the shadow masks such that a Fe—Ni—C compound or a reaction material such as Fe 3 C is formed as a result of the reaction between the carbon monoxide and the shadow masks. The carbon compound is employed and precipitated in a matrix of the metallic plates used to make the shadow masks, thereby hardening the same. At this time, the amount of carbon contained in the shadow mask is 0.01 to 2.0 parts by weight based on the weight of the shadow mask.
As can be seen in the graphs, the tensional strength of the shadow mask manufactured using the method of the present invention approximates that of the prior shadow mask not having undergone the annealing process and is significantly greater (roughly 100 Mpa) than the conventional annealed shadow mask. Further, the elongation rate of the inventive shadow mask is far greater than the non-annealed conventional shadow mask, and slightly improved over the annealed conventional shadow mask.
Accordingly, defects to the shadow mask occurring during the various manufacturing processes are minimized, and the shifting and deformation of the shadow mask caused by external shocks are reduced. Further, it is easier to roll-form the metallic plates used to manufacture the shadow mask after it has undergone the heat-treating process, and grains can be more evenly formed such that a sufficient elongation rate can be obtained. Additionally, since the modulus of elasticity of the inventive shadow mask is increased, shaking caused by external vibrations and vibrations generated by speakers is reduced.
The present invention is explained in more detail with reference to the following example.
EXAMPLE 1
A predetermined number of metallic plates, having a plurality of apertures formed over a predetermined area to form aperture portions, were stacked and loaded on a tray. Next, a pre-heating furnace was set and maintained at 650° C., after which the tray having the stacked metallic plates thereon was placed in the pre-heating furnace.
A reacting furnace was heated to a temperature over 150° C., and a carburizing gas comprising a RX gas and a propane gas was fed into the reacting furnace at a rate of 15 liters per minute for the RX gas and 3 liters per minute for the propane gas. Subsequently, the temperature in the reacting furnace was increased to 850° C., and the gaseous atmosphere therein was suitably maintained, after which the metallic plates in the pre-heating furnace were transferred to the reacting furnace.
The metallic plates were heat-treated in the carburizing gas atmosphere inside the reacting furnace for 1 hour, then the temperature in the reacting furnace was reduced to 150°C. while the atmosphere therein was maintained in the present state. After this temperature was reached, the injection of the gas into the reacting furnace was discontinued. Next, the metallic plates were removed from the reacting furnace, then press-formed into the desired shadow mask shape.
The amount of carbon contained in the shadow masks was found to be 0.01 parts by weight based on the weight of the shadow mask.
Although the present invention has been described in detail hereinabove, it should be clearly understood that many variations and/or modifications of the basic inventive concepts herein taught which may appear to those skilled in the present art will still fall within the spirit and scope of the present invention, as defined in the appended claims. | Disclosed is a shadow mask for a cathode ray tube (CRT) and a method of manufacturing the same. The shadow mask includes a solid solution hardening material and a precipitation hardening material. The method includes the steps of heat treating a metallic plate having a plurality of apertures formed therein using a carburizing gas, and press-forming the metallic plate into a shadow mask shape. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a semiconductor device such as a DRAM including a plurality of MOSFET, particularly to a method for forming a contact hole through an inter-layer insulating layer.
A semiconductor element, such as a Metal-Oxide-Semiconductor Field Effect transistor (“MOSFET”) formed on a semiconductor substrate, is covered by an inter-layer insulating layer such as a silicon oxide layer. The inter-layer insulating layer has a contact hole perforated in the direction of thickness of the inter-layer insulating layer. The contact hole is filled with conductive material that makes an electric contact of the semiconductor element with a conductive layer over the inter-layer insulating layer.
Conventional methods for forming the above-mentioned contact hole include so-called Self-Aligned Contact (“SAC”) method. According to an example of the conventional SAC method, a silicon nitride (SiN) layer is first formed to cover sidewall of the gate of the transistor. Then, an inter-layer insulating layer is formed on the silicon nitride layer. Because of the difference of etching rates, the silicon nitride layer functions as an etch-stopping layer. Therefore by etching the inter-layer insulating layer, a contact hole is formed on a portion of the inter-layer insulating layer under which the silicon nitride layers are not formed.
However, according to the conventional SAC method, it is required to perform process steps for forming the silicon nitride layer and patterning the silicon nitride layer. Therefore, forming a contact hole as a whole includes complicated process steps, and manufacturing cost for a semiconductor device is increased.
SUMMARY OF THE INVENTION
Therefore, the present invention provides a method for manufacturing a semiconductor device by forming a contact hole through simplified process steps.
The present invention may be achieved by using a low pressure chemical vapor deposition (“LPCVD”) method for forming an inter-layer insulating layer with tetramethylcyclotetrasiloxane ([SiH(CH 3 )] 4 O 4 ) as a source gas and oxygen gas as an annexation gas under vacuum ultraviolet light.
Basically, the method for manufacturing a semiconductor device of the present invention includes a process step for forming a contact hole, which perforates through an insulating layer in the direction of thickness of the insulating layer. The insulating layer is formed to cover conductors spaced apart from one another and formed on the surface of the semiconductor substrate. In order to form the insulating layer, tetramethylcyclotetrasiloxane ([SiH(CH 3 )] 4 O 4 ) as a source gas and an oxygen gas as an adjunction gas are provided into a reaction chamber of a LPCVD apparatus where the semiconductor substrate is placed. Then, the insulating layer is formed under vacuum ultraviolet light illuminating the semiconductor substrate.
By forming the insulating layer according to the method described above, the insulating layer has a surface profile corresponding to a convex and concave profile of the conductors on the semiconductor substrate. Further portions of the insulating layer, corresponding to the surface portions of the semiconductor substrate are formed to be relatively thin. Therefore, by etching the whole insulating layer, the relatively thin portions of the insulating layer is removed. That is, a contact hole is formed through the insulating layer without performing conventional process steps, such as forming a silicon nitride layer and patterning the silicon nitride layer.
The process step for etching the insulating layer may preferably be a step for performing a dry etching almost uniformly on the overall surface of the insulating layer, so that the relatively thin portions can be removed without damaging other portions. Further, as described above, since it is possible to perform a “blanket” dry etching, there is no need to use an etching mask for forming a contact hole.
BRIEF DESCRIPTION OF THE DRAWINGS
A further understanding of the nature and advantage of the present invention will become apparent by reference to the remaining portions of the specification and drawings.
FIG. 1 is a schematic diagram showing a cross sectional view of a CVD apparatus related to a method according to an embodiment of the present invention.
FIG. 2 is a graph showing an FTIR analysis result of an insulating layer according to the present invention.
FIGS. 3 a to 3 e are cross sectional views of a semiconductor device showing process steps for forming contact holes according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Now, referring to attached drawings, embodiments of the present invention are described in detail.
Now, referring to FIG. 1, here is shown an LPCVD apparatus 10 for performing the method for manufacturing a semiconductor device according to the present invention. The LPCVD apparatus 10 is used for forming an insulating layer, for example a silicon nitride layer, on a semiconductor substrate.
As shown in FIG. 1, the LPCVD apparatus 10 includes a box type housing 12 , the inner space of which functions as a reaction chamber 11 , a negative pressure source 14 , such as a vacuum pump, coupled to the housing 12 through a pipe 13 for maintaining the reaction chamber under a low pressure condition, a susceptor 16 for holding and supporting a semiconductor wafer 15 made of, for example, silicon in the reaction chamber 11 , and a vacuum ultraviolet light source 17 , such as a Xe 2 excimer laser source. The vacuum ultraviolet light source 17 may be selected from various kinds of laser sources which can radiate short wavelength lights of 200 nm or less or ultraviolet lights having wavelengths in vacuum ultraviolet light range.
An experimental result according to the present invention, which can show the effect of the present invention, is described, hereinafter.
A plurality of wiring conductors 15 a having width of 0.5 um and height of 0.5 um are formed on the surface of the semiconductor wafer 15 . Each of the wiring conductors 15 a is spaced apart from the adjacent one by, for example, 0.7 um. The semiconductor wafer 15 is supported by the susceptor 16 with the surface, on which the wiring conductors 15 a are formed, of the wafer 15 facing up. Temperature of the semiconductor wafer 15 is controlled by controlling temperature of the susceptor 16 and maintained to be the same as the room temperature of the chamber.
The vacuum ultraviolet light source 17 includes a quartz window 17 a as a radiation window having a quartz plate of 20 mm in thickness. The light source 17 is supported the housing so that the quartz window 17 a is located over the semiconductor wafer 15 . The vacuum ultraviolet light is radiated onto the semiconductor wafer 15 through the quartz window 17 a.
In the experiment, in order to form an insulating layer which covers the wiring conductors 15 a on the semiconductor wafer 15 , tetramethylcyclotetrasiloxane ([SiH(CH 3 )] 4 O 4 ) (“TMCTS”) as a source gas and oxygen gas (O2) as an annexation gas are provided into a reaction chamber 11 .
The distance between the semiconductor wafer 15 supported by the susceptor 16 and the quartz window 17 a of the vacuum ultraviolet light source 17 is maintained to be about 15 mm, and the illuminance of the vacuum ultraviolet light source is 10 mW/cm 2 directly under the quartz window 17 a . The semiconductor wafer 15 is irradiated by the vacuum ultraviolet lights having the illuminance 10 mW/cm2. Under these conditions, both of the TMCTS and the oxygen gas are provided into the chamber 11 at a same rate of 50 sccm. The reaction pressure of the chamber is 300 mTorr.
As described in detail below, it is preferable to heat the quartz window 17 a to a temperature over the temperature of the vacuum ultraviolet light source 17 in order to prevent the insulating layer from growing on the surface of the quartz window 17 a and resulting in degradation of the quartz window 17 a.
After about 15 minutes of operating the LPCVD apparatus 15 under the above-described conditions, an insulating layer having thickness of about 1.5 um is formed. Further, it is observed that the insulating layer has a “selective growth” characteristic. In other words, the insulating layer has a surface profile according to the convex and concave profile of the wiring conductors 15 a , and portions of the insulating layer between any pair of the wiring conductors 15 a are extremely thinner than other portions of the insulating layer, which can be verified by using a Scan Electron Microscope (“SEM”).
FIG. 2 shows a spectroscopic analysis result of the insulating layer by using a Fourier transform infrared spectroscopy.
In the graph, the horizontal axis is for wave numbers [cm −1 ], which is reciprocals of wavelengths, of the infrared lights irradiated onto the sample, the insulating layer, and the vertical axis is for absorbance [random unit].
According to the Fourier transform infrared spectroscopy, infrared light of a wavelength corresponding to the characteristics of a sample is absorbed by the sample at a very high absorbance if the infrared light is irradiated on the sample while the wavelength of the infrared light is continuously shifted. Therefore, it is possible to identify the sample material by obtaining the wave number of the infrared light at which the absorbance is the highest.
According to the analysis result shown in FIG. 2, silicon dioxide SiO 2 and di-silicon oxide Si 2 O are shown to be main ingredients of the insulating layer. Both of these two ingredients are electrically nonconductive. Especially, since the di-silicon oxide Si 2 O is an organic material and has smaller dielectric constant than the silicon dioxide SiO 2 , the insulating layer including both materials has good characteristics as an inter-layer insulating layer of a semiconductor device.
Therefore, for example, by performing dry etching for removing the silicon dioxide almost uniformly on the overall portion of the insulating layer enough to remove the above described relatively thin portions, it is possible to form a hole perforating to the surface of the semiconductor wafer 15 without damaging the wiring conductors 15 a.
As described above, since this hole perforates to the surface of the semiconductor wafer 15 through the insulating layer, it is possible to use this hole as a contact hole. As widely known in the art, the contact hole is filled with conductive material, or a conductive film is formed on the insulating layer in order that an electric contact with the semiconductor wafer 15 can be established.
FIGS. 3 ( a ) to 3 ( e ) are cross sectional views of a MOSFET of a semiconductor device showing process steps for forming contact holes coupled to drain/source of the MOSFET according to an embodiment of the present invention.
As shown in FIG. 3 ( a ), a field oxide layer 19 is formed on a semiconductor substrate 18 , such as a silicon semiconductor substrate, according to the well-known LOCOS process. A gate oxide layer 21 made of silicon dioxide is formed on an active layer 20 defined by the field oxide layer 19 , according to, for example, a thermal oxidation process. A plurality of gates 22 are formed to be extended in parallel to each other on the gate oxide layer 21 according to a well-known photolithography process.
Each of the gates 22 is, for example, 0.18 um in width. The total thickness of the gate oxide 21 and the gate 22 is, for example, 0.3 um. Each of the gates 22 is formed to be spaced apart from the adjacent one by 0.2-0.7 um on the semiconductor substrate 18 .
The gate 22 may be made of metal material, such as tungsten, or metal alloy, such as Al—Si—Cu alloy. The gate 22 may also be made of a conductive polysilicon, well known in the art, including conductive impurities. Both sides of each of the gates 22 on the active area 20 of the semiconductor substrate 18 have impurity areas 23 for sources and/or drains formed by, for example, ion implantation process.
Further, as shown in the drawings, conductor lines 24 , which are extensions of the gates 22 , are formed on the field oxide layer 19 .
As shown in FIG. 3 ( b ), an insulating layer 25 is formed to cover the gates 22 and the conductor lines 24 on the semiconductor substrate 18 , where the gates 22 are formed on the active area 20 and the conductive lines are formed on the field oxide layer 19 .
In order to form the insulating layer 25 , the semiconductor substrate 18 , where the gates 22 and conductor lines 24 are formed as shown in FIG. 3 ( a ), is supported for the surface, on which the gates 22 and conductor lines 24 are formed, to face up by the susceptor 16 of the LPCVD apparatus 10 , shown in FIG. 1 . The insulating layer 25 is formed under the same conditions as described above.
As shown in FIG. 3 ( b ), the insulating layer 25 is mostly formed on the gates 22 and conductor lines 24 , which are made of conductive materials and constitute convex portions on the semiconductor substrate 18 , under the conditions as described above. Therefore, the insulating layer 25 has a wave-like surface profile according to the convex and concave profile of the convex portions, the gates 22 and conductor lines 24 .
Further, the insulating layer 25 is restrained from forming between the convex portions 22 and 24 . Therefore, the insulating layer 25 has relatively thin portions 25 a between the convex portions 22 and 24 .
After forming the insulating layer 25 under the above-described conditions, a well-known dry etching for silicon dioxide is performed on the overall portions of the desired area of the insulating layer 25 . The relatively thin portions 25 a of the desired area of the insulating layer 25 is completely removed.
In order to perform the dry etching selectively on the desired area of the insulating layer 25 , it is possible to use an etching mask. However, since the relatively thin portions 25 a of the insulating layer 25 are easier to be removed than the other portions of the insulating layer 25 , the etching mask does not need to be aligned as precisely as conventionally done.
As shown in FIG. 3 ( c ), by performing the etching process, the relatively thin portion 25 a of the desired area of the insulating layer 25 is removed, the impurity area 23 of the semiconductor substrate 18 is exposed and a contact hole 26 is formed.
As shown in FIG. 3 ( d ), after forming the contact hole 26 , in order to fill in the contact hole 26 and cover the other portions of the insulating layer 25 , for example, a conductive polysilicon 27 is formed.
Finally, as shown in FIG. 3 ( e ), unnecessary portions of the polysilicon 27 on the insulating layer is removed by photolithography and etching process. An electric contact with the impurity area 23 through the insulating layer 25 is established by the remaining polysilicon 27 a in the contact hole 26 of the insulating layer 25 .
Over this contact 27 a , additional wiring layers (not shown) and insulating layers (not shown) may be formed.
According to the embodiment of the present invention, it is possible to form an insulating layer 25 having a surface profile corresponding to the convex and concave profile of the gates 22 and the conductor lines 24 on the semiconductor substrate. Further, the insulating layer 25 has a relatively thin portion 25 a at a place corresponding to the place between any pair of the gates 22 or the conductor lines 24 . By performing etching process on overall portion of the insulating layer 25 , it is possible to form a contact hole perforating the insulating layer 25 by etching the thin portion 25 a of the insulating layer 25 without performing processes of forming and patterning a nitride layer, which is required for a conventional SAC process.
The etching process is a dry etching process performed almost uniformly on overall portions of the desired area of the insulating layer. By this dry etching process, it is possible to remove only the relatively thin portions 25 a without damaging the other portions than the relatively thin portions 25 a of the insulating layer 25 . Therefore, it is possible to perform a “blanket” dry etching on the insulating layer. Further, since it is not needed to use highly precise masks, it is possible to form a contact hole relatively easily.
Since formation the relatively thin portions 25 a of the insulating layer 25 is depend on the distance between adjacent convex portions 22 and/or 24 , it is possible to restrain the insulating layer 25 from forming by increasing the distance between adjacent convex portions 22 and/or 24 . Therefore, it is preferable to design a circuit layout so that the distance between adjacent convex portions 22 and/or 24 becomes relatively short. In other words, the density of gates 22 and/or conductor lines 24 becomes high on an area of the semiconductor substrate 18 where the contact hole is not needed. Further, distance between adjacent convex portions 22 and/or 24 becomes relatively long. In other words, the density of gates 22 and/or conductor lines 24 becomes low on an area of the semiconductor substrate 18 where the contact hole is needed.
In the above description, it is described to apply the method of the present invention to processes for manufacturing a MOSFET. The present invention, however, can also be applied to processes for forming a contact hole for a memory cell capacitor of a DRAM.
Further, the present invention can also be applied to processes for forming a transistor of the peripheral area of memory cells or other various kinds of semiconductor devices.
According to the present invention, it is possible to form a contact hole relatively easily without using a conventional SAC process.
Therefore, it is possible to simplify manufacturing processes for a semiconductor device and to decrease manufacturing costs. | In a method for manufacturing a semiconductor device, a semiconductor substrate is provided. On the substrate, conductors spaced apart from one another are formed. Then, an insulating layer is formed on the conductors and the substrate. The insulating layer is formed by a chemical vapor deposition using tetramethylcyclotetrasiloxane as a source gas and oxygen as an adjunction gas. The chemical vapor deposition is performed while the substrate is irradiated by vacuum ultraviolet light. Finally, a part of the insulating layer is removed in a substantial uniform way to form a contact hole through the insulating film. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of an earlier filed provisional patent application entitled, “NOVEL DESIGN AND DESIGN METHODOLOGY FOR SWIRL INDUCING AORTIC OUTFLOW CANNULA WITH A DIFFUSER TIP FOR PEDIATRIC AND NEONATAL CARDIOPULMONARY BYPASS PROCEDURES” having Ser. No. 61/689,280 which was filed on Jun. 1, 2012.
BACKGROUND OF THE INVENTION
Each year 1 in 100 children are born with a congenital heart defect, representing 40,000 children each year in the United States and 1,300,000 children worldwide with clinically significant congenital heart disease (“CHD”). Twenty five percent (25%) of pediatric CHD patients require invasive treatment to correct or palliate these defects and therefore undergo complex biventricular and univentricular repairs. These repairs involve cardiopulmonary bypass (“CPB”) procedures during surgery, as well as circulatory support in the pre or post operative periods. A prolonged CPB can potentially lead to neurological complications and developmental defects in up to 50% of these young patients i.e. infants and children from 2 to 25 kg with congenital or acquired cardiovascular disease.
During CPB, tiny arterial cannulae (2-3 mm inner diameter), with micro-scale blood-wetting features transport relatively large blood volumes (0.3 to 1.0 L/min) resulting in high blood flow velocities. These severe flow conditions are likely to result in platelet activation, release of pro-inflammatory cytokines, and further result in vascular and blood damage. The cannulae are required to provide high blood volume flow rates during neonatal and pediatric cardiopulmonary bypass procedures, resulting in high velocity jet flows. These severe flow conditions initiate platelet activation, release inflammatory cytokines, and further result in vascular and blood damage. Through the design of internal flow control features and a modified cannula outflow tip, it has been made possible to result in outflow jets with low exit force at high flow rates produced with low driving pressure drops, having minimal jet wake blood damage.
Recent investigations have indicated the high hemolytic risk of standard cannulae used in the setting of neonatal CPB surgery and post intervention recovery has been reported to remain suboptimal. Common arterial cannulation sites are located at the aorta, femoral, axillary or subclavian (with or without a side graft), external iliac, and innominate artery. Arterial perfusion by cannulation of the ascending aorta is regarded as an important advance in cardiovascular surgery and is the focus of the present invention since the technique eliminates the issues of retrograde aortic perfusion and the need for a second incision for femoral cannulation during CPB. The aortic cannula must ideally be placed high up in the ascending aorta (as discussed in R. Garcia-Rinaldi, et al., “Simplified aortic cannulation,” Ann Thorac Surg, vol. 36, pp. 226-7, August 1983) but improper technique can occasionally result in profuse bleeding as a result of improper cannula placement. To date, CPB has been studied in regard to clinical stroke-risk (see D. B. Andropoulos, et al., “Neuroprotection in Pediatric Cardiac Surgery: What is On the Horizon?,” Prog Pediatr Cardiol, vol. 29, pp. 113-122, Aug. 1, 2010), but there have been few reported studies deriving cannula design and device use strategy from fluid dynamics associated with arterial cannulation (see T. A. Kaufmann, et al., “Flow distribution during cardiopulmonary bypass in dependency on the outflow cannula positioning,” Artif Organs, vol. 33, pp. 988-92, November 2009; T. A. Kaufmann, et al., “The impact of aortic/subclavian outflow cannulation for cardiopulmonary bypass and cardiac support: a computational fluid dynamics study,” Artif Organs, vol. 33, pp. 727-32, September 2009; Y. Tokuda, et al., “Three-dimensional numerical simulation of blood flow in the aortic arch during cardiopulmonary bypass,” Eur J Cardiothoracic Surg, vol. 33, pp. 164-7, February 2008; A. F. Osorio, et al., “Computational fluid dynamics analysis of surgical adjustment of left ventricular assist device implantation to minimise stroke risk,” Comput Methods Biomech Biomed Engin, vol. 21, p. 21, Dec. 21, 2011), all underscoring the association of biomechanical risks with aortic cannulation. Despite these risks, outflow cannula design and cannulation methods have received little attention compared to the effort expended to assure the safety and efficacy of the mechanical circulatory support blood pumps. There is a definitive need for engineering small yet hemodynamically efficient arterial outflow cannulae that can provide high blood volume flow rates but with low exit force and outflow velocity, for use in extracorporeal circulation during neonatal CPB procedures, while minimizing recognized biomechanical risks related to infection, bleeding, hemolysis and thromboembolism during mechanical circulatory support.
Unlike adult CPB perfusion cannulae (U.S. Pat. No. 5,354,288 to Cosgrove, and U.S. Pat. No. 6,387,087 to Grooters, for example) where outflow is designed to have low velocity jets that prevent dislodgement of atherosclerotic plaque with adherent blood thrombi that can potentially cause thromboembolism, the design goal for the neonatal and pediatric population is quite different. In order to assess desirable jet wake hemodynamics in small cannulae, the jet's potential core length, resistance to outflow, and normalized index of hemoylsis as major parameters to designs so as to provide high blood volume flow rates but with low exit force and outflow velocity from far smaller cannula inner diameters that those used in adults—the latter being a requirement for minimizing disruption of the child's artery during cannulation. The focus of cannula design today and the goal of this invention are therefore to minimize risk of vascular injury and risks of biomechanical origin as well as to simultaneously improve outflow rate versus driving pressure drop perfusion characteristics, which become increasingly unfavorable at reduced outflow diameters, in the case of conventional end-hole type standard cannula configurations evidenced by the prior art. In the case of the specific application aortic cannulation, the present invention may additionally improve perfusion to the head-neck vessels of the aortic arch and therefore improve cerebral perfusion, mitigating neurological complications commonly reported (neurological morbidity is as high as 30% in infants and children) in conjunction with CPB in young patients. See Fallon, et al., “Incidence of neurological complications of surgery for congenital heart disease,” Arch Dis Child, vol. 72, pp. 418-22, May 1995 and H. L. Pua and B. Bissonnette, “Cerebral physiology in paediatric cardiopulmonary bypass,” Can J Anaesth, vol. 45, pp. 960-78, October 1998.
BRIEF SUMMARY OF THE INVENTION
The present invention relates generally to arterial cannulae and aorta cannulae. The prior art discloses the use of small diameter cannulae for minimizing disruption to the neonatal or pediatric arteries, used to return oxygenated blood from the heart-lung machine back to the arterial circulation during CPB. The present invention is the result of a novel design approach based on the paradigm of controlling the development of fluid jets in cannula tip geometries. High performance computing computational fluid dynamics (“CFD”), particle image velocimetry (“PIV”), and flow visualization techniques in a proprietary cuboidal cannula jet testing rig are used as a design tools to compare internal hemodynamics in the early jet region of a conventional tubular cannula device having a standard end-hole, against several embodiments of the proposed novel arterial cannula design which is an elongated tube with an expanded multi-lobe swirl inducer chamber and a diffuser cone end.
This invention further relates to a hemodynamically superior arterial cannula tip designed to delay onset of turbulence in the cannula exit flow wake, while simultaneously reducing exit force of the flow, for minimizing risk of internal vascular injury, improving outflow rate versus driving pressure drop perfusion characteristics and further improving cerebral perfusion, in the case of its application to aortic cannulation. The invention encompasses a method of delivering blood to an artery using a swirl-inducing cannula having a diverging diffuser during cardiopulmonary bypass surgery, which has been specifically tailored to the requirements of neonatal and pediatric procedures.
For specific application to neonatal and pediatric CPB perfusion, and especially in the case of aortic perfusion, design considerations include a small inner diameter of a cannula to minimize disruption of the arterial flow, an expanded multi-lobe swirl inducer responsible for reducing the wall shear stress experienced by the blood in the cannula and also simultaneously improving vorticity of the coherent flow core in order to propel flow forward in a manner delaying the Reynolds number (“Re”) for onset of turbulence in the flow, and finally a diverging diffuser that improves pressure-drop versus flow-rate characteristics and reduces outflow jet exit force (and outflow velocity) while simultaneously facilitating improved cerebral perfusion by mitigating backflow from the head-neck vessels of the aortic arch. The diverging diffuser tip is axis-symmetric and in one embodiment linearly increases the diameter of the cannula until the outflow and in another embodiment may non-linearly increase the diameter of the cannula until the outflow tip.
The swirl inducer design has potential applicability to adult CPB perfusion and as an attachment to existing cannula tips for purposes of improved flow hemodynamics, perfusion characteristics, as well as insertion orientation control. In an ideal use case or mode of operation, the blood flow (typically Re 650 to 3000) exiting the cannula's diffuser along the direction of the transverse aortic arch, heading towards the curvature of the descending aorta, in a manner that mitigates direct flow impingement on the walls of the transverse aortic arch or the head-and-neck vessel branches, therefore, minimizing stroke risk due to transport of dislodged thrombi from the mechanical circulatory support systems into the head-neck vessels.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a frontal view of a cannula having a cannula tip inserted into the ascending aorta. The overall size of the device and the relative size of the aorta may vary depending upon the rated diameter and specific design parameters of the cannula tip.
FIG. 2 illustrates an enlarged view of a cannula including an embodiment of a cannula tip.
FIG. 3 illustrates an embodiment of a cannula tip showing an embodiment of the diverging diffuser type of outlet.
FIG. 4 illustrates a sectional view taken through section 4 - 4 of FIG. 3 .
FIG. 5 illustrates a sectional view taken through section 5 - 5 of FIG. 3 .
FIG. 6 illustrates an embodiment of the diverging diffuser type of outlet and a plurality of swirl inducing lobes.
FIG. 7 illustrates a sectional view taken through section 7 - 7 of FIG. 6 . For ease of viewing, the size of the cross section depicted in FIG. 7 is larger than it would otherwise be.
FIG. 8 illustrates a sectional view taken through section 8 - 8 of FIG. 6 . For ease of viewing, the size of the cross section depicted in FIG. 8 is larger than it would otherwise be.
FIG. 9 illustrates a sectional view taken through section 9 - 9 of FIG. 6 . For ease of viewing, the size of FIG. 9 is depicted as larger than it would otherwise be.
FIG. 10 illustrates a sectional view taken through section 10 - 10 of FIG. 6 . For ease of viewing, the size of FIG. 10 is depicted as larger than it otherwise would be.
FIG. 11 illustrates an embodiment of the diverging diffuser type of outlet and a plurality of more pronounced swirl inducing lobes.
FIG. 12 illustrates a sectional view taken through section 12 - 12 of FIG. 11 . For ease of viewing, the size of FIG. 12 is depicted as larger than it would otherwise be.
FIG. 13 illustrates a sectional view taken through section 13 - 13 of FIG. 11 . For ease of viewing, the size of FIG. 13 is depicted as larger than it would otherwise be.
FIG. 14 illustrates a sectional view taken through section 14 - 14 of FIG. 11 . For ease of viewing, the size of FIG. 14 is depicted as larger than it would otherwise be.
FIG. 15 illustrates a sectional view taken through section 15 - 15 of FIG. 11 . For ease of viewing, the size of FIG. 15 is depicted as larger than it would otherwise be.
FIG. 16 illustrates a sectional view taken through section 16 - 16 of FIG. 11 . For ease of viewing, the size of FIG. 16 is depicted as larger than it would otherwise be.
FIG. 17 illustrates a graphical depiction of pressure gradient versus flow rate across the tip of the cannula, along the axis of the cannula jet, for selected embodiments of the invention disclosed herein.
DETAILED DESCRIPTION
Cannula of the type described herein directs the flow of blood from blood pumping apparatus, which is known in the art, so that it exits the cannula tip along a particular artery or in the case of an aortic artery, in a predetermined direction 5 along the transverse aortic arch 7 heading towards the curvature of the descending aorta, as may be seen by referring to FIG. 1 in conjunction with FIG. 2 .
It is recognized to be advantageous to have the blood flow enter the aorta in a manner that mitigates high wall shear stress owing to harsh jet impingement on the walls of the transverse aortic arch or the head-and-neck vessel branches which may lead to intimal vascular damage, while also minimizing stroke risk due to dislodged thrombi from the mechanical circulatory support systems. It is also understood that cerebral perfusion can be improved in the aortic arch by virtue of the diffuser tip of the invention which lowers the velocity of the outflow cannula jet, averting likely backflow at the head-neck vessels of the aortic arch owing to the Venturi Effect, and therefore reducing likelihood of neurological complications associated with CPB which has been reported to be widely prevalent in the pediatric/neonatal population. Despite advances in surgical techniques, leading to decreased morbidity after repair of complex congenital cardiac conditions, neurologic morbidity is still significant. Given that the incidence of neurological morbidity is as high as 30% in infants and children undergoing CPB, in sharp contrast with 2-5% among adults, the issue of arterial perfusion deserves attention in young patients.
The invention disclosed herein presents three embodiments which attain these objectives. While some of these embodiments are discussed from the standpoint of the special case of aortic insertion, it is to be understood that they are applicable to the more general case of insertion into other arterial vessels as well.
Referring to FIGS. 1 and 2 , FIG. 1 discloses a cannula tip 3 c in the configuration of the third embodiment to be discussed in greater detail below, for purposes of illustration and ease of viewing. The cannula tip 3 c has been partially inserted into an artery, and for purposes of this illustration, the artery is illustrated as an aorta 6 . It is to be understood that any of the three embodiments discussed herein can be used in the manner of the cannula tip 3 c illustrated in FIG. 1 . The diffuser tip is a flexible embodiment which can be introduced into the aorta through minimal arterial disruption the size of only for the neck of the diffuser tip.
First Embodiment
Referring now to FIG. 3 , a cannula tip 3 a is illustrated. As noted above, it should be understood that this first embodiment and the second embodiments as well, can be used in the manner illustrated by FIG. 1 .
Blood is able to enter inlet 2 a and flow along longitudinal axis 8 a in downstream direction 4 from inlet 2 a , through cannula tip body 9 a and cannula tip 3 a and out of diverging portion 11 a , as will be discussed in greater detail. As the blood flow exits cannula tip 3 a , it continues to flow in a direction 5 (direction 5 is illustrated in FIG. 1 ). This orientation will take the flow in the direction of descending aorta 10 and away from aortic arch 7 , an important feature which will be discussed in greater detail below.
Still referring to FIG. 3 , cannula tip 3 a has an approximately cylindrical cannula tip body 9 a and has a cross sectional area depicted in FIG. 4 as cylindrical. Cannula tip body 9 a has inlet 2 a which has first diameter 23 a and a diverging portion 11 a which has a larger circular cross sectional area having a second predetermined diameter 25 a as depicted in FIG. 5 . The surface 12 a of diverging portion 11 a makes an angle 14 with the longitudinal axis 8 a of cannula tip 3 a . In an embodiment angle 14 is 7 degrees.
As blood passes through the cannula tip body 9 a , it is diffused through diverging portion 11 a and its larger cross sectional area having second predetermined diameter 25 a . Diverging portion 11 a is illustrated as having a predetermined length 13 a as illustrated in FIG. 3 . In an embodiment, predetermined length 13 a is 1 centimeter. Diverging portion 11 a is further disclosed as having a truncated conical shape with an expanded circular cross sectional area located in downstream direction 4 from the other portion of cannula tip body 9 a . Diverging portion 11 a serves as an outlet for the blood flow from the blood pumping apparatus into an artery (not illustrated). Although diverging portion 11 a , and diverging portions 11 b and 11 c in the second and third embodiments respectively, are disclosed as being conical in shape, other diverging shapes are possible. In an embodiment, for example, diverging portions 11 a , 11 b , and/or 11 c can have a curved or flared configuration.
The expanded cross sectional area of diverging portion 11 a diffuses the flow of blood and results in a decreased flow velocity of the jet or flow of blood from cannula tip 3 a as well as other improved flow characteristics of the blood flow as it enters into either an artery or aorta 6 . Among the improvements to the flow characteristics of the blood flow is the observed ability of the flow to maintain a laminar flow pattern for a greater distance into artery or aorta 6 . This improved flow pattern in turn, is believed to reduce stress on the arterial walls of artery or aorta 6 and also a reduced likelihood of sub-lethal hemolysis blood damage as a result of fluid shear stresses around the cannula jet.
It has been established through experimentation and analysis that causing the flow of blood in cannula tip to rotate within the cannula tip provides additional advantages with regarding to the flow's ability to maintain a laminar flow profile for greater distance after it enters an artery. More specifically, the addition of a swirl inducing means within the cannula tip causes the blood flow to rotate around the longitudinal axis of the cannula tip and forestalls turbulent flow of blood for a greater distance after it has entered an artery.
Second Embodiment
It must be kept in mind that while this second embodiment and the third embodiment described below reflect the invention herein disclosed in terms of aortic insertion, this disclosure is also applicable to arterial insertion in general.
Referring now to FIGS. 6, 7, 8, 9, and 10 , FIG. 6 depicts a cannula tip 3 b that has cannula tip body 9 b and an inlet 2 b which has a first predetermined diameter 23 b and a diverging portion 11 b in a downstream direction 4 from inlet 2 b . Diverging portion 11 b has a second predetermined diameter 25 b as illustrated in FIG. 10 and is further illustrated as having a predetermined length 13 b as measured from throat 21 b (as described below) to second predetermined diameter 25 b . In an embodiment, predetermined length 13 b is 1 centimeter.
Cannula tip body 9 b includes a swirl inducing portion 16 b located between inlet 2 b and diverging portion 11 b . Swirl inducing portion 16 b is illustrated as having a third predetermined diameter 27 b as shown in FIG. 8 which in an embodiment is illustrated and swirl inducing portion 16 b is three times the diameter of the inlet 2 b and swirl inducing portion 16 b has four lobes 18 b oriented in a helical orientation 90 degrees apart around the longitudinal axis 8 b of cannula tip 3 b . In another embodiment, the swirl inducing portion 16 b is at least three times the diameter of the inlet 2 b . In another embodiment, the swirl inducing portion 16 b is at least about three times the diameter of the inlet 2 b . In another embodiment, swirl inducing portion 16 b has at least four lobes 18 b oriented in a helical orientation 90 degrees apart around the longitudinal axis 8 b of cannula tip 3 b.
The effect of lobes 18 b is to impart a helical flow to the blood in cannula tip body 9 b about longitudinal axis 8 b . In an embodiment, the four lobes 18 b are disclosed as partially convex in a radially outward direction from longitudinal axis 8 b . In another embodiment, the four lobes 18 b are disclosed as partially circular in a radially outward direction from longitudinal axis 8 b . Each of the four lobes 18 b begins at a location along cannula tip 3 b in the vicinity of section 7. (In an alternate embodiment (not shown), there are at least four lobes. In another alternate embodiment (not shown), there are at least about four lobes.) Proceeding in downstream direction 4 , the diameter of the swirl inducing portion 16 b increases to a third predetermined diameter 27 b as illustrated in FIG. 8 . Still referring to FIG. 6 together with FIGS. 7, 8, 9, and 10 , continuing along the longitudinal axis 8 b in downstream direction 4 , the diameter of cannula tip 3 a decreases and the lobes 18 b diminish until a throat 21 b is formed as illustrated by FIG. 9 . Throat 21 b is circular in cross section and has a diameter which is approximately the same diameter as-inlet 2 b.
Still continuing in downstream direction 4 , the blood flow enters diverging portion 11 b . In a manner similar to the first embodiment, diverging portion 11 b is conical in shape and has a second predetermined diameter 25 b (as illustrated in FIG. 10 ) located in downstream direction 4 from swirl inducing portion 16 b as illustrated in FIG. 6 . It should be noted that in an embodiment, diverging portion 11 b can be provided with a flared configuration as noted above. Still referring to FIG. 6 , diverging portion 11 b has surface 12 b and acts as a diffuser for the blood flow. Diverging portion 11 b also has a predetermined length 13 b as illustrated in FIG. 6 . The surface 12 b of diverging portion 11 b makes an angle 14 b with the longitudinal axis 8 b of the cannula tip 3 b . In an embodiment, angle 14 b is 7 degrees. In still another embodiment, length 13 b is 1 cm.
In-silico and in-vitro experimentation has indicated a very significant improvement in the flow characteristics of blood entering an artery in general, artery or aorta 6 in particular, as a result of the combination of swirl inducing portion 16 b and diverging portion 11 b . The temporal unsteadiness of the blood flow into an artery 6 is notably reduced in comparison with a standard end-hole cannula tip of similar diameter. Specifically, analysis of the blood flow has confirmed an enhanced laminar flow regime when unsteady flow was observed for conventional prior art end-hole cannulae, and the desirable laminar flow characteristics are maintained for a greater distance into that artery.
Third Embodiment
Referring now to FIG. 11 in conjunction with FIGS. 1, 12, 13, 14, 15, and 16 , a larger and more pronounced swirl inducing portion 16 c is disclosed. Inlet 2 c of cannula tip 3 c as shown in FIG. 11 has first predetermined diameter 23 c (as shown in FIG. 12 ) and has roughly the same cross sectional area as inlet 2 b as shown in FIG. 7 in the second embodiment. However, the third predetermined diameter 27 c of swirl inducing portion 16 c (as illustrated in FIG. 14 ) has been increased to four times the first predetermined diameter 23 c of inlet 2 c as may be seen in FIG. 12 . In another embodiment, the third predetermined diameter 27 c of swirl inducing portion 16 c is at least four times the first predetermined diameter 23 c of inlet 2 c . In still another embodiment, the third predetermined diameter 27 c of swirl inducing portion 16 c is at least about four times the first predetermined diameter 23 c of inlet 2 c.
In a general embodiment, swirl inducing means includes a diverging profile followed by a converging profile. In an embodiment, swirl inducing portion 16 c is a swirl inducing means which includes a diverging profile followed by a converging profile. The cross sectional area of throat 21 c is shown in FIG. 15 to be approximately the same diameter as first predetermined diameter 23 c of inlet 2 c . As a result, the diameter of swirl inducing section 16 c increases in downstream direction 4 from first predetermined diameter 23 c to third predetermined diameter 27 c and then decreases in the area of throat 21 c to approximately the first predetermined diameter 23 c of inlet 2 c . This, in turn, creates a diverging profile from first predetermined diameter 23 c of inlet 2 c to third predetermined diameter 27 c of swirl inducing portion 16 c , followed by a converging profile from third predetermined diameter 27 c to throat 21 c . Diverging portion 11 c has second predetermined diameter 25 c and is further illustrated as having a predetermined length 13 c as illustrated in FIG. 11 . In an embodiment, predetermined length 13 c is 1 centimeter. As in the first and second embodiments, diverging portion 11 c diffuses the flow of blood thereby reducing its exit velocity, and surface 12 c of diverging portion 11 c makes an angle 14 c with longitudinal axis 8 c . In an embodiment, angle 14 c is 7 degrees. As noted previously, embodiments of diverging portion 11 c can be provided with either a conical or a flared configuration.
FIGS. 11, 13, and 14 disclose four lobes 18 c , which are helically disposed about longitudinal axis 8 c but are more pronounced and more defined than lobes 18 b in the second embodiment. (In an alternate embodiment (not shown), the cannula tip may have a plurality of lobes comprising of at least four lobes. In another alternate embodiment (not shown), the cannula tip may have a plurality of lobes comprising of at least about four lobes.) Furthermore, lobes 18 c encompass a 360 degree “twist” or helical rotation along longitudinal axis 8 c of swirl inducing portion 16 c . In another embodiment, lobes 18 c encompass at least a 360 degree “twist” or helical rotation along longitudinal axis 8 c of swirl inducing portion 16 c . In another embodiment, lobes 18 c encompass at least about a 360 degree “twist” or helical rotation along longitudinal axis 8 c of swirl inducing portion 16 c . This larger and more pronounced swirl inducing portion 16 c has the effect of rotating blood flowing through cannula tip 3 c through a greater angle than in the second embodiment, which has proven to be of greater advantage in some applications. The enhanced swirl added to the flow of blood has been demonstrated to be superior to conventional end-hole cannulae in term of flow rate versus pressure drop perfusion characteristics.
This is more particularly illustrated in FIG. 17 , which is a graphical depiction of the results of an in-silico analysis studying pressure flow characteristics measured 70 mm along the blood flow jet axis (a virtual continuation of longitudinal axis 8 a and 8 c ) for an existing prior art 2 mm end-hole cannula tip, a cannula tip configured as in the third embodiment, and a cannula tip configured as in an alternative embodiment having an angle 14 c of 10 degrees.
Those skilled in the art will recognize that it is advantageous to have a low pressure gradient, reflected by the slope or shallowness of each of the graphs shown on FIG. 17 . As may be seen from FIG. 17 , the less desirable steep gradient or slope is attributed to the end-hole cannula tip while the more desirable shallow gradient is reflected by the cannula tip in the configuration of the third embodiment. Thus, it may be seen that the invention disclosed herein is able to deliver markedly improved pressure flow characteristics for blood flowing from cannula tips 3 a , 3 b , and 3 c as opposed to the prior art. This in turn results in reduced pressure on arterial walls, lower turbulence of the blood flow, and reduced sub-lethal hemolysis blood damage. In-silico observations have also confirmed that cerebral perfusion improved with the use of embodiments 3 a , 3 b , and 3 c.
It should also be noted that in the case of cannualization of the aorta 6 , the angle of incidence of the blood flow jet has in impact on the formation of undesirable vortices and flows within aorta 6 . It has been determined by in-silico studies to be beneficial to direct the blood flow jet so that it does not impinge directly upon the walls of the transverse aortic arch 7 . Referring back to FIG. 1 , cannula tip 3 c and its longitudinal axis 8 c are illustrated as having been oriented so as to direct the blood flow jet away from the aortic arch 7 in direction 5 toward descending aorta 10 . Due to the improved cohesiveness of the blood flow jet resulting from the embodiments 3 a , 3 b , and 3 c described herein, the blood flow jet remains in laminar flow for a greater distance and can be more successfully directed toward descending aorta 10 . Furthermore, complex vertical structures are greatly reduced prior to the blood flow jet impinging on the descending aorta 10 . This in turn has been observed to result in lowered hemolysis and backflow into the brachiocephalic artery. | A novel arterial cannula tip includes an elongated body having an expanded four-lobe swirl inducer and a diverging diffuser. The swirl inducer presents micro-scale blood-wetting features that help to enhance the jet or core of the flow of blood sufficiently to delay the onset of turbulence and facilitate a strongly coherent blood outflow jet as it enters the cannulated artery, while the diverging diffuser reduces exit force and promotes and laminar flow which mitigates intimal vascular damage owing to high wall shear stresses at regions of jet impingement. When used in conjunction with an aortic cannula, the device facilitates neuroprotection by way of improved cerebral perfusion. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a socket for a ball point pen suitable for use with low viscosity aqueous ink, and more particularly to a socket for a ball point pen which is designed to deliver a proper amount of ink quickly from an ink cartridge to a writing ball when the cartridge is inserted into the ball point pen.
2. Description of the Prior Art
Most of the prior art ball point pens using aqueous ink have the ink reservoir in the barrel filled with aqueous ink. When therefore, a long period of time passes before the ball point pen is actually used after being manufactured, the ink held in the ink passageways provided in the socket to connect the writing ball with the cartridge often becomes so dry as to flow with great difficulty or not at all when the user is going to commence writing, rendering the ball point pen utterly unavailable for practical application. To eliminate the above-mentioned difficulties accompanying most of the ball point pens using aqueous ink, there has been developed such type of ball point pen as is designed to be fitted in use with a cartridge filled with aqueous ink. With a known ball point pen, however, the ink passageways provided in the socket are so narrow that under natural conditions, the ink held in the cartridge is delivered only by capillary action to the writing ball through the passageways. Therefore, the aforesaid developed type of ball point pen has the drawback that ink takes too long to reach the writing ball after the cartridge is inserted into the pen body, preventing the pen from being immediately put to use. For quick ink delivery, the user often manually squeezes the ink-filled cartridge fitted into the socket after removing the pen body in order to apply pressure on the ink held in the cartridge. With a general ball point pen, however, a clearance between the writing ball and the edge of the tip portion of the socket is smaller than in the ordinary ball point pen using viscous ink, preventing the air remaining in the ink passageways from easily escaping out of the ball point pen through the forward end of the socket. As a result, the air itself exerts a resistive force within the ink passageways, not only obstructing the quick influx of fresh ink thereinto, but also preventing the ink already held in the passageways from being delivered to any proper outlet due to the prevalence of the air resistance. Accordingly, the ink is unavoidably forced out of the pen body through an air duct provided at the forward end of the pen barrel, undesirably wetting the forward end.
SUMMARY OF THE INVENTION
It is accordingly an object of this invention to provide a socket for a ball point pen, the sleeve of which is provided inside with ink passageways and a communication section causing the ink passageways to communicate with the atmosphere, thereby enabling aqueous ink to be supplied to a writing ball smoothly and quickly from the very start of writing.
Another object of the invention is to provide a socket for a ball point pen which prevents aqueous ink from soiling a barrel by being forced out therefrom through an air duct even when an ink cartridge mounted in the socket is manually squeezed to apply pressure to the ink to enable the ink to quickly flow from the cartridge.
According to this invention, a socket for a ball point pen comprises a hollow sleeve for receiving a writing ball at the forward end; a rod member inserted into the sleeve in a fluid tight state so as to abut against the writing ball at the forward end; ink passageways defined between the sleeve and rod and open to both ends of the sleeve; and a communication section provided in the sleeve to cause the ink passageways to communicate with the atmosphere.
The communication section plays the part of conducting the air remaining in the ink passageways to the atmosphere as aqueous ink is successively brought into the passageways, thereby enabling a proper amount of aqueous ink to be quickly delivered to the writing ball through the passageways and also preventing the ink from leaking through the air duct to soil the forward end of the barrel of the ball point pen as often occurs when it is attempted quickly to force the ink into the passageways from the ink cartridge connected to the socket by manually squeezing the cartridge.
BRIEF DESCRIPTION OF THE DRAWING
This invention will be described by way of example with reference to the accompanying drawings.
FIG. 1 is a longitudinal sectional view of an embodiment of a socket for a ball point pen according to this invention;
FIG. 2 is a cross sectional view on line 2--2 of FIG. 1;
FIG. 3 is a longitudinal sectional view of the tip portion of a ball point pen with the socket of FIG. 1 inserted therein;
FIG. 4 is a cross sectional view on line 4--4 of FIG. 3;
FIG. 5 is a longitudinal sectional view of a socket according to another embodiment of the invention for a ball point pen; and
FIG. 6 is a cross sectional view on line 6--6 of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Throughout the drawings, the similar parts are denoted by the same numerals.
Referring to FIGS. 1 and 2, a socket 10 has a hollow cylindrical sleeve 12. As seen from FIG. 1, the sleeve 12 receives a writing ball 14 in the forward end portion 12a, which in turn is crimped or deformed to prevent the ball 14 from falling out.
As is apparent from FIG. 2, a rod member 16 having a flat plane 16a formed at two opposite peripheral portions and presenting a drum shape in cross section as a whole is inserted into the sleeve 12 in close contact (FIG. 2) with the inner wall 12b thereof, except for the flat planes 16a.
The flat planes 16a of the rod member 16 and the inner wall 12b of the sleeve 12 define two ink passageways or ink conducting chambers 18.
The rod member 16 is formed of wear-resistant and corrosion-resistant material, such as nylon impregnated with molybdenum disulfide (MoS 2 ), carbon fiber-reinforced plastic (CFRP) or bearing metal material. A funnel-shaped seat 20 (FIG. 1) is provided at the forward end 16b of the inserted rod 16 to receive the writing ball 14, thereby fixing its position in the axial direction of the socket 10.
The sleeve 12 has part of its peripheral wall bored with a slit-like communication section or chamber 22 lengthwise extending from the rear end 12c of the sleeve 12 to the proximity of the forward end 12a thereof. In other words, that portion of the sleeve 12 which extends from the proximity of the forward end 12a to the rear end 12c has a C-shaped cross section as shown in FIG. 2. The communication chamber 22 is defined by a pair of spatially facing parallel wall surfaces 24 of the sleeve 12. The communication chamber 22 is open to the rear end 12c of the sleeve 12 so as to be easily machined.
FIG. 3 illustrates the forward end portion of the barrel 26 of a ball point pen using the socket 10. The barrel 26 receives a feed bar 28 having its peripheral wall provided with a plurality of annular projections 28a. The smaller diameter cylindrical forward end portion 28b of the feed bar 28 is inserted in a fluid tight state into a cylindrical hole 30 bored in the tip portion 32 of the barrel 26.
The feed bar 28 is provided with a narrow ink groove 34 (see FIG. 4) whose deepest part reaches the central line of the feed bar 28 and which extends all along the feed bar 28 except for the forward end portion 28b. A long cylindrical hole 36 penetrates the forward end portion 28b and part of the main body of the feed bar 28 in such a manner that the hole 36 is concentric with the forward end portion 28b of the feed bar 28. The socket 10 is inserted into the long cylindrical hole 36 so as to cause that portion of the communication chamber 22 which is disposed near the forward end 12a of the sleeve 12 to be exposed out of the tip portion 32 of the barrel 26. In the rear end of the feed bar 28 is mounted a cartridge (not shown) filled with aqueous ink, which is conducted through the groove 34 to the passageways 18. An air duct 40 is provided in the forward portion of the barrel 26 so as to cause a control chamber 38 defined by the inner wall of the barrel 26 and the peripheral wall or annular projections 28a of the feed bar 28 to communicate with the atmosphere. The control chamber 38 normally contains both aqueous ink and air.
When there is a change in the temperature within the barrel 26 or in the pressure applied to the ink passing through the groove 34, the air duct 40 plays the part of allowing air to be brought into the control chamber 38 from the atmosphere or conversely to be discharged from the control chamber 38 into the atmosphere, thereby fixing the pressure applied to the aqueous ink flowing through the groove 34 and consequently enabling the ink to be supplied to the passageways 18 of the socket 10 smoothly at a constant rate. A ring member 42 is placed in the hole 30 of the tip portion 32 of the barrel 26 and disposed ahead of the forward end portion 28b of the feed bar 28. The ring member 42 tightly holds the peripheral wall of the socket 10 inserted therein to prevent the socket 10 from readily falling out of the tip portion 32 of the barrel 26. Further, the ring member 42 prevents ink from running over the outer peripheral wall of the socket 10 to leak from the engagement section between the socket 10 and tip portion 32.
There will now be described the operation of a ball point pen using the socket of this invention. When a cartridge filled with aqueous ink is mounted in the rear end of the feed bar 28, the ink passes by capillary action through the groove 34 into the passageways 18 at the rear end of the socket 10. The air which is filled in the passageways 18 before the arrival of the ink is expelled to the atmosphere through the communication chamber 22 due to the influx of the ink. Accordingly, the ink brought into the passageways 18 displaces the air contained therein and is quickly and smoothly conducted to the writing ball 14. The cartridge is sometimes manually squeezed, for example with one's fingers, to attain the quick delivery of ink to the writing ball 14 from the cartridge soon after it is fitted to the feed bar 28. In this case, the air remaining in the passageways 18 immediately escapes into the atmosphere through the communication chamber 22 as the ink rapidly comes into the passageways 18 due to the pressures applied to the ink. Accordingly, the ink quickly reaches the writing ball 14 with little air resistance, substantially eliminating the possibility of the ink overflowing from the groove 34 and leaking to the atmosphere from the air duct 40 due to the overburdened capacity of the control chamber 38 and in consequence soiling the outer surface of the barrel 26.
In contrast, the prior art socket for a ball point pen lacks a portion corresponding to the communication chamber 22 used in the socket of this invention. Therefore, the air remaining in the passageways has to be discharged into the atmosphere through a narrow clearance between the sleeve and writing ball in order to be displaced by the ink brought into the passageways, naturally causing the ink not only to take too long to reach the writing ball but also to run over the ink groove due to the prevalence in the passageways when the ink cartridge is manually squeezed for quick delivery of ink therefrom, as is sometimes attempted. In such case, the overflowing ink runs out of the pen through the control chamber and air duct to soil the pen barrel.
It is seen from the foregoing description that a socket according to this invention for a ball point pen eliminates the drawbacks accompanying the prior art socket.
FIGS. 5 and 6 jointly illustrate a socket according to another embodiment of this invention for a ball point pen. The difference between the preceding embodiment of FIGS. 1 to 4 and that of FIGS. 5 and 6 is that in the second embodiment, the slit-like connection chamber 22 is replaced by a hole-shaped communication chamber 122 which is provided in a hollow cylindrical sleeve 112 near its forward end portion 112a to establish communication between the ink passageways 18 and the atmosphere. This chamber 122 which corresponds to the communication chamber 22 of the preceding embodiment formed in the socket 10 penetrates the sleeve 112 in the radial direction to attain communication between the ink passageways 18 and the atmosphere.
Throughout FIGS. 5 and 6, numerals 110, 112b, 112c respectively denote the socket, and the inner wall and rear end of the sleeve 112. The other numerals show the same parts as those of the preceding embodiment of FIGS. 1 to 4.
When the socket 110 is inserted into the tip portion 32 of the barrel 26, the communication chamber 122 is brought outside of the tip portion 32, causing the ink passageways of air conducting chambers 18 to communicate with the atmosphere through the communication chamber 122. The socket 110 of the second embodiment shown in FIGS. 5 and 6 is operated with the same effect as the socket 10 of the first embodiment of FIGS. 1 to 4, description thereof being omitted by way of eliminating duplication. | A socket for a ball point pen comprises a hollow sleeve receiving a writing ball at the forward end, a rod member forcefully inserted into the sleeve to be pressed at the forward end against the writing ball, and ink passageways defined between the sleeve and rod member so as to extend throughout the socket. The sleeve is provided with a communication section for causing the ink passageways to communicate with the outside of the socket, thereby attaining a reliable delivery of ink from the ink passageways to the writing ball and preventing ink from leaking out of the pen body through an air passage provided at the forward end portion of the barrel of the ball point pen. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to a process for preparing a synthetic wood product.
It is known that an elongated foamed article can be prepared by extruding a normally hard, thermoplastic resin from a die while in a softened state. If a die having a single orifice and which is normally used for the preparation of a board is employed, however, the elongated article obtained does not have a structure wherein foamed portions of high density exist alternately with foamed portions of low density. The foamed article does not have, therefore, a ring structure as seen in natural wood. The foamed articles obtained by these conventional processes although not having appearance which actually resembles natural wood, are sometimes called synthetic wood.
A process is also known for preparing a foamed structure in which foamed portions of higher density are contained therein alternately with foamed portions of lower density, both portion extending throughout the entire structure. In the process a foamable resin is extruded through a die provided with a number of apertures and mounted on an extruder to form a number of foamed resin strands, each of which has a high density surface skin and a low density inner portion, which strands are different in their average densities. The strands are then coalesced into a unitary foamed article. In the foamed article thus obtained, each of the strands acts as if it were one annual ring, and as a result, the foamed article shows a property similar to natural wood. Such a process is disclosed in Japanese Patent Publications No. 47-40293, No. 47-40294 and No. 47-51945 and U.S. Pat. No. 3720572.
Because the synthetic wood obtained by the above process has a structure wherein a number of foamed strands, having various average densities, are coalesced, density differences are provided even in the inner portions. Thus, the synthetic wood has an appearance of straight grains and mechanical properties resembling natural wood. Further, characteristically the straight grains do not disappear even with planing off or other fabrications. Due to such advantages, the synthetic wood has a wide variety of applications in many fields.
The synthetic wood described above, however, sometimes has disadvantages when used in certain specific applications. For example, the synthetic wood is easily torn away along the coalesced surfaces formed between the foamed strands therein, and thus the synthetic wood has a low bending strength in the direction perpendicular to the longitudinal direction of the strands. As a result, when the synthetic wood is made into a broad board, it is not suitable for use in applications wherein bending strength may be needed in the width direction of the board. A need exists, therefore, for a synthetic wood having an appearance of straight grains on the surface thereof and a high bending strength in the width direction. The present invention has been made in order to meet the above need.
SUMMARY OF THE INVENTION
The present invention provides a process wherein a foamable resin is extruded through a die having an orifice having recesses or grooves around its periphery running in the width direction of said orifice to form a foamed article having the shape of the grooves or recesses (peaks and valleys) on the surface and thereafter the peaks are pressed, or compressed, while the article is still in a softened state to eliminate the peaks. As a result, there is obtained a foamed board having on its surface a striped pattern consisting of high density foamed portions and low density foamed portions, said high density portions being produced by pressing at the places wherein the protruding peaks are formed when the foamable resin is extruded - said low density portions being at the valleys. Further, the foamed board has a surface pattern resembling the annual rings of natural wood. Moreover, the foamed board is imparted with the striped pattern only on its surface portions, and is evenly foamed in its inner portions. Thus, the board obtained according to the invention has a high bending strength in the width direction and an appearance similar to natural wood and has, therefore, improved properties which have not been attained by the known processes.
According to the present invention, an improvement in a process for preparing a synthetic wood, which process includes the step of extruding a thermoplastic resin containing a foaming agent from a die mounted on an extruder, is provided with: employing as the die, a die having an orifice for forming a cross section of a desired profile, and having on the peripheries of the orifice grooves or recesses at least on the outlet side; extruding a foamable resin from the die to form a porous shaped article having peaks and valleys on its surfaces corresponding to the grooves or recesses; and thereafter pressing the peaks while the article is still in a softened state to level the peaks so as to provide a flat surface wherein the peaks are on the same level with the valleys and whereby higher density portions are formed at places corresponding to the peaks than at places corresponding to the valleys.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is further explained by referring to the drawings, in which:
FIG. 1 is a front view of a die used in the present invention.
FIG. 2 is a front view of a foamed article immediately after being extruded from a die according to the present invention.
FIG. 3 is a view of foamed article which has been extruded, passed through a guide and then pressed by rolls according to the present invention.
FIGS. 4 to 6 are front views of a die which can be used in the present invention, wherein various types of grooves and recesses for an orifice are shown, and in particular;
FIG. 4 is a front view of a die provided with an orifice which has a cross section having grooves or recesses, said grooves or recesses having a steep angle m on the left and lesser angle n on the right.
FIG. 5 is a front view of a die provided with an orifice having a cross section containing a plurality of small rectangles positioned at equal distances from one another.
FIG. 6 is a front view of a die provided with an orifice having a cross section containing grooves or recesses of a variety of shapes.
FIG. 7 shows a horizontal section and top view of one embodiment of the present invention.
DETAILED DESCRIPTION
Referring to FIG. 1, die 2 is mounted on the forward end 1 of an extruder. Die 2 is surrounded by heaters 3 and provided with orifice 4 therein. Orifice 4 is approximately in the form of a board at the outlet side and has corrugated portions 5 on each of the upper and lower surfaces at the outlet end - the corrugated portions undulating in the width direction of board. Supporting members 6 for supporting cooling pipes are mounted on the upper and lower portions of orifice 4.
Referring to FIG. 2, there is shown a state, wherein a foamable resin is extruded from die 2 provided with orifice 4 having corrugated portions 5 as shown in FIG. 1. When extruded, the foamable resin becomes a shaped article 8 having on the upper and lower surfaces so-called peaks and valleys or corrugations, corresponding to corrugated portions 5 around orifice 4. Pipes 7 are fixed to the vicinity of the orifice by the supporting members 6. Cooling air may be circulated through pipes 7 to cool the surfaces of pipes 7. Pipes 7 are arranged so that each of their surfaces may contact only the protruding peaks on each of the upper and lower surfaces of shaped article 8. The peaks and valleys extend in the longitudinal direction and length of the article, and only the peaks of the article are continuously cooled by pipes 7.
FIG. 3 shows a process wherein a foamed article having peaks and valleys on its surface which has been prepared in the manner illustrated in FIG. 2 is pressed or compressed from the surface, and forms high density portions at locations corresponding to the peaks now-compressed, and low density portions at locations corresponding to the valleys. In FIG. 3, shaped, foamed article 8 is at first passed through guide 9, then through a forming frame 10, whereby the external shape of the aticle is adjusted. Forming frame 10 is closely contacted with outside surface of box 11 containing cooling water therein. Thereafter, foamed article 8 is pressed by a number of rolls 12, which are arranged in parallel crosses, while article 8 is being cooled in contact with the cooling water, so as to level the peaks with the valleys and to form a flat surface. After thus being pressed, high density portions 82 are formed on the portions of the article corresponding to the portions of the article where the peaks were located. As a result, there is obtained a synthetic wood 13 having alternately high density portions and low density portions on the surfaces. Because the surface of article 8 is in a softened state at a time of pressing, the pressing has an influence only on the surface and does not cause or only minimally causes changes in the inner portion of the article.
The present invention is characterized in that the recesses or grooves, i.e., corrugations, are provided at the periphery of the outlet side of the orifice in the die used therein. The recesses are first fully explained hereinbelow, and then the high density portions formed in the final article are explained in connection with the recesses.
In general, the purpose of the recesses is to provide the surface of the final article with high density portions, and accordingly to impart the final article with a pattern similar to annual rings. In view of this purpose, the recesses should have dimensions within a pertinent range. In particular, height h from one valley to the contiguous peak should be within a pertinent range, as seen in FIG. 4, and distance f from one peak to the contiguous peak should also be within a pertinent range. If the height h is too big, then it becomes difficult to level the peak with the valley by pressing the peak, and if the distance f is too big in comparison with the height h, then density gradient becomes too small from the high density portion to the low density portion, and consequently the final article cannot have an appearance of natural wood. Thus, it is preferable that the height h is about 0.5 - 10 mm, most preferably about 1 - 5 mm. The distance f between the contiguous peaks is preferably less than 20 mm, most preferably about 10 - 2 mm. The recesses may have various shapes such as annular, triangular, or rectangular shapes on the outlet surface of the die. Preferably the recesses may be extended from the outlet surface to an inner portion away from the surface.
In FIG. 4, die 2 is provided with orifice 4 having width w and approximate thickness t, and recesses 5 formed on upper and lower peripheries of orifice 4. The recesses 5 in FIG. 4 are formed by cutting away several portions, each of which has a triangular cross-section having a steep slope m on the left and a lesser slope n on the right. The foamed article extruded from orifice 4 is in the form of a board, the surface of which has protruding portions corresponding in shape to the recesses around the orifice 4. Each of the protruding portions has a steep slope m on the left and lesser slope n on the right. The protruding portions, when pressed in a softened state, form high density portions the densities being highest at positions corresponding to the tops of the peaks and gradually decreasing according to the distances from the tops of the peak to the contiguous valleys on the right or left. In the high density portions, the density gradient is sharp on the left, because it has been formed by the left slope m, and gentle on the right, because it has been formed by the right slope n. Thus, width and density gradients of the high density portions may be varied by changing the cross-sectional shapes of recesses 5.
Referring to FIG. 5, die 2 is provided with orifice 4 having width w and approximate thickness t, and recesses 5 formed on upper and lower peripheries. The recesses 5 are rectangular in shape. The foamed article extruded from orifice 4 is in the form of a board, the surface of which has protruding portions of rectangular cross-section corresponding to the recesses 5 of the orifice 4. The peak in each of the protruding portions forms a plane parallel to the surface of the board, and both side surfaces in each of the protruding portions form planes perpendicular to the surface of the board. When the protruding portions are pressed in a softened state, they form high density portions in the final article. The high density portions are located at places corresponding to the plane peaks, and the remaining portions form low density portions. Transitions from the high density portions to the low density portions or vice versa are very clear, and transition portions form linear lines which have no substantial widths.
In FIG. 6, die 2 is provided with orifice 4 having width w and approximate thickness t, and recesses 5 formed on upper and lower peripheries of orifice 4. The recesses 5 are composed of many portions cut away, which have various sections and are located at various intervals. When foamable resin is extruded from the orifice 4, there is a formed a foamed article having peaks and valleys on its surface. When the surface is pressed, a synthetic wood product may be obtained in which high density portions and low density portions are alternately positioned in parallel relation, and transition portions between two contiguous portions have various width and density gradients.
Said recesses 5 are preferably formed deeply in the orifice from the outlet surface of the die towards the inner portion of the die. In general, it is necessary that the recesses 5 are formed deeply in the orifice in order to obtain a highly foamed article. It is not necessary, however, that recesses 5 be formed deeply in the orifice if a low foamed article is desired. In the case where a low foamed article is desired to be obtained, recesses 5 may be formed only in the vicinity of the outlet end of the die, and recesses 5 may be tapered so as to be progressively enlarged on a steep slope close to the outlet surface. Such tapered recesses are preferable in that they are easily formed in the die.
As mentioned above, a flattening process as illustrated in FIG. 3 may be continuously carried out immediately after foamed article 8 having peaks and valleys has been obtained in an extruding process as illustrated in FIG. 2. The flattening process, however, may also be carried out separately from the extruding process. In the latter case, the foamed article 8 is cooled and once taken out in the form of a board having peaks and valleys on the surface, as extruded. The article is then heated again from the surfaces to soften only the surface portions thereof, and thereafter the article is either continuously passed through a number of rolls which are arranged in parallel crosses, or placed in a heated press, in order to press only a surface layer of the article.
When the foamed article having peaks and valleys is pressed to level the peaks with the valleys, while the surface of the article is in a softened state, high density portions are produced in places where the peaks have been located. The high density portions are produced only in the surface layer of the article and no density change is formed in the inner portion of the article.
As for the resin material, so-called hard thermoplastic resin, i.e., a resin highly resistant to scratching and abrasion, should be used in the present invention but not soft thermoplastic resin. This is quite natural since it is intended that the end product should be similar to wood in physical characteristics. The hard thermoplastic resin may be, for example, a homopolymer of ethylene, styrene, propylene, vinyl chloride, or methyl methacrylate, or a copolymer of any of these. These resins may be used alone or by mixing one with one another.
Various known foaming agents may be used as the foaming agent in the present invention. The known foaming agents can be roughly classified into two groups, one of which is a solid compound that decomposes at elevated temperatures, and the other group includes liquid or gaseous compounds. The solid compounds are compounds having the property that, when heated above the softening temperature of a resin, decompose to generate gas which expands or foams the resin. The liquid or gaseous compounds are liquid or gaseous compounds that are dissolved in a resin under high temperatures and/or high pressures, and which when the resin containing the compound is brought into a lower temperature and/or under less pressure, and decreased in solubility in the resin and liberated from the resin, and expand the resin. As examples of the former compounds, there may be mentioned azo-dicarbonamide, dinitrosopentamethylenetetramine, and sodium bicarbonate. Examples of the latter compounds are hydrocarbons such as propane, butane, pentane, hexane, and halogenated hydrocarbons which are generally called "Freon" (Trademark) such as monochloromethane, trichloromonofluoromethane and the like. Among these foaming agents, the latter hydrocarbons and halogenated hydrocarbons are advantageous because they are easy to handle and because there is little fear of decomposition, and because the foaming density may be controlled as desired even with a minor quantity of them. The foaming agent may be incorporated into or mixed with the resin prior to charging into an extruder, or in the course of passing through an extruder.
Various materials other than the foaming agent may also be added to the resin. The materials are, for example, auxiliary foaming agents, fillers, coloring agents, stabilizers, plasticizers and the like. Among these, the auxiliary foaming agents are those which help the primary foaming agent foam up the resin, for example, citric acid for sodium bicarbonate. Some of the fillers may act as nuclei for foaming when the resin is foamed, and thus if a suitable amount of the filler is contained in the resin, a great number of minute cells are formed therein. The coloring agents are useful in imparting the foamed article with an appearance resembling natural wood and also with a pattern like annual rings because the coloring agents produce and intensify different shades according to variation of densities in a foamed article.
FIG. 2 shows an example of extrusion wherein cooling pipes 7 are used. The action of the pipes in explained as follows:
Without cooling pipes 7 in FIG. 2, it is possible to obtain an article having peaks and valleys on its surfaces. However, if cooling pipes 7 are not used, the peaks and valleys are not formed in such well-defined shapes as those of recesses or grooves 5 provided in die 2, but the peaks are somewhat deformed and height differences between the peaks and the valleys are lessened. However, if the cooling pipes are provided so that the surface of each of the pipes may be contacted with only tops of the individual peaks formed on the extruded article, then individual peaks are clearly formed, because the tops are cooled by cooling pipe 7, and after the peaks have been pressed, high density portions are clearly formed in the synthetic wood product. Other suitable cooling means may also be used to cool the surface of the extruded resins.
The synthetic wood product obtained by the present invention has a number of high density stripes and low density stripes, both stripes are alternately situated on the surfaces, and extend through the longitudinal direction of the product. The product, therefore, has a surface appearance resembling natural wood. When a coloring material is added to the resin in order to impart a color of natural wood to the resin, the product presents shade differences in color corresponding to density differences, and thus the product tends to have a greater resemblance to natural wood in appearance. Moreover, the synthetic wood product has high density stripes only on its surface layer, and has high surface hardness as a whole, therefore the surface of the product is difficult to damage. Further, the product differs from the known synthetic wood having an annual ring structure in that the product according to the invention has high bending strength in its width direction, because the product is not consituted of many coalesced resin strands. Furthermore, according to the present invention, it is easy to adjust a distribution of high density stripes and low density stripes formed on the synthetic wood product, merely by varying shapes and sizes of the recesses provided on the peripheries of the orifice.
In order to obtain a synthetic wood board product having a broad width, it is necessary to allow the formable resin to flow uniformly in the width direction of the orifice in die 2. For this purpose, die 2 may be provided with an intermediate plate indicated by numeral reference 14 in FIG. 7. Intermediate plate 14 has a structure such that a number of perforations are uniformly distributed across the face of a plate which as a uniform thickness over entire face of the plate. The perforations provided in the center portion of the plate have the same diameter throughout their lengths, however, the perforations in the peripheral portion are enlarged in their diameters at the resin inlet side. The land length of the enlarged portion is greatest in the outermost perforation and decreases gradually as the perforations are located in close position to the center. When a die having such plate is used, an extruded resin meets with great resistance in the central portion of intermediate plate 14, but with little resistance in the peripheral portion. In general, a resin has a tendency to flow easily in the central portion of an orifice but not in the peripheral portion. The tendency, however, can be adjusted by an intermediate plate 14 so that the resin may flow uniformly across the width of the orifice and therefore by the use of intermediate plate 14 it is easy to prepare a board having a broad width. Although FIG. 7 illustrates intermediate plate 14 provided with perforations having enlarged portions at the resin inlet side, the perforations may have the enlarged portions at the resin inlet side. Further, the perforations may be distributed unevenly on the face of the plate, i.e., a greater number of perforations at the peripheral portions, instead of providing perforations with enlarged portions.
In order to obtain a synthetic wood board having a broad width, it is also necessary to supply to die 2 a large amount of resin which is at an identical temperature. to this end, there may be used a temperature regulator which is indicated by numeral reference 15 in FIG. 7. Temperature regulator 15 is constructed by inserting a torpedo-like member 17 into an outer sheath 16, and an annular passage 18 is defined between them. Torpedo 17 houses a cavity, whereto two pipes extend, and a heating or cooling medium is circulated through said pipes to heat or cool torpedo 17. Outer sheath 16 is provided with a groove along the outer surface of the outer sheath, whereto pipes extend, and outer sheath 16 is heated or cooled in the same manner. Thus, the resin passing through annular passage 18 is heated or cooled through both outer sheath 16 and torpedo 17, and the resin temperature can be controlled within a narrow range.
Intermediate plate 14 and temperature regulator 15 are use in some examples stated below.
By way of examples, the present invention is further explained in order to clarify features and effects of the present invention. Parts referred to in the examples are parts by weight unless otherwise indicated.
EXAMPLE 1
Foamable resin material was prepared by intimately mixing 100 parts of polystyrene beads which contain about 2 weight % of butane, with 2 parts of fine powdery talc acting as a cellnucleating agent and 0.1 part of a brown pigment, and the foamable resin material was thereafter charged into an extruder having an internal diameter of 40 mm. In the extruder, a screw was rotated at the rate of 40 rotations per minute, the polystyrene was heated at 135-145°C and extruded from a die. Temperature regulator 15 was provided between the die and the forward end of the extruder as shown in FIG. 7, and intermediate plate 14 was also provided in the die.
The orifice in the die had the shape shown in FIG. 5. In FIG. 5, the orifice has a slit constituting a bases for a desired article, and thickness t in the slit was 5 mm and width w in the slit was 50 mm, height h and width j in recesses a were 2 mm and 2.5 mm, respectively, and nine recesses a were provided on each of upper and lower peripheries. Land length of the orifice was 15 mm.
Cooling pipes 7 were provided on the forward end of die 2 as shown in FIG. 2, and air was circulated into pipes 7. Foamable resin extruded from the orifice was at first introduced into a forming guide 9, which has inner dimensions of 24 × 100 mm, then into a forming frame 10, which had inner dimensions of 20 × 90 mm, and thereafter into a cooling box 11 containing water, wherein the surface of the thus foamed article was completely flattened by rolls, which were arranged in parallel crosses, and thus obtained a synthetic wood product.
For comparison, another synthetic wood product was obtained in the same procedure, except that there was removed cooling pipes 7, and accordingly the foamable resin was not cooled at the peak by pipes 7.
Both synthetic wood products had an appearnace similar to natural wood having a straight grained pattern wherein high density portions were colored in deep brown, low density portions in light brown, and the high density portions were formed alternately with the low density portions. Each border between the above two portions were clearly observed as a line having no substantial width.
Surface hardness and density of the respective synthetic wood products were measured. It was found that the synthetic wood products had different values in the surface hardness and surface density, depending upon whether cooling pipes 7 were used or not. The products, however, had identifcal hardness and density in the inner portions. Further, it was found that it was only in the surface layer within about 1 mm in depth from the surface that were produced high density portions and low density portions, and that both products were uniformly foamed in the inner portions except for the above surface layer. The results are as follows:
Measured portions Hardness.sup.(1) Density__________________________________________________________________________ High density portion g/cm.sup.3 (deep color) 75 - 80 0.60When cooling Low density portionpipes were used (light color) 41 - 46 0.27 Central portion in the foamed article 60 - 65 0.48 High density portion (deep color) 60 - 65 0.48When no cooling Low density portionpipes were used (light color) 38 - 43 0.26 Central portion in the foamed article 20 - 25 0.19__________________________________________________________________________
1. The hardness was measured by means of Type-D-durometer according to ASTM-D-2240-64T.
Bending strength was found to be 60 kg/cm 3 in the direction perpendicular to the extruding direction of the synthetic wood product. The bending strength was measured in the following manner: There was used an apparatus of Tensilon UTM-1 type made by Toyo Measuring Instrument Company Limited. Test pieces having the dimensions of 20 mm (thickness) × 90 mm (width) × 50 mm (length) (extruding direction runs in the side of 50 mm) were cut from the respective synthetic wood products, each of which pieces was supported by two points, each of the points being at a distance of 10 mm from both ends of the side having 90 mm length (and therefore the interval of above two points was 70 mm), and each of which pieces was pressed by adding a pressing force parallel to the side of 20 mm onto the pieces at the rate of 30 mm/min, thus the bending strength was measured.
For further comparison, a conventional synthetic wood product was prepared by extruding foamable polystyrene to form a number of foamed strands having low density foamed skin, and by coalescing them to form a foamed article having annual ring structure (average density 0.2 g/cm 3 ). With respect to the thus obtained product, bending strength in the direction perpendicular to the extruding direction was measured in the same manner as stated above. The bending strength was 15 kg/cm 2 . Comparing this to the above values, it was confirmed that the synthetic wood product prepared by the present invention had a greater bending strength.
EXAMPLE 2
100 parts of polypropylene was mixed with 1.0 part of fine powdery talc (cell-nucleating agent) and 0.1 part of blue pigment, and the thus obtained mixture was charged into an extruder having inner diameter of 40 mm connected in series with another extruder having inner diameter of 50 mm. Both extruders were heated at 200°-250°C. Pentane was added to the mixture in the extruders at the rate of about 3 parts of pentane against 100 parts of polypropylene. Temperature of the die was maintained at 155° - 160°C. In this example, temperature regulator 15 and intermediate plate 14 were provided as shown in FIG. 7, and these were as same as in Example 1.
Orifice in the die was formed so as to have a rough shape as shown in FIG. 4, which orifice was provided with many triangular recesses on the resin outlet side, though the number of the recesses was not identical with that of the recesses in FIG. 4. In particular, the orifice had such shape that, in FIG. 4, t was 3 mm, w 50 mm, f 3 mm, h 2 mm, length proportion of side m to side n was 1 : 2, and 16 triangular recesses were provided on each of the upper and lower peripheries. Land length of the die was 15 mm. Foamable polypropylene was extruded from the orifice in the die, and the thus extruded article cooled by cooling pipes 7 only at its peaks as in Example 1. Then the peaks were pressed in the same manner as in Example 1 to form a synthetic wood product having a cross section of 20 mm (thickness) × 90 mm (width) and a density of 0.27 g/cm 3 .
The synthetic wood product had appearance similar to natural wood having straight grains, wherein deep blue portions having high density were formed alternately with light blue portions having low density. However, transitions between the high and low density portions were all gradual, and density gradients were steep on sides m and less on the sides n. Further, the high and low density portions were positioned only in surface layer within the depth of 1 mm from the surface of the product, and the inner portions were uniformly foamed. Regarding the product, hardness and density were measured in the same manner as in Example 1, and the hardness and density in the high density portions were found to be 40 - 45 and 0.47 g/cm 3 , respectively, those in the low density portions 22 - 28, and 0.30 g/cm 3 , respectively, and those in the inner portions 15 - 20 and 0.25 g/cm 3 , respectively. Bending strength in the width direction of the product was 66 kg/cm 2 .
For comparison, a conventional synthetic wood product was prepared in almost the same manner as in Example 1, by extruding foamable polypropylene to form a number of foamed strands having low density skin, and by coalescing the strands to form a foamed article having annual ring structure (average density 0.27 g/cm 3 ). With respect to the thus obtained product, bending strength in the direction perpendicular to the extruding direction was measured in the same manner as stated above. As a result, the bending strength was found to be 9kg/cm 2 . From a comparison of these values, it was made clear that the synthetic wood product obtained by the present invention had a greater bending strength.
EXAMPLE 3
100 parts of polystyrene were mixed with 2 parts of fine powdery talc (cell-nucleating agent) and 0.12 part of brown pigment, and the thus obtained mixture was charged into the extruder used in Example 2. The extruder was heated to 190° - 220°C, about 2.5 parts of butane was added under pressure to the mixture in the extruder, and die was maintained at the temperature of 145°- 150°C.
Orifice in the die was formed so as to have a rough shape such as that shown in FIG. 6, which orifice was constituted from a basic slit and many recesses of various shapes added to the slit. The basic slit had, as in FIG. 6, thickness t of 2.5 mm and width w of 150 mm. Among the recesses, a recess located at the center on the upper periphery in the width direction had a rectangular cross section, width f 1 of which was 10 mm and height h 1.5 mm. The other recesses were progressively decreased in width f according as the recesses were situated more distant from the center recess, although height h was maintained at 1.5 mm in all the recesses. Thus, the outest recess had width f n of 3 mm. Land length of the die was 10 mm.
Foamable polystyrene was extruded from the orifice in the die, and the thus extruded article was treated in the same manner as in Example 1 with the use of cooling pipes 7, to obtain a synthetic wood product having a thickness of 10 mm, width of 260 mm, and average density of 0.17 g/cm 3 .
The synthetic wood product had high and low density portions which were alternately located on the surface and extended through the longitudinal direction of the product, high density portions being deep brown in color and low density portions light brown. Thus the product had an appearance similar to natural wood. Transitions from the high density portions to the low density portions and vice versa, took place gradually spreading over some ranges except in center portion, and the transitions took place only in the surface layer within about 1 mm in depth from the surface. Surface hardness and density in various portions of the product were found to be 36 - 42 and 0.38 g/cm 3 , respectively, those in the low density portions 24-27 and 0.26 g/cm 3 , respectively, and those in the inner portions 10 - 15 and 0.13, respectively. Further, the product had great bending strength in the width direction.
EXAMPLE 4
In this example, the pressing process was carried out separately from the extruding process. In particular, foamed board which has peaks and valleys on its surface was at first cooled and taken out as a shaped article, then the board was heated again from its surface, and the peaks were pressed to flatten the surface.
In the extruding process, there was used the same resin material containing talc and pigment, the same extruder and die as used in Example 3, but not using forming guide 9, forming frame 10, and rolls 12 arranged in parallel crosses, shown in FIG. 3, in the extruding process. The foamed board was obtained by maintaining the other conditions identical with those in Example 3. The board had peaks and valleys, height differences between which were 1 - 2 mm, and the board had the average thickness of 20 mm, the width of 300 mm, and the average density of 0.13 g/cm 3 . (No substantial density difference was found between the peaks and valleys.)
The foamed board was placed in a press heated at 100°C, pressed until the board had the thickness of 12 mm, maintained in this state for a minute, immediately thereafter cooled to 50°C. A board product was obtained the surface of which was flattened. The board product had a thickness of 12 mm, an average density of 0.22 g/cm.sup. 3, deep brown high density portions and light brown low density portions on the surface thereof, and an appearance similar to natural wood.
With respect to the board product, hardness and density were measured in the same manner as in Example 3. As a result, hardness and density in the deep brown high density portions were found to be 55 - 60 and 0.42 g/cm 3 , respectively; hardness and density in the light brown low density were found to be 40 - 45 and 0.30 g/cm 3 , respectively, and hardness and density in the inner portion 10 - 15 and 0.14 g/cm 3 , respectively. Comparing the above values with values obtained in Example 3, it was found that the synthetic wood product in Example 4 had greater hardness and greater density differences than that in Example 3. This is due to formation of the surface skin which has high density and covers entire surface of the product, on account of after-pressing.
EXAMPLE 5
Resin material, extruder and extruding conditions used in this Example were the same as those used in Example 1, except that there was used a die having an orifice 4 such as in FIG. 1, which die was provided with many semicircular recesses on both peripheries 5. In particular, the orifice consisted of a basic slit with semicircular, recesses, the basic slit had a width of 50 mm, a thickness of 5 mm, and each of peripheries 5 was provided with 18 semicircular recesses, the diameters of which were all 1.2 mm. Land Length of the die was 15 mm.
Foamable resin was extruded from the orifice to obtain a board having peaks and valleys, which peaks were contacted with cooling pipes 7, advanced continuously, and treated in the same manner as in Example 1.
The synthetic wood product obtained had a cross section of 20 mm × 90 mm and a density of 0.2 g/cm 3 . The product had deep brown high density portions and light brown low density portions, both of which were positioned alternately of each other at equal intervals only in the surface layer of the product, and extended in the extruding direction. The product had transition portions from the high density portions to the low density portions, and vice versa, in which transition portions density changes occurred gradually within a range of some width, and an appearance similar to natural wood having straight grains. The synthetic wood product had a bending strength of 60 kg/cm 2 in the direction perpendicular to the extruding direction. The product had a greater bending strength compared with the conventional synthetic wood which comprises many coalesced resin strands. | An improvement in a process for preparing a foamed thermoplastic article in which a foamable thermoplastic resin is passed through an orifice of a die and is permitted to expand after passing through said orifice. The improvement includes
A. passing the foamable thermoplastic resin through an orifice, the outer periphery of which contains a plurality of recesses,
B. allowing the resin to expand to form a soft-surfaced porous shaped article having peaks and valleys corresponding to the recesses of the orifice, and
C. pressing the surface of said article so as to level the peaks.
A smooth-surfaced shaped article is produced having a surface structure characterized by high density portions corresponding to the peaks and low density portions corresponding to the valleys and resembling natural wood. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to blowing lances, and more particularly to blowing lances used in the refining of a metal by blowing a gas onto the surface of a molten metal bath.
During a refining process, for example during the refining of cast iron or of an iron compound, a refining gas, mostly oxygen, is blown from above onto a molten metal bath.
A blowing lance for blowing from above onto the molten metal bath during a refining process is known. The lance includes a head with nozzles which generate up to 4 or 6 supersonic refining gas jets which impinge on the bath surface at predetermined impact spots. Such a lance is generally characterized by a gas flow rate, which is dependent on the supply pressure of the gas, and by a supersonic gas outflow speed, which is a function of the same supply pressure. In the course of the following description, a lance of this type will be designated by the expression "a conventional lance".
Different techniques have been developed for intensifying the stirring of the metal bath, and bringing continuously new molten metal into contact with an oxidizing gas, avoiding the occurrence of an oversaturation of the oxidizing gas in the bath and for avoiding a local overheating at the impact of the jets.
One such technique is disclosed in Luxembourg Patent No 87 855 (corresponding to U.S. patent application, Ser. No. 803,167, both of which are assigned to Paul Wurth S.A., a Corporation of Luxembourg and which are incorporated herein by reference) which discloses a blowing lance for generating an even number of gas jets where the impingement spots on the surface of the molten metal bath can be rotated in a continuous manner along a circular path during the refining operation. If compared to the above-mentioned conventional lance, this lance distinguished itself by providing a better stirring of the metal bath, by an improved spreading of the oxidizing gas and by a better repartition of the reaction heat in the vicinity of the impact spots of the jets. A head of this lance, according to U.S. patent application Ser. No. 803,167, includes a rotating part or rotor, which is exposed directly to the heat and to the splashes of the bath, but which, presently can not be integrated into the cooling circuit of the lance. As a result, this blowing lance head has a substantially shorter lifetime than the head of a conventional blowing lance, for which the cooling of the static terminal dome section, with fixed tuyeres therein, can easily be achieved.
Another technique, well known in conjunction with the LD-CL Process (CL=Circulating Lance), makes use of an inclined lance body able to circulate around a vertical axis, so as to sweep or scan the surface of the bath with one jet or with a plurality of jets. This LD-CL lance shows advantages which are similar to those mentioned for the lance with rotating jets of U.S. patent application Ser. No. 803,167. The implementation of the circulating lance requires however important mechanical means as well as a complete transformation of the suspension equipment for the lances.
Luxembourg Patent No 87 353 (corresponding to U.S. Pat. No. 4,993,691), both of which are incorporated herein by reference, discloses an adjustable Laval tuyere which allows, generating within a blowing lance, a supersonic gas flow where the speed and the flow rate are adjustable independently of one another. It is therefore possible to obtain with this device jets of varying hardness (or penetration) for different flow rates.
A conventional lance, equipped with such an adjustable Laval tuyere, provides of course the possibility of increasing the flow rate of the oxidizing gas during the refining operation and to thus intensify the stirring of the bath. However, a conventional lance used in combination with a Laval tuyere has several drawbacks, e.g., during use, an overconcentration of the oxidizing gas in the bath may result and/or a local overheating of the bath at the impingement points of the jets on the bath may also result.
SUMMARY OF THE INVENTION
The above-discussed and other drawbacks and deficiencies of the prior art are overcome or alleviated by the blowing lance of the present invention. In accordance with the blowing lance of the present invention, a lance for refining metals by blowing a gas onto the surface of a metal bath, comprises an adjustable tuyere which generates a supersonic refining gas flow where the flow rate and the speed are independently adjustable. The blowing lance also includes a blowing head with a set of fixed tuyeres opening into a front dome of said blowing head and dividing the supersonic gas flow into individual free jets. The present invention allows the intensifying of the stirring of the bath without increasing the risk of overheating of the metal bath or of overconcentration of the oxidizing gas at the spots where the jets are impinging on the bath. The blowing lance further includes a cyclic modulator for varying the flow rate through the set of fixed tuyeres by progressively obturating a first subset of the fixed tuyeres for the passage of the gas and for simultaneously and progressively freeing a second subset of the fixed tuyeres for the passage of the gas during the first part of a modulation cycle and vice versa during the second part of the modulation cycle.
The blowing lance cyclically modulates the flow rate of the individual jet between a minimum value and a maximum value, so that the flow rate in certain of the jets does not vary synchronously with the flow rate in the remaining jets, that is to say the flow rates do not increase or decrease at the same time and they do not reach their minimum value or their maximum value at the same moment.
During operation, the blowing lance develops a specific fluid motion in the bath with the help of a plurality of gas jets which have fixed impingement points on the bath surface. This fluid motion specifically increases the afflux of the molten material towards said fixed impingement points of the jets. The stirring of the bath is improved, without giving rise to overconcentrations of the oxidizing gas in the bath and/or to a local overheating at the spots where the jets are striking the bath.
A more detailed explanation of the lance operation on a molten metal bath in accordance with the present invention is described below.
A gas jet striking the surface of a liquid displaces from its impact spot a volume liquid and it creates in this way a depression in the surface of the liquid. The volume of the liquid displaced by a jet is a parameter which is increasing mainly with the flow rate of the jet. It follows therefrom that if the flow rate of the gas increases, the volume of the depression grows and the impact zone of the jet becomes a source generating a flow of liquid which is driven out of the impact zone.
If, on the other hand, the flow rate of a gas jet decreases, the depression created in the surface of the liquid is filled up, under the influence of gravity, and the impact zone of the jet is becoming in this way a sink generating a flow of liquid which moves towards the impact zone of the jet.
It also follows that if the flow rate of a jet is modulated between a minimum value and a maximum value it generates a more important stirring of the liquid than a jet with a steady flow rate equalling the integrated average of the modulated flow rate.
By juxtaposing sources and sinks, this is to say the jets with an increasing flow rate and those with a decreasing flow rate, one succeeds in intensifying the movements of the liquid in the bath. One creates indeed a kind of "fluid motors", which are composed of cyclically reversible couples of a source and a sink creating alternating flows of material between the impact zones of the modulated jets.
As a consequence the stirring of the bath is considerably increased as compared to a lance with non-modulated fixed jets dispensing the same flow rate of refining gas.
Industrial practice has shown that the results achieved with a lance working according to the above explained principle are at least equivalent to the results obtained with the lances with revolving jets.
As a result of an appropriate choice of the frequency and of the modulation function (i.e., the evolution of the flow rates with time and the shifting of the cycles between the individual jets) one has moreover succeeded in producing superposition phenomenon of fluid motion in the bath, thus creating a fluid motion with a resonance character. These phenomenons further increase the motion of the material in the bath and they have a positive influence on the cinetics of the metallurgical reactions as well as on the melting of scrap which might be added to the bath.
The manner in which the flow rate varies in the various jets is a function of the characteristics, as for example the geometrical configuration, of the means used to achieve the cyclic modulation of the flow rate of each individual jet.
It will e.g., be appreciated that it is possible to have a total instantaneous flow rate of all the jets that is nearly constant.
It might for example be of advantage to create couples of jets whereof one jet has a maximum flow rate at the moment when the other jet has a minimum flow rate, or vice versa.
It might also be of advantage to choose the geometrical distribution of the jets and the cyclic distribution of the flow rates in such a way, that the horizontal components of the dynamic forces acting on the lance, and which are due to an inclination of the jets, show a zero resultant at any moment of the cycle.
The above-discussed and other features and advantages of the present invention will be appreciated and understood by those skilled in the art from the following detailed description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring now to the drawings, wherein like elements are numbered alike in the several FIGURES:
FIG. 1 shows a longitudinal cross sectional view, following two perpendicular plans, of the blowing head belonging to a lance according to the present invention;
FIG. 2 shows a longitudinal cross sectional view, following two perpendicular plans, of the adjustable Laval tuyere belonging to a lance according to the present invention;
FIG. 3a and FIG. 3b show each a plan view of the impact points on the surface of the bath during the first and the second half of a cycle; and
FIG. 4a and FIG. 4b show a section AA through the modulating device during the first and the second half of a cycle.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2, the proposed blowing lance 1 comprises a lance body 2 welded to a blowing head 3. The lance body 2 includes a mantle comprising four coaxial sleeves 4, 5, 6 and 7 for example four welded steel pipes. The sleeves are kept spaced apart with the help of spacers and they are linked to the head 3 of the lance so as to delimit a water cooling circuit 9 between the sleeves 4, 5, 6 and 7 of the mantle and the walls of the blowing head 3.
It will be understood that the blowing lance of the present invention requires the suspension of the lance assembly and the feeding sources supplying the fluids, namely oxygen and nitrogen as well as cooling water which are not shown.
The inner wall of the conduit 16 in the lance body 2 delimits an annular chamber 10, defining a longitudinal axis a-a'. A supporting rod 11 is coaxial to the axis a-a' and is supporting a whole assembly constituting a part of an adjustable tuyere 12 such as a Laval tuyere which is described in U.S. Pat. No. 4,993,691. The supporting rod 11 comprises preferably of a tube which allows the incorporation of electrical cables (not shown) for supplying electrical current to the various control mechanisms which will be described at a later stage. According to another embodiment, the supporting rod 11 and the inner wall may themselves be used as electrical conductors feeding the electrical courant to said control mechanisms.
The Laval tuyere 12 further includes a translation body 13 connected to the support rod 11 through the intermediary of a control mechanism comprising a linear step by step motor 14 and a cylindrical sleeve 15. Within this sleeve 15 the translation body 13 can move up and down along the axis a-a' of the blowing lance 1. As can be seen in FIG. 2, the end of the translation body 13 has the shape of a kind of needle whereof the profile follows a continuous aerodynamical transition curve, so as to reduce to a minimum the generation of turbulences in the stream of the refining gas.
Within the mantale 7 of the lance body 2 is arranged a coaxial conduit 16 for the refining gas, namely the primary oxygen. At the height of the translation body 13, the coaxial conduit 16 comprises one part 17 made up of a converging part and of a neck which extends into a cylindrical conduit. The converging part and the fixed neck form, together with the needle of the translation body 13, an adjustable Laval tuyere 12. The characteristics or parameters of this Laval tuyere 12 can be modified by shifting the translation body 13 in the direction of the axis a-a'. This Laval tuyere allows the control of the flow rate of the refining gas independently from the supersonic speed of the jet of refining gas at the outlet of the Laval tuyere 12. The operation of the adjustable Laval tuyere 12 has been specified more in detail in U.S. Pat. No. 4,993,691.
Downstream with respect to part 17 of the conduit 16 conveying the refining gas, the blowing lance 1 includes, according to the present invention, a cyclic modulator 18 (see FIG. 1) located centrally in the supersonic flow of refining gas.
The cyclic modulator 18 is located above an inlet piece 28 provided with four inlets 29. Inlets 29 function to divide the main supersonic flow of the refining gas in an aerodynamically correct manner into four supersonic jets, whereof the flow rates would be nearly the same in the absence of the cyclic modulator 18.
Four fixed tuyeres 30, which have a constant cross section, start from piece 28 and they reach down to the terminal dome 32 of the lance head wherein they delimit four outlet orifices 31. While four fixed tuyeres are shown herein, it will be understood that any number of fixed tuyeres may be utilized.
The aforementioned four outlets 31 are spaced apart by an angle of 90° on a circumference having its center on the axis a-a' of the lance 1. While a 90° space is depicted for four outlets 31 and inlets 29 it will be understood that for any number of outlets 31, it is advantageous to provide generally an equal space between those outlets, e.g. for a total of eight outlets, a space of approximately 45° between them would be advantageous. The axis of the fixed tuyeres 30 are consequently inclined by an angle α with respect to said axis a-a' of the lance. The choice of this angle is, among other factors, a function of the geometry of the vessel and of the distance of the head of the lance above the bath. Generally, the angle α may be between 10° and 15°.
The cyclic modulator 18 functions as a kind of rotor and has an upper cylindrical part 19 which is suspended to a supporting device 20 including an upper bearing 21 and a lower bearing 22. In this embodiment the upper bearing 21 and the lower bearing 22 of the cyclic modulator 18 are roller bearings having housings which are fixed in a tight by removable manner to the wall 7 of the lance body 2. The fixing means can be different from those shown in FIG. 1, which indeed constitute only a preferred embodiment.
One or several servomotors 23, located between the wall 7 of the lance body 2 and the conduit 16, confer a rotating movement to the cyclic modulator 18 where the angular speed can be regulated.
In view of the rotation, the shaft of the servomotor 23 is provided with a pinion 24 which is operating a toothed ring 25 mounted on the supporting and moving device 20.
Connectors for supplying electricity and control signals to the servomotors 14 and 23 are located between the wall 7 and the conduit 16 although they have not been shown on the figures. It should be noted that the space between the wall 7 and the conduit 16 is advantageously filled with a neutral gas, such as nitrogen. This gas is advantageously kept under a slight overpressure with respect to the refining gas (e.g., oxygen) flowing through the central duct of the lance 1. This measure guarantees that any penetration of the oxygen, liable to cause ignitions in the servomotors and in their connectors, is avoided. In order to avoid statical electrical discharges between the different elements, mainly between the rotor and the fixed parts, equipotential measures, such as connectors 26, are foreseen.
The cyclic modulator 18 includes upper cylindrical part 19 and a rotary obturator 35, these parts being preferably connected one to another, so as to allow an easy dismanteling. The upper cylindrical part 19, which has a cylindrically shaped interior, extends over a given distance in said lance and, in spite of being subject to a rotating movement, it forms a stabilizing distance for the supersonic flow of the refining gas. The rotary obturator 35 is installed above the four inlets 29 provided in the piece 28.
According to a preferred embodiment of the rotary obturator 35, the latter comprises a tube 36 wherein are fixed two symmetrical pieces 37 at diametrically opposed locations. The inner diameter of the tube 36 is preferably chosen so that the projection of an inner section of tube 36 on the inlet piece 28 completely covers said four inlets 29, and that the contour of the projection is tangential to the four inlets 29. The shape of the pieces 37 can be described as being obtained by cutting, along an oblique plan, a full solid cylinder which has the same inner diameter and height of the tube 36. The section is operated in such way that the intersecting plan is tangential to one base of the cylinder and that it cuts off from the other base of the cylinder a circular segment having an opening angle of approximately 90° (see FIG. 4). While two symmetrical pieces 37 are depicted, it will be understood that the number of pieces 37 will be a function of the number of inlets 29.
This embodiment of the rotary obturator 35 has been selected with regard to manufacturing advantages. It advantageously fulfills its function although the opposition of the phases of the two pairs of jets is not perfect.
The operation principle of the cyclic modulator 18, as well as the generation of the fluid motion in the bath, according to the principle of reversible couples of sources and sinks, can be analyzed with the help of the FIGS. 3a, 3b and 4a, 4b.
The obturator 35 is rotated by the servomotor 23 through the intermediary of the cylinder 19 and, at the moment t o , it partially closes the two diametrically opposed inlets 29A, whereas it leaves entirely free the access to the two other diametrically opposed inlets 29B which are set off by an angle of 90° with respect to the two first outlets (see FIG. 4a). As a result thereof, the flow rate is at a minimum in the two tuyeres 30A connected to the two inlets 29A, whereas it is at a maximum in the two tuyeres 30B connected to the two inlets 29B (see FIG. 3a). During a first 180° revolution after the moment to, the flow rate will increase in the two tuyeres 30A and decrease in the two tuyeres 30B. The impact zones of the jets A1, A2 coming out of the tuyeres 30A make up the sources and the impact zones of the jets B1, B2 coming out of the tuyeres 30B make up the sinks (see FIG. 3a). Consequently a flow of material is established in the bath between the source zones and the sink zones. After having completed the first 180° revolution the obturator 35 closes to a maximum the pair of inlets 29B and it completely frees the access to the pair of inlets 29A (see FIG. 4b). As a result thereof the flow is now at a maximum in the tuyeres 30A and at a minimum in the tuyeres 30B.
During a second 180° revolution, which brings the obturator back into its initial position at the moment t o , the flow rate will increase in the two tuyeres 30B and decrease in the two tuyeres 30B. The impact zones of the jets B1, B2 coming out of the tuyeres 30B are making up sources and the impact zones of the jets Al, A2 coming out of the tuyeres 30A are making up sinks. The material flow in the bath is consequently reversed as compared to the situation pertaining to the first 180° revolution (see FIG. 3b).
This preferred embodiment of the lance has the advantage that the radial forces (perpendicular to the axis of the lance), exerted onto the blowing head 3 by the jets leaving the lance under an angle α with respect to the vertical direction, have a resultant equal to zero at any moment of the cycle. The lance according to the preferred embodiment is consequently not exposed to lateral stresses due to the jets during its operation.
In addition the lance may also have several post-combustion tuyeres 34 which are located on a circumference around the orifices of the tuyeres dispensing the primary refining gas. These post-combustion tuyeres 34 are connected to a secondary gas flow in the annular space between the walls 6 and 7 of the mantle of the lance 1.
The present invention supplies, in view of operating a refining process, a blowing lance which allows creation in the bath of fluid motion favouring the rush of material towards the impact spots of the gas jets and it increases the stirring of the liquid bath during its refining treatment, without thereby creating at the impact points of the jets, situations of overconcentration of the oxidizing gas and/or of local overheating.
The invention achieves, despite a simple mechanical design, metallurgical results which are at least equal to the results achieved with the prior art revolving jets lances, having a much more complicated mechanical design.
As the dome 32, which is constituting the extremity of the lance facing the liquid bath, is completely water cooled, the blowing head is characterized by a high lifetime.
All the movable parts are under shelter in the interior of the lance which is integrally water cooled and they are thus protected against the extremely severe environment prevailing above the surface of the metal bath.
Another advantage lies in the fact that the modulating device 18 can be added easily to an already existing lance.
Although the invention has been described in conjunction with a preferred embodiment, it will be understood that the invention may be practiced by using a number of jets which is higher or lower than four, or by selecting different shifts of the cycles between the flow rates in the jets, or by operating with other modulating functions (flow rate/time).
While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation. | A blowing lance for refining metals by blowing a gas onto a surface of a metal bath is presented. This lance has an adjustable tuyere for generating a supersonic refining gas flow and a blowing head with a set of fixed tuyeres opening into a front dome of the blowing head and dividing the supersonic gas flow into individual free jets. A cyclic modulator modulates a flow rate through the set of fixed tuyeres so that the flow rate in a first subset of tuyeres does not vary synchronously with the flow rate in a second subset of tuyeres, i.e., the flow rates in both subsets of tuyeres increase or decrease at the same time and they do not reach their minimum value or their maximum value at the same moment. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is related to a switching regulator, and more particularly, to a switching regulator for fixing an operating frequency by controlling a constant-time trigger, according to an output voltage and a phase signal.
[0003] 2. Description of the Prior Art
[0004] Power supply devices play an essential role in modern information technology. Among all the power supply devices, a DC-DC switching regulator has been very popular and is mainly used to provide regulated DC power sources to electronic components. Please refer to FIG. 1 , which illustrates a schematic diagram of a DC-DC switching regulator 10 of the prior art. The DC-DC switching regulator 10 is used to provide power for a load Load 1 , and includes an upper gate switch 100 , a lower gate switch 102 , a constant time trigger circuit 104 , a comparator 106 , an inductor L 1 , a capacitor C 1 , a reference voltage Vref 1 and an inverter INV 1 . The constant time trigger circuit 104 can output a signal pulse with constant time width to control operations of the upper gate switch 100 and the lower gate switch 102 . Every time when the output voltage Vout 1 reaches a level smaller than the reference voltage Vref 1 , the comparator 106 outputs a signal to the constant time trigger circuit 104 , such that the constant time trigger circuit 104 can output the signal pulse, to turn on the upper gate switch 100 and turn off the lower gate switch 102 . Then, the input voltage source Vin 1 starts delivering electric energy to the inductor L 1 and then to the load Load 1 via the upper gate switch 100 . Since the signal pulse outputted from the constant time trigger circuit 104 is with constant time width, the upper gate switch 100 can be turned on for a constant period of time when the output voltage Vout 1 is smaller than the reference voltage Vref 1 . If the output voltage Vout 1 becomes higher than the reference voltage Vref 1 after the constant period of time, the upper gate switch 100 will be turned off for a time interval of indefinite length. When the upper gate switch 100 is turned off, the output voltage of the DC-DC switching regulator 10 starts falling, and only when the output voltage Vout 1 is less than the reference voltage Vref 1 , the upper gate switch 100 will be turned on again. In other words, the DC-DC switching regulator 10 uses a PWM (pulse width modulation) type of control to regulate the power delivery to the load Load 1 by turning on and off the upper gate switch 100 .
[0005] Meanwhile, since the operating period of the PWM signal is the summation of the turn-on time and the turn-off time of the upper gate switch 100 , when the load Load 1 changes, the duty cycle of the PWM signal will be changed accordingly, but since the turn on time of the constant time trigger circuit 104 has been fixed, and only the turn off time can be changed, it implies the operating period (as well as the operating frequency) of the PWM signal will also be changed when the output load changes. As can be seen in the DC-DC switching regulator 10 , there are some components (e.g. inductor L and capacitor C for energy efficiency enhancement and ripple reduction) whose operating characteristics are highly dependent on the operating frequency of the DC-DC switching regulator 10 . If the operating frequency roams in a wide range, it becomes impossible for the designer to optimize the designs of those frequency-sensitive components. In this case, some negative results might be present; for example, in the DC-DC switching regulator 10 , the ripples of the output voltage Vout 1 will become too large for proper operation in some applications.
[0006] Please refer to FIG. 2 , which illustrates a schematic diagram of a DC-DC switching regulator 20 of the prior art which can fix its operating frequency. The DC-DC switching regulator 20 differs from the DC-DC switching regulator 10 by adding some components for fixing the operating frequency. The DC-DC switching regulator 20 includes an upper gate switch 200 , a lower gate switch 202 , a constant time trigger circuit 204 , a comparator 206 , an inductor L 2 , a capacitor C 2 , a reference voltage Vref 2 a and an inverter INV 2 . Besides, a frequency fixing circuit 250 is added to the DC-DC switching regulator 20 . The frequency fixing circuit 250 further includes an error amplifier 252 , a compensator 254 , a frequency-to-voltage converter 256 and a voltage reference Vref 2 b. Noticeably, the constant time trigger circuit 204 also differs from the constant time trigger circuit 104 by adding an extra control input end 204 a. Since the control input end 204 a can be utilized to adjust the turn-on time of the constant time trigger circuit 204 for the purpose of frequency fixing, the turn-on time of the constant time trigger circuit 204 is not always fixed. When the frequency tends to change, the constant time trigger circuit 204 can adjust the length of its turn-on time according to the control signals received from the control input end 204 a. Furthermore, the constant time trigger circuit 204 can combine with the frequency to voltage converter 256 , the error amplifier 252 and the compensator 254 to form a closed loop, to force the output voltage V 256 of the frequency to voltage converter 256 to track the reference voltage Vref 2 b, such that the frequency (or period) of the PWM signal outputted by the constant time trigger circuit 204 can be fixed.
[0007] However, although the operating frequency of the DC-DC switching regulator 20 can be fixed and let the designer optimize the designs of the frequency sensitive components to reduce the output ripples, the architecture and the related circuit of the DC-DC switching regulator 20 still deserve further investigation - - - to realize the frequency fixing functions, it requires complex circuitry to implement the frequency to voltage converter 256 , the error amplifier 252 and the compensator 254 . In other words, it will take relatively large chip area, and the production cost is still higher than expected.
SUMMARY OF THE INVENTION
[0008] It is therefore a primary objective of the claimed invention to provide a switching regulator which can fix its operating frequency by controlling a constant-time trigger, according to an output voltage and a phase signal.
[0009] The present invention discloses a switching regulator for fixing a frequency, which comprises a power stage circuit, for receiving an input voltage and outputting an output voltage according to an control signal, comprising an upper gate switch, a lower gate switch coupled to the upper gate switch, and an output inductor coupled to the upper gate switch and the lower gate switch; a reference voltage generator for generating a reference voltage; a comparator for outputting a comparing result according to the output voltage and the reference voltage; a constant-time trigger circuit for outputting the control signal according to the comparing result and a compensating signal; and a frequency compensator for outputting the compensating signal according to the output voltage and a phase signal, wherein the phase signal is corresponding to the magnitude of the voltage across the lower gate switch of the power stage circuit.
[0010] The present invention further discloses a frequency compensator for a switching regulator, which comprises a voltage-to-current converter for outputting a converted current according to the phase signal; and a current-to-voltage converter for outputting a compensating signal according to the converted current and the output voltage.
[0011] These and other objectives of the present invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 illustrates a schematic diagram of a DC-DC switching regulator of the prior art.
[0013] FIG. 2 illustrates a schematic diagram of a DC-DC switching regulator of the prior art which can fix an operating frequency.
[0014] FIG. 3 illustrates a schematic diagram of a DC-DC switching regulator according to an embodiment of the present invention.
[0015] FIG. 4 illustrates a schematic diagram of a circuit of a frequency compensator used in a DC-DC switching regulator according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0016] Please refer to FIG. 3 , which illustrates a schematic diagram of a DC-DC switching regulator 30 according to an embodiment of the present invention. The DC-DC switching regulator 30 is mainly utilized to provide an output voltage Vout 3 to a load Load 3 , which is denoted as a current source Iout 3 . The DC-DC switching regulator 30 comprises a power stage circuit 32 , a comparator 306 , a reference voltage Vref 3 , an inverter INV 3 , a constant time trigger circuit 304 and a frequency compensator 310 . The power stage circuit 32 comprises an upper gate switch 300 , a lower gate switch 302 , an inductor L 3 , and a capacitor C 3 . The architecture of the DC-DC switching regulator 30 is similar to that of the DC-DC switching regulator 20 , while the frequency compensator 310 of the DC-DC switching regulator 30 controls the constant time trigger circuit 304 according to an inductor current IL 3 of the inductor L 3 and an output voltage Vout 3 , to fix an operating frequency. The control input end 304 a can be utilized to adjust the turn-on time of the constant time trigger circuit 304 for the purpose of frequency fixing. The working principle of the frequency compensator 310 is introduced as follows.
[0017] In the DC-DC switching regulator 30 , the output voltage Vout 3 can be derived by examining the voltage across the inductor L 3 and can be expressed by the following equation:
[0000]
Vout
3
=
1
Ts
·
∫
0
Ton
(
Vin
3
-
IL
3
·
Rds
1
)
·
t
+
1
Ts
·
∫
Ton
Ts
(
0
-
IL
3
·
Rds
2
)
·
t
.
[0018] The symbols Ts, Ton, IL3, Rds1 and Rds2 denote the length of the operation period, the length of the turn-on time of the upper gate switch 300 , the inductor current, the on resistance of the upper gate switch 300 and the on resistance of the lower gate switch 302 , respectively. The first term on the right hand side of the above equation is contributed by the condition when the upper gate switch 300 is on and the lower gate switch 302 is off; meanwhile, the second term on the right hand side is contributed by the condition when the upper gate switch 300 is off and the lower gate switch 302 is on. These two terms determine the magnitude of the output voltage Vout 3 . And, when the input voltage Vin 3 , the output voltage Vout 3 and the inductor current IL 3 are relatively stable, the above equation can be rearranged as the following equation:
[0000] Ts·V out3= T on·( V in3− IL 3· Rds 1)+[0−( Ts−T on)·( IL 3· Rds 2)].
[0019] By rearranging the above equation, the operation period Ts can be expressed as:
[0000]
Ts
=
Ton
·
Vin
3
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vout
3
+
(
IL
3
·
Rds
2
)
=
Ton
·
Vin
3
Vout
3
·
1
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vin
3
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0020] According to function of the constant time trigger circuit 304 , the length of the turn-on time Ton is determined internally by the output voltage Vout 3 and the input voltage Vin 3 , and the Ton can then be expressed as:
[0000]
Ton
=
K
1
·
Vout
3
Vin
3
,
[0000] where the parameter K 1 is a constant parameter and is decided by the internal circuit of the constant time trigger circuit 304 . Then, the equation for Ts can now be rearranged and expressed as the following equation:
[0000]
Ts
=
K
1
·
1
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vin
3
1
+
(
IL
3
·
Rds
2
)
Vout
3
.
[0021] Typically, the parameter K 1 is equal to 2.5 μsec for a switching regulator operated at 400 KHz.
[0022] By closely examining the above equation, the operating frequency of the DC-DC switching regulator 30 will be changed if the values or the magnitudes of the inductor current IL 3 , the output voltage Vout 3 , the input voltage Vin 3 , the on resistance of the upper gate switch Rds 1 and/or the on resistance of the lower gate switch Rds 2 change, and the stability of the operating frequency of the DC-DC switching regulator will be affected. According to more detailed numerical simulation, the term in the denominator, which is
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
,
[0000] of the above equation is the one which is much influential to the stability of the operating frequency. According to the above equation for Ts, if the influence of the term in the denominator can be removed, the operating frequency of the DC-DC switching regulator will be much more stable.
[0023] Therefore, in the present invention, in order to stabilize the operating frequency of the DC-DC switching regulator 30 , the equation to determine the turn-on time can be modified and expressed as follows:
[0000]
Ton
=
K
1
·
Vout
3
+
IL
3
·
Rds
2
Vin
3
.
[0024] In the equation above, the term Vout 3 +IL 3 ·Rds 2 in the nominator is used to replace the original nominator (Vout 3 ) in the equation for determining the turn-on time Ton. This is equivalent to increase the output voltage Vout 3 by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times, such that the Ton Time can also be increased by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times, then the above equation for the period of operation Ts can be modified as follows:
[0000]
Ts
=
K
1
·
[
1
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vin
3
]
.
[0025] As can be observed in the above equation, the term in the denominator,
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
,
[0000] has been removed, and the operating frequency of the DC-DC switching regulator 30 becomes much more stable. To implement the working principles stated above, the frequency compensator 310 of the present invention is designed to generate the special voltage Vout 3 +IL 3 ·Rds 2 , and the constant time trigger circuit 304 will determine the pulse width of the turn-on time according to the latest equation for Ton. Noticeably, a phase signal PSIG is measured at one end of the inductor L 3 and is equal to the voltage IL 3 ·Rds 2 , which is also the voltage difference across the lower gate switch 302 when the device is on.
[0026] Please refer to FIG. 4 , which illustrates a schematic diagram of a circuit of the frequency compensator 310 used in the DC-DC switching regulator 30 according to an embodiment of the present invention. The circuit of the frequency compensator 310 illustrated in FIG. 4 can be utilized to generate the voltage Vout 3 +IL 3 ·Rds 2 , and comprises a voltage-to-current converter 310 a and a current-to-voltage converter 310 b . The voltage-to-current converter 310 a is utilized to convert the voltage level of the phase signal PSIG, which is equal to IL 3 ·Rds 2 , into a converted current I_ 3 . Then, the current-to-voltage converter 310 b transforms the converted current I_ 3 into a voltage (by a resistor) and generates the sum of the voltage IL 3 ·Rds 2 and the output voltage Vout 3 .
[0027] To detail further, the voltage-to-current converter 310 a comprises two resistors R 1 , R 2 , a current mirror CM 1 , two current sources CS 1 , CS 2 , and a current switch SW 1 . The current mirror CM 1 comprises two transistors M 1 , M 2 of the same type. Both of the current sources CS 1 , CS 2 can supply the same magnitude of current I_ 1 into the transistors M 1 , M 2 , respectively. The current mirror CM 1 further assures the currents flowing through the transistor M 1 and the transistor M 2 are of the same magnitude. Therefore, if the output current is I_ 3 , then the voltage-to-current converter 310 a can assure that a current I_ 2 flowing through the resistor R 2 is equal to the current I_ 1 plus the output current I_ 3 . If the phase signal PSIG, which is IL 3 ·Rds 2 , is applied to the input end of the voltage-to-current converter 310 a , the output current I_ 3 will be proportional to the phase signal IL 3 ·Rds 2 , and can be expressed as follows:
[0000]
I_
3
=
IL
3
·
Rds
2
R
,
[0000] where R is the resistance of the resistor R 2 .
[0028] Furthermore, the output current I_ 3 of the voltage-to-current converter 310 a can be fed into the current-to-voltage converter 310 b . The current-to-voltage converter 310 b comprises a current mirror CM 2 and a resistor R 3 . The current mirror CM 2 comprises two transistors M 4 and M 5 of the same type. The current mirror CM 2 will duplicate the input current I_ 3 and make the current flowing through the resistor R 3 to be equal to I_ 3 . The current I_ 3 can be converted into a voltage difference by flowing through the resistor R 3 . Since the voltage of the input end of the current-to-voltage converter 310 b is Vout 3 , the voltage in the output end of the current-to-voltage converter 310 b can be derived as follows:
[0000]
Vout
3
+
I_
3
·
R
=
Vout
3
+
IL
3
·
Rds
2
R
·
R
=
Vout
3
+
IL
3
·
Rds
2.
[0029] As can be observed, the output voltage of the current-to-voltage converter 310 b as well as the frequency compensator 310 is equal to Vout 3 +IL 3 ·Rds 2 . Therefore, by taking the output voltage Vout 3 and the phase signal IL 3 ·Rds 2 as the inputs of the frequency compensator 310 , the voltage Vout 3 +IL 3 ·Rds 2 can be generated by the circuit illustrated in FIG. 4 .
[0030] Noticeably, some other voltages which are proportional to Vout 3 +IL 3 ·Rds 2 can also be used to adjust the length of the turn-on time Ton, and the
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] term in the denominator can also be removed. People with ordinary knowledge in the art should readily to know there are numerous alterations can be made. For example, a voltage, which is equal to
[0000]
1
3
·
(
Vout
3
+
IL
3
·
Rds
2
)
,
[0000] can also be applied to remove the denominator,
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
.
[0000] To realize this, the circuit in the frequency compensator 310 can be modified by changing the resistance of R 3 from R to R/3, and the input voltage from Vout 3 to
[0000]
Vout
3
3
.
[0000] Under this condition, a common voltage divider can be added to generate the voltage
[0000]
Vout
3
3
[0000] from Vout 3 . By this method, the voltage
[0000]
1
3
·
(
Vout
3
+
IL
3
·
Rds
2
)
[0000] can be generated to adjust the turn-on time Ton. In this case, the period of operation becomes:
[0000]
Ts
=
1
3
·
K
1
·
[
1
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vin
3
]
.
[0031] It can be observed from the above equation that a constant parameter ⅓ has appeared in the equation, and the internal circuit of the constant time trigger circuit 304 which is related to the parameter K 1 , can be readily modified by the designer to select a proper operating frequency (or period). As stated above in this alternative embodiment of the present invention, the influence of the denominator term,
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
,
[0000] can also be removed.
[0032] To sum up, the frequency compensator 310 of the present invention is utilized to generate the special voltage Vout 3 +IL 3 ·Rds 2 , and to increase the output voltage Vout 3 by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times, such that when the load experiences a sudden change, the turn-on time Ton can be increased by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times, and the operating frequency can be kept nearly constant.
[0033] Furthermore, in many applications, where both the upper gate switch and the lower gate switch use the same type of power transistors, the on resistance of the lower gate switch Rds 2 is very close to the on resistance of the upper gate switch Rds 1 , then the term
[0000]
[
1
+
IL
3
·
(
Rds
2
-
Rds
1
)
Vin
3
]
[0000] in the nominator of the above equation will be very close to 1, and the period of operation Ts will be very close to a constant value. However, even the upper gate switch 300 and the lower gate switch 302 are not of the same type, the operating frequency can be stabilized by increasing the output voltage Vout 3 by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times, and thus, the present invention can be used to increase the turn-on time Ton by
[0000]
1
+
(
IL
3
·
Rds
2
)
Vout
3
[0000] times.
[0034] Also, noticeably, instead of utilizing the phase signal PSIG to get a voltage signal corresponding to the magnitude of the output current, some alternatives can also be utilized to get the magnitude of the output current (e.g. by using a proprietary sensing resistor in the output current path to sense the magnitude of the current). The present invention can utilize the frequency compensator 310 to replace the phase signal PSIG by any signal which is corresponding to the magnitude of the output current to perform the functions of fixing the operating frequency.
[0035] On the other hand, compared with the DC-DC switching regulator of the prior art, the architecture of the present invention becomes much simpler. The DC-DC switching regulator 20 of the prior art needs to sample the PWM signal generated by the constant time trigger circuit 204 , and if the period of operation is longer than the desired value, the turn-on time Ton is adjusted to fix the operating frequency. To implement the architecture of the prior art, the circuit needs to realize an error integration process; therefore, it will include at least an OTA (operational transconductance amplifier), and a large on-chip capacitor. However, the present invention only needs a compact circuit to decide the summation of the output voltage Vout 3 and the voltage across the lower gate switch 302 . According to experimental results, the present invention spends only about 20% of the chip area of the circuit of the prior art. Also, according to the experiment, the operating frequency can be fixed in a narrow range (with variation less than 10%) for a wide range of load current (3˜10 Amperes), with Rds 1 =9 mini-ohms, and Rds 2 =4 mini-ohms.
[0036] The present invention regulates the operating frequency of the DC-DC switching regulator in a nearly fixed manner, such that the design of the frequency sensitive components of the DC-DC switching regulator becomes much simpler and more effective to reduce the output ripples. The present invention develops a theoretical background for adjusting the turn-on time of the constant time trigger circuit by referring to the output voltage and the voltage across the lower gate switch (phase signal). Meanwhile, the present invention develops a compact circuit to calculate the summation of the output voltage and the phase signal, such that the turn-on time and the operating frequency can be adjusted effectively according to the theory being developed. The experiment done in the lab proves that the theory and the circuit of the present invention are function correct and cost effective.
[0037] Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. | A switching regulator for fixing a frequency which includes a power stage circuit, for receiving an input voltage and outputting an output voltage according to an control signal; a reference voltage generator for generating a reference voltage; a comparator for outputting a comparing result according to the output voltage and the reference voltage; a constant-time trigger circuit for outputting the control signal according to the comparing result and a compensating signal; an a frequency compensator for outputting the compensating signal according to the output voltage and a phase signal; wherein the phase signal is corresponding to the magnitude of the voltage across the lower gate switch of the power stage circuit. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to a rotary indicating plate type digital display device.
In rotary indicating plate type digital display devices of a clock, etc., the driving system for a minute drum and an hour drum has heretofore included two types. One of them continuously drives both the minute drum and the hour drum, while the other intermittently drives both the minute drum and the hour drum. With the former type, a shear arises in the indicated characters of the hour and the minute, and hence, the number of hour indicating plates need be made large. Besides, the independent corrections of the hour and the minute are difficult. Further, in order that the change of the minute indication from "59" to "00" and the change of the hour indication may be carried out at the same time, specific minute indicating plates, for example, minute indicating plates for indicating "45" - "59" are provided with projecting pieces, and an engaging spring which shifts to the front of the hour indicating plate in interlocking relationship with the projecting piece is provided between the hour drum and the minute drum. In consequence, the spacing between the hour drum and the minute drum becomes large. Moreover, when a calender mechanism is provided, the date or the day of the week does not change exactly at 12.00 p.m., but errors of several minutes are involved. On the other hand, the latter type requires a driving torque which is greater than in the former. In addition, a comparatively large noise is generated every minute by the intermittent drive and such noise is offensive to the ear.
SUMMARY OF THE INVENTION
According to this invention, there is provided a rotary indicating plate type digital display device comprising a rotary indicating mechanism for the minute indication and which is continuously driven, a cam which interlocks with the minute drive mechanism, and a rotary indicating mechanism for the hour indication which is intermittently driven by the cam.
An object of this invention is to effect the change of the hour indication at the same time that the minute indication changes from "59" to "00."
Another object of this invention is to realize a drive system which requires only a comparatively small driving torque.
Still another object of this invention is to diminish the shear in indicated characters by intermittently driving a drum for the hour indication.
Yet another object of this invention is to make it possible to independently correct the minute indication and the hour indication.
BRIEF DESCRIPTION OF THE DRAWING
The above and other objects and features of this invention will become apparent from the following description and the statement of the appended claims when considered with reference to the accompanying drawing in which:
FIG. 1 is a front view, partially in section, showing an embodiment of this invention,
FIG. 2 is a sectional view taken along line II--II in FIG. 1,
FIG. 3 is a sectional view taken along line III--III in FIG. 1,
FIG. 4 is a front view of an indicating plate, and
FIGS. 5 to 12 are front views of various minute-indicating plates with indicating characters printed thereon.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a time indicating portion of the device has sixty minute-indicating plates 1, . . . , and twenty-four hour-indicating plates 2, . . . . which lie on the left of the minute indicating plates. On the left of the time indicating portion, thirty-one date-indicating plates 3, . . . . are disposed above, while seven day-of-the-week indicating plates 4, . . . . are disposed below.
First, a driving mechanism A for the minute-indicating plates 1, . . . will be explained. The rotation of a motor (not shown) is transmitted to a pinion 5.
The pinion 5 meshes with a gear 6. A tooth 6a is formed on the right side surface of the gear 6 as shown in FIG. 2, and it meshes with a pawl 7. A seat 8a is rotatably supported on an arbor 8, as seen in FIG. 1, and at one end of the seat 8a, the gear 6 is rotatably supported, and the pawl 7 is secured whereas at the other end of the seat 8a is mounted an intermediate gear 9 which meshes with a minute driving gear 10. The minute driving gear 10 is formed integrally with a minute drum 11. The minute drum 11 is rotatably supported on a main shaft 12, and has the sixty minute-indicating plates 1 rockably or pivotably mounted thereon at equal intervals along its outer periphery. The minute-indication is made by two minute indicating plates. Each time one elapses, the upper indicating plate turns over and falls, and the next minute increment of time is indicated. A cam 13 is secured to the minute driving gear 10. The cam 13 is formed with a crest 13a and a trough 13b.
Description will now be made of a driving mechanism B for the hour-indicating plates 2, . . . An hour drum 14 rotates together with the main shaft 12 through a pin 15 which is planted on the main shaft 12. Along the outer periphery of the hour drum 14, the twenty-four hour-indicating plates 2 are rockably or pivotably mounted at equal intervals. Referring to FIGS. 1 and 2, an hour driving lever 16 is rockably supported on an arbor 17. It is formed at one end with a sliding part 16a which the cam 13 follows, and at the other end with a hook part 16b which catches the minute-indicating plate 1. An hour driving pawl 18 for the hour driving lever 16 is rockably mounted by a pin 19. A coiled spring 20 is retained so as to bestow a turning or biasing force which tends to turn the hour driving lever 16 clockwise in FIG. 2 about the arbor 17. By the turning of the hour driving lever 16 in the clockwise direction in FIG. 2, a ratchet wheel 21 secured to the main shaft 12 has one detent fed by the hour driving pawl 18.
A corresponding mechanism will now be described. A minute correcting gear 24 is secured at the fore end of an arbor 23 of a minute correcting knob 22, and it meshes with the minute driving gear 10. An hour correcting knob 25 is secured to a pipe or tubular member 26 which is free to rotate relative to the arbor 23, and to which an hour correcting lever 27 is secured. The hour correcting lever 27 has a U-shaped elastic part 27a, which is formed at its fore end with a driving pawl 27b engageable with the ratchet wheel 21. By securing a pin 28 to the pawl part and snugly fitting the pin into a guide hole 29a provided in a supporting plate 29, the ratchet wheel 21 is so controlled as to prevent two or more detents from being fed. At the end of the hour correcting lever 27 remote from the elastic part 27a, there is formed a guide groove 27c, whose rocking angle is controlled by a pin protruding from the supporting plate 29. The lever 27 is given a counterclockwise turning force by a coiled spring 31, so that the driving pawl 27b is held at a position spaced from the ratchet wheel 21. Retaining pieces 32 and 33 keep the minute-indicating plate 1 and the hour-indicating plate 2 at rest till the time of their turning-over and falling, respectively. The hook part 16b is formed so that it can engage with only the minute-indicating plate 1a indicative of "59" minutes among the minute-indicating plates 1.
A calendar mechanism will now be explained. The date-indicating plates 3 and the day-of-the-week indicating plates 4 are rockably mounted at equal intervals on a date drum 36 and a day-of-the-week drum 37 secured to arbors 34 and 35, respectively. Driving mechanisms for the respective indicating plates 3 and 4 will be described with reference to FIG. 3. A date driving ratchet wheel 38 is secured at an end of the date drum 36. Day-of-the-week driving pins 39, . . . protrude from one end of the day-of-the-week drum 37.
At the fore end of the main shaft 12, a cam 40 is secured. The cam 40 has a crest 40a and a trough 40b. An upper part of a driving lever 41 is formed with a guide groove 42a which engages with a guide pin 43 planted on a side plate 42, a central part is formed with a through hole 42b through which the main shaft 12 penetrates, and a lower part has a pin 44 planted thereon which engages with a guide groove 42c provided in the side plate 42. Accordingly, the driving lever 41 is slidable in the vertical direction and the sliding amount thereof is controlled within a predetermined range. The driving lever 41 is formed with a date driving pawl 45 and a sliding piece 46 which slides on the cam face of the cam 40. The driving lever 41 is drawn upwards in FIG. 3 by a coiled spring 47. A day-of-the-week driving lever 48 is rockably supported by a pin 49, and a guide groove 50 formed in the lever 48 is coupled by the pin 44. The fore end part of the day-of-the-week driving lever 48 is engageable with the driving pins 39.
A correcting device for the calendar mechanism will be described with reference to FIG. 3. A correcting lever 53 having two arms 53a and 53b is secured to an arbor 52 of a correcting knob 51 (in FIG. 1). A date correcting lever 54 is rockably supported on an arbor 55. At one end of the lever 54 is a pawl 54a engageable with the ratchet wheel 38. At the other end is an engaging piece 54b engaging with the arm 53a of the correcting lever 53 and a coiled spring 56. A day-of-the-week correcting lever 57 is rockably supported on an arbor 58. At one end of the lever 57 is a pawl 57a engageable with the pins 39 while at the other end is an engaging piece 57b engaging with the arm 53b. A coiled spring 59 is retained between the levers 57 and 48. In order to prevent both the correcting lever 54 and 57 from feeding two or more detents, their rocking angles are controlled in such way that the extreme ends of the engaging pieces 54b and 57b are respectively engaged with stopper windows 60 and 61 provided in the side plate 42. A click spring 62 has its upper end part 62a resiliently engaged with the ratchet wheel 38, and has its lower end part 62b resiliently engaged with the pins 39 on the left side surface of the day-of-the-week drum 37. Retaining pieces 63 and 64 (in FIG. 1) keep the date-indicating plate 3 and the day-of-the-week indicating plate 4 at rest till their turning-over and falling, respectively.
Referring now to FIG. 4, description will be made of the shape of the minute-indicating plate 1 and the printing of minute indicating characters.
The minute-indicating plates 1, . . . have projections 1a and 1a on both the sides. The center line or substantially the lower edge 1b becomes the center of rocking. The left corner of the upper edge is formed into a square 1c, while the right corner is cut into an arc 1d. A notch 1e is provided at the upper edge of the indicating plate 1. The notch 1e corresponds to the retaining piece 32 when "59" is indicated in case of printing the minute-indicating characters as will be stated below. Sixty of the minute-indicating plates 1, . . . of such identical shape are prepared.
The printing of the time indicia or indicating characters will now be described. The front surface of the minute-indicating plate 1 at the time when the rocking center edge 1b lies at the base of the plate and the arc ld lies at the upper right corner, as shown in FIG. 4, is termed the surface A, while the rear surface is termed the surface B. The upper half of "00" is printed on the surface A 1 of the first minute-indicating plate as illustrated in FIG. 5, while the lower half of "01" is printed on the surface B 1 , which appears by turning over the first plate with respect to the lower edge 1b, as illustrated in FIG. 6. The upper half of "01" is printed on the surface A 2 of the second minute-indicating plate as illustrated in FIG. 7, and the lower half of "02" on the surface B 2 as illustrated in FIG. 8. Likewise, the upper half of "02" is printed on the surface A 3 of the third minute-indicating plate as illustrated in FIG. 9, and the lower half of "03" on the surface B 3 as illustrated in FIG. 10. In the same way, predetermined indicating characters are printed on the surfaces A and B of the fourth to fifty-ninth minute-indicating plates. The last sixtieth minute-indicating plate is as shown in FIGS. 11 and 12, and is bilaterally inverse with respect to the other minute-indicating plates. The upper half of "59" is printed on the front surface at the time when substantially the lower edge 1b is the center of rocking and the upper right corner is the square 1c, that is, the rear surface B' 60 , while the lower half of " 00" is printed on the surface A' 60 which appears by turning over the sixtieth plate with respect to the lower edge 1b. When the minute-indicating plates printed as described above are mounted on the minute drum 11, the square corner 1c of the last minute-indicating plate protrudes beyond the remaining minute-indicating plates as illustrated in FIG. 1. The retaining part 16b is engageable with only the protruding part (the square corner 1c of the last minute-indicating plate).
Although the minute-indicating plates 1 has been described above as being formed by printing the indicating characters after press punching, it can be quite similarly formed by performing the press punching after the printing.
The mode of operation of the device will now be explained. Upon the rotation of the motor, the motor pinion 5 is rotated. In interlocking relationship therewith, the gear 6, pawl 7, seat 8a, intermediate gear 9 and minute driving gear 10 are rotated. In consequence, the minute drum 11 is rotated, the upper stage one of the minute-indicating plates 1 comes away from the retaining piece 32 and turns over and falls, and the next minute indication is established. Since the indicating plates of from "00" to "58" are located so that the upper right corner of the indicating plate at the upper stage is the arc 1d as illustrated in FIG. 4, the hook 16b of the hour driving pawl 16 does not fasten the upper right corner of the minute-indicating plate. Accordingly, the upper stage of indicating plate 1 turns over and falls for the next indication when the minute drum 11 is fed to a position at which the plate gets clear of the retaining piece 32. In this manner, the minute-indicating plates 1 are driven in succession to display the minute increment of time. At the indication of "59," the minute-indicating plate 1 is located so that the right upper corner is the square 1c, and the notch 1e lies so as to just oppose the retaining piece 32. Therefore, when the minute drum 11 is fed, the notch 1e passes through the retaining piece 32 and is freed therefrom before the time at which the upper stage of minute-indicating plate 1 is to fall. The upper stage of indicating plate, however, does not turn over and fall because the hook 16b of the hour driving lever 16 engages the corner 1c of the indicating plate. Upon elapse of one further minute, the sliding part 16a of the hour driving lever 16 drops from the crest 13a to the trough 13b of the cam 13.
Due to such a construction, the hour driving lever 16 rocks clockwise, and the hook 16b moves upwards to release the minute-indicating plate 1. Then, the minute-indicating plate 1 turns over and falls, and the next minute "00" is indicated.
Even if the retaining piece 32 engaging with the upper stage of indicating plate 1 releases the engagement before the hook 16b is disengaged from this indicating plate, such is rather desirable for the precision of the lower digit indication. Simultaneously with the indication change of the minute-indicating plates from "59" to "00," the ratchet wheel 21 is fed by one detent by means of the driving pawl 18, the main shaft 12 is rotated to disengage the hour-indicating plate 2 from the retaining piece 33 through the hour drum 14, and the hour-indicating plate 2 turns over and falls, so that the next hour indication is made thereby displaying the hour increment of time.
Since, in this manner, the hour drum 14 is intermittently driven by the hour driving lever 16 coacting with the cam 13, the center line of the hour-indicating plates 2 is normally kept stationary at the center line of the display plane. The minute-indicating plates 1 are subjected to continuous drive as the minute drum 11 is interlocked with the rotation of the drive motor. Therefore, when the sixty minute-indicating plates 1 are included as in this embodiment, a movement over 6° in terms of the central angle is continuously performed downwards from above the center line of the display plane. That is, in this embodiment, the shear between the indicated characters of the hour and the minute is at most 3° in terms of the central angle, and this value is not exceeded. Owing to the intermittent drive of the hour drum 14, any mechanism for checking the hour-indicating plates from turning over and falling till the correct time, such as is required in the case of the continuous drive, is unnecessary. Accordingly, the minute drum 11 and the hour drum 14 may be disposed in a manner to lie almost in contact, and the spacing between both the drums is diminished.
When the main shaft 12 is rotated by just one revolution by the sequential turnings owing to the above operation, the cam 40 also undergoes one revolution. With the rotation of the cam 40, the lever 41 is gradually pushed down by the sliding piece 46. FIG. 3 shows the state of the sliding piece 46 immediately before dropping from the crest 40a to the trough 40b. When the sliding piece 46 drops to the trough 40b at the next moment, the lever 41 is instantly slid upwards by the coiled spring 47. At this time, the date driving pawl 45 feeds the ratchet wheel 38 by one detent. Simultaneously therewith, the day-of-the-week driving lever 48 is rocked through the pin 50, to feed one pin 39. Owing to the rotation of the ratchet wheel 38 by one detent, one date-indicating plate 3 is caused to turn over and fall through the date drum 36, and the next date is indicated. Owing to the feed of the pin 39, one day-of-the-week indicating plate 4 is caused to turn over and fall through the day-of-the-week drum 37, and the next day-of-the-week is indicated.
Manual corrections of the indications will now be described. When the minute correcting knob 22 is turned, the arbor 23, minute correcting gear 24 and minute driving gear 10 are rotated, and the minute-indicating plate 1 is fed in the same way as described above. The rotation of the minute driving gear 10 at this time results in that the pawl 7 merely slides on the tooth 6a of the gear 6 through the intermediate gear 9 as well as the seat 8a, and it bestows no rotation. Consequently, the gear 6 is not rotated, and any unreasonable influence is not exerted on the motor, etc. When the hour correcting knob 25 is turned, the hour correcting lever 27 is rocked through the pipe 26. The driving pawl 27b therefore feeds the ratchet wheel 21 by one detent, and the hour-indicating plate 2 is thus driven in the same way as described above. When the hour correcting lever 27 is to return to the original position by the coiled spring 31, the elastic part 27a bends and causes the driving pawl 27b to escape from the detent of the ratchet wheel 21, and hence, the ratchet wheel 21 is not damaged.
In case of correcting the date, the correcting knob 51 is turned counterclockwise. Then, the arbor 52 and the lever 53 rotate counterclockwise in FIG. 3, and the engaging piece 54b of the date correcting lever 54 is pushed down. The pawl 54a therefore moves upwards. At this time, the ratchet wheel 38 is fed by one detent, and the date-indicating plate 3 is driven. In case of correcting the day-of-the-week, the correcting knob 51 is turned clockwise. Then, the arbor 52 and the lever 53 rotate clockwise in FIG. 3, and the engaging piece 57b of the day-of-the-week correcting lever 57 is depressed. The pawl 57a therefore moves upwards, and engages with the pin 39 to feed it. Then, the day-of-the-week indicating plate 4 is fed in the same way as described above. | A rotary time-indicating plate-type digital display device comprises a rotary minute drum carrying a set of minute-indicating plates and a rotary hour drum carrying a set of hour-indicating plates. A drive system effects continuous rotation of the minute drum to individually turn over successive minute-indicating plates to display the time in minutes and effects intermittent rotation of the hour drum to individually turn over successive hour-indicating plates to display the time in hours. A lower system coacts with the minute and hour drums to effect synchronous turning over of the minute-indicating plate which indicates the 59th minute and each successive hour-indicating plate. An adjusting mechanism is disposed adjacent the minute drum for enabling adjustment of both the minute and hour drums to set the time displayed by the indicating plates. | 6 |
[0001] This invention relates generally to tools and more particularly to socket adaptors
BACKGROUND ART
[0002] Various types of tools use socket adaptors with each adaptor particularly sized to correspond to the desired hole or nut size. When performing tasks it is desirable that the tool operator has ability to switch adaptor sizes rapidly. Some previous inventors have attempted to fulfill this need.
[0003] U.S. Pat. No. 5,168,782 to Cromwell filed Apr. 1, 1991 describes a tool extension adaptor for attaching two different sized tools, such as a socket wrench to an air gun, by reversing the adaptor.
[0004] U.S. Pat. No. 5,752,418 to Robins filed Jan. 3, 1997 displays a dual sized adaptor for a socket wrench capable of projecting or telescoping alternative sized ends.
[0005] Neither of these inventors have applied the pivoting concept for switching adaptor sizes.
OBJECTS OF INVENTION
[0006] An object of this invention is to provide a dual sized socket adaptor whose size is easily changed by swiveling 180 degrees about a pivot.
[0007] A further object of this invention is to produce a socket adaptor with ability to rapidly interchange two different bits whose use would save time and labor.
[0008] Still another object of the invention is to allow flexibility in socket adaptor use without sacrificing the strength and torque associated with a hardened tempered steel socket drive shaft.
SUMMARY OF INVENTION
[0009] A socket adaptor incorporating a built in, two headed bit that can be reversed by pivoting the bit 180 degrees enabling the user to choose either of two bits without having to remove the socket as required with conventional socket wrenches. The bit head is reversible with a specific size socket or bit on one end and a different size on its opposite end. For example, one end might be adapted to {fraction (9/16)} inch with opposite end fitted for ¾ inch. Combination of other commonly used socket sizes and screwdriver bits etc. would be available.
DESCRIPTION OF DRAWINGS
[0010] [0010]FIG. 1A cross section view
[0011] [0011]FIG. 1B cross section view with pivot arm swindled
[0012] [0012]FIG. 2 front view
[0013] [0013]FIG. 3 side view
[0014] [0014]FIG. 4 side view
[0015] [0015]FIG. 5 side view
[0016] [0016]FIG. 6 front view
DESCRIPTION OF PREFERRED EMBODIMENT
[0017] In FIG. 1A the holder ( 1 ) supports a pivot arm ( 2 ) along a pivot axis ( 3 ). The pivot arm ( 2 ) has 2 pivot arm sockets ( 4 ) at its opposite ends. In this example one pivot arm socket ( 4 ) contains a phillips screwdriver head ( 5 ) and the other pivot arm socket ( 4 ) contains a common screwdriver head ( 6 ).
[0018] In FIG. 1B the pivot arm ( 2 ) is in a swiveled position.
[0019] In FIG. 2 the holder ( 1 ) is attached to an air gun ( 7 ) (which is interchangeable with a ratchet or drill) and supports the pivot arm ( 2 ) along the pivot axis ( 3 ). The pivot arm ( 2 ) has 2 pivot arm sockets ( 4 ) at its opposite ends. In this example one pivot arm socket ( 4 ) contains a phillips screwdriver head ( 5 ) and the other pivot arm socket ( 4 ) contains a common screwdriver head ( 6 ).
[0020] In FIG. 3 the holder ( 1 ) supports the pivot arm ( 2 ) along the pivot axis ( 3 ). The pivot arm ( 2 ) has 2 pivot arm sockets ( 4 ) at its opposite ends. In this example one pivot arm socket ( 4 ) contains a phillips screwdriver head ( 5 ) and the opposite pivot arm socket ( 4 ) contains a drill bit ( 8 ).
[0021] In FIG. 4 the holder ( 1 ) supports a pivot arm ( 2 ) along a pivot axis ( 3 ). The pivot arm ( 2 ) has 2 pivot arm sockets ( 4 ) at its opposite ends. In this example one pivot arm socket ( 4 ) contains a phillips screwdriver head ( 5 ) and the opposite end pivot arm socket has a common screwdriver head ( 6 ).
[0022] In FIG. 5 the holder ( 1 ) supports a pivot arm ( 2 ) along a pivot axis ( 3 ). In this case, the pivot axis ( 3 ) is of a screw headed type ( 10 ). Instead of a pivot arm socket ( 4 ) this pivot arm has male extender ( 11 ) for receipt of standard socket ( 9 ). Also shown is a pin ( 12 ) to lock the pivot arm ( 2 ) in place.
[0023] In FIG. 6 the holder ( 1 ) supports a pivot arm ( 2 ) about a pivot axis ( 3 ) having a screw head ( 10 ). This pivot axis ( 2 ) has 2 male extenders ( 11 ) at opposite ends each for acceptance of a standard socket ( 9 ) | A dual size adaptor for use in connection with an air gun, ratchet or drill with a holder having a pivot arm for reversing different size/types screwdriver heads, drill bits or sockets. | 1 |
[0001] This application is a continuation under 35 U.S.C 120 of U.S. application Ser. No. 09/784,567, filed Mar. 15, 2001 which is a continuation of U.S. application Ser. No. 09/368,984, filed Aug. 5, 1999, which is a continuation-in-part of co-pending U.S. application Ser. No. 09/135,946, filed Aug. 18, 1998, now abandoned, which was a continuation-in-part of 08/809,145, filed Mar. 26, 1997, the national stage of International Application PCT/IB95/00689, filed Aug. 24, 1995, now U.S. Pat. No. 5,852,031, issued Dec. 22, 1998. PCT/IB95/00689 was a continuation of U.S. application Ser. No. 08/315,470, filed Sep. 30, 1994, now abandoned.
[0002] Compounds of this invention have affinity for serotonin (5HT) receptors, especially the serotonin 1a receptor (5HT 1A ), and are therefore useful for treatment of diseases or conditions which are caused by disorders of the serotonin system.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to the use of pharmacologically active 2,7-substituted octahydro-1H-pyrido[1,2-a]pyrazine derivatives, and their acid addition salts. The compounds of this invention are ligands for serotonin receptor subtypes, especially the 5HT 1A receptor, and are therefore useful in the treatment of disorders that can be treated by altering (i.e., increasing or decreasing), serotonin mediated neurotransmission.
[0004] The pharmacologically active 2,7-substituted octahydro-1H-pyrido[1,2-a]pyrazine derivatives of the formula I, as defined below, are also ligands for dopamine receptor subtypes, especially the dopamine D4 receptor. They are useful in treating conditions or disorders, schizophrenia for example, that can be treated by altering (ie., increasing or decreasing) dopamine mediated neurotransmission. The dopamine receptor binding activity of these compounds is described in more detail in U.S. Ser. No. 08/809,145, supra, now U.S. Pat. No. 5,852,031. This application (08/809,145) is incorporated herein by reference in its entirety.
[0005] Serotonin plays a role in several psychiatric disorders, including anxiety, Alzheimer's disease, depression, nausea and vomiting, eating disorders, and migraine. (See Rasmussen et al., “Chapter 1. Recent Progress in Serotonin (5HT) 1A Receptor Modulators”, in Annual Reports in Medicinal Chemistry, Section I, 30, pp. 1-9, 1995, Academic Press, Inc.; Antigas et al., Trends Neurosci., 19 (9), 1996, pp. 378-383; and Wolf et al., Drug Development Research, 40, 1997, pp. 17-34.) Serotonin also plays a role in both the positive and negative symptoms of schizophrenia. (See Sharma et al. Psychiatric Annals., 26 (2), February, 1996, pp. 88-92.)
SUMMARY OF THE INVENTION
[0006] This invention relates to a method of treatment of diseases or conditions which are caused by disorders of the serotonin system which comprises administering to a mammal in need of such treatment a compound of the formula
[0007] wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, quinolyl, furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl;
[0008] Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl;
[0009] A is O, S, SO, SO 2 , C═O, CHOH, or —(CR 3 R 4 )—;
[0010] n is 0, 1 or 2;
[0011] each of Ar and Ar 1 may be independently and optionally substituted with one to four substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, thiocyano, —SR, —SOR, —SO 2 R, —NHSO 2 R, —(C 1 -C 6 )alkoxy, —NR 1 R 2 , —NRCOR 1 , —CONR 1 R 2 , Ph, —COR, COOR, —(C 1 -C 6 )alkyl, trifluoromethoxy, and -(C 1 -C 6 )alkyl substituted with one to six halogens, —(C 3 -C 6 )cycloalkyl, or trifluoromethoxy;
[0012] each and every R, R 1 , and R 2 is independently selected from the group consisting of hydrogen, —(C 1 -C 6 )alkyl, —(C 1 -C 6 )alkyl substituted with one to thirteen halogens selected from fluorine, chlorine, bromine and iodine, phenyl, benzyl, —(C 2 -C 6 )alkenyl, —(C 3 -C 6 )cycloalkyl, and —(C 1 -C 6 )alkoxy;
[0013] each and every R 3 and R 4 is independently selected from a group consisting of hydrogen, methyl, ethyl, n-propyl, and i-propyl;
[0014] diastereomeric and optical isomers thereof; and
[0015] pharmaceutically acceptable salts thereof.
[0016] This invention also provides a method of treatment of a disease or condition which is caused by a disorder of the serotonin system or a disorder of the dopamine system which comprises administering to a mammal in need of such treatment a compound of the formula
[0017] wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, quinolyl, furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl;
[0018] Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl;
[0019] A is O, S, SO, SO 2 , C═O, CHOH, or —(CR 3 R 4 )—;
[0020] n is 0, 1 or 2;
[0021] each of Ar and Ar 1 may be independently and optionally substituted with one to four substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, thiocyano, —SR, —SOR, —SO 2 R, —NHSO 2 R, —(C 1 -C 6 )alkoxy, —NR 1 R 2 , —NRCOR 1 , —CONR 1 R 2 , Ph. —COR, COOR, —(C 1 -C 6 )alkyl, trifluoromethoxy, and —(C 1 -C 6 )alkyl substituted with one to six halogens, —(C 3 -C 6 )cycloalkyl, or trifluoromethoxy;
[0022] each and every R, R 1 , and R 2 is independently selected from the group consisting of hydrogen, —(C 1 -C 6 )alkyl, —(C 1 -C 6 )alkyl substituted with one to thirteen halogens selected from fluorine, chlorine, bromine and iodine, phenyl, benzyl, —(C 2 -C 6 )alkenyl, —(C 3 -C 6 )cycloalkyl, and —(C 1 -C 6 )alkoxy;
[0023] each and every R 3 and R 4 is independently selected from a group consisting of hydrogen, methyl, ethyl, n-propyl, and i-propyl; or a
[0024] diastereomeric or optical isomers thereof; or a
[0025] pharmaceutically acceptable salt thereof; in an amount effective to treat said disease or condition.
[0026] This invention also provides a method of treating a disorder or condition selected from the group consisting of migraine, headache, cluster headache, anxiety, depression, dysthymia, major depressive disorder, panic disorder, obsessive-compulsive disorder, posttraumatic stress disorder, avoidant personality disorder, borderline personality disorder, phobia, a disorder of cognition, a memory disorder, a learning disorder (including age related memory disorder) a neurodegenerative disease (including Alzheimer's disease), anxiety and/or depression associated with senile dementia or Alzheimer's disease, cancer (including prostate cancer), cerebral infarct (including that caused by stroke, ischemia or traumatic head injury), a sexual disorder, dizziness, an eating disorder, pain, chemical dependency or addiction, peptic ulcer, and attention deficit hyperactivity disorder in a mammal, comprising administering to said mammal an amount of a compound of the formula
[0027] wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, quinolyl, furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl;
[0028] Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl;
[0029] A is O, S, SO, SO 2 , C═O, CHOH, or —(CR 3 R 4 )—;
[0030] n is 0, 1 or 2;
[0031] each of Ar and Ar 1 may be independently and optionally substituted with one to four substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, thiocyano, —SR, —SOR, —SO 2 R, —NHSO 2 R, —(C 1 -C 6 )alkoxy, —NR 1 R 2 , —NRCOR 1 , —CONRR, Ph, —COR, COOR, —(C 1 -C 6 )alkyl, trifluoromethoxy, and —(C 1 -C 6 )alkyl substituted with one to six halogens, —(C 3 -C 6 )cycloalkyl, or trifluoromethoxy;
[0032] each and every R, R 1 , and R 2 is independently selected from the group consisting of hydrogen, —(C 1 -C 6 )alkyl, —(C 1 -C 6 )alkyl substituted with one to thirteen halogens selected from fluorine, chlorine, bromine and iodine, phenyl, benzyl, —(C 2 -C 6 )alkenyl, —(C 3 -C 6 )cycloalkyl, and —(C 1 -C 6 )alkoxy;
[0033] each and every R 3 and R 4 is independently selected from a group consisting of hydrogen, methyl, ethyl, n-propyl, and i-propyl; or a
[0034] diastereomeric or optical isomers thereof; or a
[0035] pharmaceutically acceptable salt thereof; effective to treat said disorder or condition.
[0036] In one embodiment of this method, the disorder or condition being treated is migraine, headache, or cluster headache.
[0037] In another embodiment, the disorder or condition being treated is anxiety, depression, dysthymia, major depressive disorder, panic disorder, obsessive-compulsive disorder, posttraumatic stress disorder, avoidant personality disorder, borderline personality disorder, or phobia.
[0038] In another embodiment, the disorder or condition being treated is a disorder of cognition, a memory disorder, a learning disorder (including age related memory disorder), or a neurodgenerative disease (including Alzheimer's disease). In another embodiment, the disorder is a learning disorder other than age related memory disorder. In a further embodiment, the disorder or condition is a neurodegenerative disease other than Alzheimer's disease. In still a further embodiment, the disorder or condition being treated is anxiety and/or depression associated with senile dementia or Alzheimer's disease.
[0039] In another embodiment of this method, the disorder or condition being treated is cancer. In one embodiment the cancer is prostate cancer; in another embodiment the cancer is a cancer other than prostate cancer.
[0040] In another embodiment, the disorder or condition being treated is cerebral infarct. The cerebral infarct can be a cerebral infarct caused by stroke, ischemia or traumatic head injury, or the cerebral infarct can have another cause.
[0041] In other embodiments of this method, the disorder or condition being treated is a sexual disorder, dizziness, an eating disorder, pain, chemical dependency or addiction, attention deficit hyperactivity disorder (ADHD), or peptic ulcer.
[0042] In another embodiment of this method, the condition is cerebral infarct and the compound of formula I is administered in combination with a 5HT 2 antagonist.
[0043] This invention also provides the above-recited methods, wherein the compound of formula I is administered in combination with a serotonin reuptake inhibitor.
[0044] This invention also provides a method of imaging an organ in a mammal, comprising administering to said mammal a radioactive form of a compound of the formula
[0045] wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, quinolyl, furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl;
[0046] Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl;
[0047] A is O, S, SO, SO, C═O, CHOH, or —(CR 3 R 4 )—;
[0048] n is 0, 1 or 2;
[0049] each of Ar and Ar 1 may be independently and optionally substituted with one to four substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, thiocyano, —SR, —SOR, —SO 2 R, —NHSO 2 R, —(C 1 -C 6 )alkoxy, —NR 1 R 2 , —NRCOR 1 , —CONR 1 R 2 , Ph, —COR, COOR, —(C 1 -C 6 )alkyl, trifluoromethoxy, and —(C 1 -C 6 )alkyl substituted with one to six halogens, —(C 3 -C 6 )cycloalkyl, or triflouromethoxy;
[0050] each and every R, R 1 , and R 2 is independently selected from the group consisting of hydrogen, —(C 1 -C 6 )alkyl, —(C 1 -C 6 )alkyl substituted with one to thirteen halogens selected from fluorine, chlorine, bromine and iodine, phenyl, benzyl, —(C 2 -C 6 )alkenyl, —(C 3 -C 6 )cycloalkyl, and —(C 1 -C 6 )alkoxy;
[0051] each and every R 3 and R 4 is independently selected from a group consisting of hydrogen, methyl, ethyl, n-propyl, and i-propyl; or a
[0052] diastereomeric or optical isomers thereof; or a
[0053] pharmaceutically acceptable salt thereof;
[0054] and detecting the emissions of the radioactive compound.
[0055] This invention also provides a method of imaging an organ in a mammal, comprising administering to said mammal a compound of the formula
[0056] wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, quinolyl, furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl;
[0057] Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl;
[0058] A is O, S, SO, SO, C═O, CHOH, or —(CR 3 R 4 )—;
[0059] n is 0, 1 or 2;
[0060] each of Ar and Ar 1 may be independently and optionally substituted with one to four substituents independently selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, nitro, thiocyano, —SR, —SOR, —SO 2 R, —NHSO 2 R, —(C 1 -C 6 )alkoxy, —NR 1 R 2 , —NRCOR 1 , —CONR 1 R 2 , Ph, —COR, COOR, —(C 1 -C 6 )alkyl, trifluoromethoxy, and —(C 1 -C 6 )alkyl substituted with one to six halogens, —(C 3 -C 6 )cycloalkyl, or trifluoromethoxy;
[0061] each and every R, R 1 , and R 2 is independently selected from the group consisting of hydrogen, —(C 1 -C 6 )alkyl, —(C 1 -C 6 )alkyl substituted with one to thirteen halogens selected from fluorine, chlorine, bromine and iodine, phenyl, benzyl, —(C 2 -C 6 )alkenyl, —(C 3 -C 6 )cycloalkyl, and —(C 1 -C 6 )alkoxy;
[0062] each and every R 3 and R 4 is independently selected from a group consisting of hydrogen, methyl, ethyl, n-propyl, and i-propyl; or a
[0063] diastereomeric or optical isomers thereof; or a
[0064] pharmaceutically acceptable salt thereof;
[0065] in combination with a radioactive agent, and detecting the emissions of the radioactive agent.
[0066] In another embodiment, the compound of formula I of the methods of the invention is wherein Ar is phenyl, naphthyl, benzoxazolonyl, indolyl, indolonyl, benzimidazolyl, or quinolyl; Ar 1 is phenyl, pyridinyl, pyridazinyl, pyrimidinyl, or pyrazinyl; A is O, S, SO 2, CHOH, or CH 2 , preferably O, S, or CH 2 ; n is 0 or 1; and wherein Ar and Ar 1 are independently and optionally substituted with up to three substituents independently selected from the group consisting of fluoro, chloro, nitro, cyano, —NR 1 R 2 , —(C 1 -C 6 )alkoxy, —COOR, —CONR 1 R 2 , and —(C 1 -C 6 )alkyl. In a more specific embodiment, Ar, Ar 1 , A, and n are as defined in this paragraph, except for that Ar and Ar 1 are not substituted with nitro.
[0067] In another embodiment, the compound of formula I of the methods of the invention is wherein Ar is optionally substituted phenyl; Ar 1 is optionally substituted and is selected from phenyl, pyridinyl, and pyrimidinyl; A is O; and n is 1.
[0068] In another embodiment, the compound of formula I of the methods is wherein when A is O, n is 1 and Ar 1 is 5-fluoropyrimidin-2-yl, then Ar may not be p-fluorophenyl.
[0069] In another embodiment, the compound of formula I in the methods of the invention is wherein A is O or S, n is 1, and Ar is phenyl or substituted phenyl.
[0070] In another embodiment, the compound of formula I in the methods of the invention is wherein A is CH 2 , and n is zero, and Ar is benzoxazolonyl or substituted benzoxazolonyl.
[0071] In another embodiment, the compound of formula I of the methods is wherein A is O, Ar is cyanophenyl, and Ar 1 is chloropyridinyl or fluoropyrimidinyl.
[0072] In another embodiment, the compound of formula I of the methods is wherein Ar 1 is 5-fluroro-pyrimidin-2-yl.
[0073] In another embodiment of the methods, Ar 1 is 5-fluoro-pyrimidin-2-yl or pyrimidin-2-yl.
[0074] In another embodiment, the compound of formula I in the methods of the invention is selected from:
[0075] (7S,9aS)-7-((3-Methyl-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0076] (7S,9aS)-7-(3-carbomethoxy-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0077] (7S,9aS)-7-(3-nitro-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0078] (7S,9aS)-7-(3-cyano-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0079] (7S,9aS)-7-(3-methoxy-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0080] (7S,9aS)-7-(3-acetamido-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0081] (7S,9aS)-7-(3-(1,1-dimethyl)ethyl-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine;
[0082] and pharmaceutically acceptable salts thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0083] The term “treating”, as used herein, refers to retarding or reversing the progress of, or alleviating or preventing either the disease, disorder or condition to which the term “treating” applies, or one or more symptoms of such disorder or condition. The term “treatment”, as used herein, refers to the act of treating a disorder or condition, as the term “treating” is defined above.
[0084] The terms “disease” and “condition”, unless otherwise indicated, encompass both chronic diseases and conditions, as well and diseases and conditions that are temporary in nature. A disease or condition treatable according to this invention can be one of sudden onset. A disease or condition covered by the present invention can be genetic and/or environmental in origin. The origin of the disease or condition need not, however, be known, so long as a subject afflicted with the disease or condition can benefit from treatment with one or more compounds described herein.
[0085] The term “disorders of the serotonin system”, as referred to herein, refers to disorders, the treatment of which can be effected or facilitated by altering (i.e., increasing or decreasing) serotonin mediated neurotransmission.
[0086] The term “disorders of the dopamine system”, as referred to herein, refers to disorders, the treatment of which can be effected or facilitated by altering (i e., increasing or decreasing) dopamine mediated neurotransmission.
[0087] A “disease or condition caused by a disorder of the serotonin system or a disorder of the dopamine system” is, for purposes of this application, any disease or condition that has at least serotonin mediated neurotransmission or dopamine mediated neurotransmission as a contributing factor. The disease or condition can have, but does not necessarily have, both serotonin mediated neurotransmission and dopamine mediated neurotransmission as contributing factors.
[0088] When a disease or condition is said herein to be “caused” by a disorder of the serotonin system or a disorder of the dopamine system, this means that the disorder is a contributing factor to the disease or condition. The disorder need not be the sole factor causing the disease or condition.
[0089] The chemist of ordinary skill will recognize that certain combinations of substituents may be chemically unstable and will avoid these combinations or alternatively protect sensitive groups with well known protecting groups.
[0090] The term “alkyl”, as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight, branched or cyclic moieties or combinations thereof.
[0091] The term “alkoxy”, as used herein, unless otherwise indicated, refers to radicals having the formula -O-alkyl, wherein “alkyl” is defined as above.
[0092] The compounds of formula I above contain chiral centers and therefore exist in different enantiomeric forms. This invention relates to all optical isomers and all other stereoisomers of compounds of the formula I and mixtures thereof.
[0093] This invention also relates to a method of treating a disorder or condition that can be treated by altering (i.e., increasing or decreasing) serotonin mediated neurotransmission in a mammal, including a human, comprising administering to said mammal an amount of a compound of the formula I, as defined above, or a pharmaceutically acceptable salt thereof, that is effective in treating such disorder or condition.
[0094] Examples of depression that can be treated according to the invention described herein include, but are not limited to, dysthymia, major depressive disorder, pediatric depression, recurrent depression, single episode depression, post partum depression, depression in Parkinson's patients, cancer patients, and post myocardial infarction patients, and subsyndromal symptomatic depression. Examples of phobias that can be treated according to the invention described herein include, but are not limited to, social phobia, agoraphobia, and specific phobias.
[0095] Examples of eating disorders that can be treated according to the invention herein include, but are not limited to, bulimia and anorexia nervosa.
[0096] Examples of chemical dependency and/or addiction treatable according to the invention described herein include, but are not limited to, dependency on, and/or addiction to, alcohol, nicotine, cocaine, heroin, phenolbarbitol or a benzodiazepine.
[0097] Examples of sexual disorders that can be treated according to the invention described herein include, but are not limited to, paraphilias, premature ejaculation, and sexual dysfunction.
[0098] This invention also relates to any of the foregoing methods, wherein the compound of the formula I, as defined above, or pharmaceutically acceptable salt thereof, is administered in combination with a serotonin reuptake inhibitor (SRI) (eg, sertraline, fluoxetine, fenfluramine, or fluvoxamine). The term “administered in combination with”, as used herein, means that the compound of formula I or pharmaceutically acceptable salt thereof is administered in the form of a pharmaceutical composition that also contains an SRI, or that such compound or salt is administered in a separate pharmaceutical composition from that in which the SRI is administered, but as part of a dose regimen that calls for the administration of both active agents for treatment of a particular disorder or condition.
[0099] This invention also relates to the above method of treating cerebral infarct such as that caused by stroke, ischemia or traumatic head injury in a mammal, wherein the compound of the formula I, as defined above, or pharmaceutically acceptable salt thereof, is administered in combination with a serotonin-2 (5HT 2 ) receptor antagonist (eg, ketanserin, pelanserin, pipamperone, spiperone, pirenperin or ritanserin) or a pharmaceutically acceptable salt thereof. Other 5HT 2 receptor antagonists that can be used in the methods of this invention are referred to in U.S. Pat. No. 5,364,857, which issued on Nov. 15, 1994. This patent is incorporated herein by reference in its entirety.
[0100] The pharmaceutically acceptable acid addition salts of compounds of the formula I may be used, as referred to above, in the various methods of this invention. The compounds of formula I are basic in nature and are capable of forming a wide variety of salts with various inorganic and organic acids. The acids that may be used to prepare pharmaceutically acceptable acid addition salts of those compounds of formula I are those that form non-toxic acid addition salts, i.e., salts containing pharmacologically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate, maleate, fumarate, gluconate, glucaronate, saccharate, formate, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, and p-toluenesulfonate.
[0101] The term “one or more substituents”, as used herein, includes from one to the maximum number of substituents possible based on the number of available bonding sites.
[0102] Formula I above includes compounds identical to those depicted but for the fact that one or more atoms (for example, hydrogen, carbon or fluorine atoms) are replaced by radioactive isotopes thereof. Such radiolabelled compounds are useful as research and diagnostic tools in, for example, metabolism studies, pharmokinetic studies and binding assays.
[0103] This invention also relates to a method, such as positron emission tomography (PET), of obtaining images of a mammal, including a human, to which a radiolabelled compound of the formula I, or pharmaceutically acceptable salt thereof, has been administered.
[0104] The compounds of formula I that are employed in the present invention, being ligands for serotonin receptor subtypes, especially the 5HT 1A receptor, within the body, are accordingly of use in the treatment of disorders of the serotonin system.
[0105] The compounds of formula I and their pharmaceutically acceptable salts (hereinafter also referred to, collectively, as “the therapeutic compounds used in the methods of this invention”) can be prepared as described in U.S. application Ser. No. 08/809,145, now U.S. Pat. No. 5,852,031, supra, incorporated herein in its entirety by reference.
[0106] Compounds of formula I in which one or more atoms are radioactive may be prepared by methods known to a person of ordinary skill in the art.
[0107] For example, compounds of formula I wherein the radioactive atom is tritium may be prepared by reacting an aryl halide Ar-X, wherein the halogen is chlorine, bromine or iodine, with gaseous 3 H 2 and a nobel metal catalyst, such as palladium suspended on carbon, in a suitable solvent such as a lower alcohol, perferably methanol or ethanol. Compounds of formula I wherein the radioactive atom is 18 F may be prepared by reacting an aryl trialkyl stannane Ar-SnR 3 , wherein R is lower alkyl, preferably methyl or n-butyl, with 18 F-enriched fluorine (F 2 ), OF 2 or CF 2 OOF in a suitably inert solvent (cf M. Namavari, et at., J. Fluorine Chem., 1995, 74, 113).
[0108] Compounds of formula I wherein the radioactive atom is 11 C or 14 C may be prepared by reacting an aryl halide Ar-X, wherein X is preferably bromine or iodine, or an aryl trifluoromethane sulfonate (Ar-OSO 2 CF 3 ) with potassium [ 11 C]cyanide or potassium [ 14 C]cyanide and a nobel metal catalyst, preferably tetrakis(triphenylphosphine)palladium, in a reaction inert solvent such water or tetrahydrofuran, and preferably a mixture of water and tetrahydrofuran. (See Y. Andersson, B. Langstrom, J. Chem. Soc. Perkin Trans. 1, 1994, 1395).
[0109] The utility of radioactive agents with affinity for 5HT 1A receptors for visualizing organs of the body either directly or indirectly has been documented in the literature. For example, C.Y. Shiue et al., Synapse, 1997, 25, 147 and S. Houle et al, Can. Nuc. Med. Commun, 1997, 18, 1130, describe the use of 5HT 1A receptor ligands to image 5HT 1A receptors in the human brain using positron emission tomography (PET). The foregoing references are incorporated herein by reference in their entireties.
[0110] The therapeutic compounds used in the methods of this invention can be administered orally, buccally, transdermally (e.g., through the use of a patch), parenterally or topically. Oral administration is preferred. In general, these compounds are most desirably administered in dosages ranging from about 1 mg to about 1000 mg per day, although variations may occur depending on the weight and condition of the person being treated and the particular route of administration chosen. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several small doses for administration throughout the day.
[0111] When used in the same oral, parenteral or buccal pharmaceutical composition as an SRI, the daily dose of the compound of formula I or pharmaceutically acceptable salt thereof will be within the same general range as specified above for the administration of such compound or salt as a single active agent. The daily dose of the SRI in such a composition will generally be within the range of about 1 mg to about 400 mg.
[0112] When used in the same oral, parenteral or buccal pharmaceutical composition as a 5HT 2 antagonist, the daily dose of the compound of formula I or pharmaceutically acceptable salt thereof will be within the same general range as specified above for the administration of such compound or salt as a single active agent. The daily dose of the 5HT 2 antagonist in such a composition will generally be within the range of about 0.1-10 parts by weight, relative to 1.0 part by weight of the compound formula I.
[0113] The therapeutic compounds used in the methods of this invention may be administered alone or in combination with pharmaceutically acceptable carriers or diluents by either of the two routes previously indicated, and such administration may be carried out in single or multiple doses. More particularly, the therapeutic compounds used in the methods of this invention can be administered in a wide variety of different dosage forms, i.e., they may be combined with various pharmaceutically acceptable inert carriers in the form of tablets, capsules, lozenges, troches, hard candies, powders, sprays, creams, salves, suppositories, jellies, gels, pastes, lotions, ointments, elixirs, syrups, and the like. Such carriers include solid diluents or fillers, sterile aqueous media and various non-toxic organic solvents, for example. Moreover, oral pharmaceutical compositions can be suitably sweetened and/or flavored.
[0114] For oral administration, tablets containing various excipients such as microcrystalline cellulose, sodium citrate, calcium carbonate, dicalcium phosphate and glycine may be employed along with various disintegrants such as starch (and preferably corn, potato or tapioca starch), alginic acid and certain complex silicates, together with granulation binders like polyvinylpyrrolidone, sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often very useful for tabletting purposes. Solid compositions of a similar type may also be employed as fillers in gelatin capsules; preferred materials in this connection also include lactose or milk sugar as well as high molecular weight polyethylene glycols. When aqueous suspensions and/or elixirs are desired for oral administration, the active ingredient may be combined with various sweetening or flavoring agents, coloring matter or dyes, and, if so desired, emulsifying and/or suspending agents as well, together with such diluents as water, ethanol, propylene glycol, glycerin and various like combinations thereof.
[0115] For parenteral administration, solutions of a therapeutic compound used in the methods of the present invention in either sesame or peanut oil or in aqueous propylene glycol may be employed. The aqueous solutions should be suitably buffered if necessary and the liquid diluent first rendered isotonic. These aqueous solutions are suitable for intravenous injection purposes. The oily solutions are suitable for intra-articular, intramuscular and subcutaneous injection purposes. The preparation of all these solutions under sterile conditions is readily accomplished by standard pharmaceutical techniques well known to those skilled in the art.
[0116] Additionally, it is also possible to administer the therapeutic compounds used in the methods of the present invention topically when treating inflammatory conditions of the skin and this may preferably be done by way of creams, jellies, gels, pastes, ointments and the like, in accordance with standard pharmaceutical practice.
[0117] The activity of the compounds of the present invention with respect to 5HT 1A binding ability can be determined according to the following procedure. Binding assays using membranes derived from HeLa cells expressing the human 5HT 1A receptor or from membranes derived from rat brain tissue can be performed according to standard procedures. For example, HeLa cells expressing the human 5HT 1A receptor can be grown in culture to confluence and then harvested by replacing the media with phosphate-buffered saline containing 5 mM EDTA and centrifuging at 1000×g for 10 minutes at 4° C. The pellet is homogenized in a 50 mM Tris buffer containing 4 mM CaCl 2 and having a pH of 7.7, using a Brinkman Polytron at setting 6 for 20 seconds and centrifuged at 48,000×g for 10 minutes at 4° C. Membranes are stored frozen at −78° C. until the time of assay. On the day of the experiment, the membranes are resuspended in a 50 mM Tris buffer (pH 7.7) containing 4 mM CaCl 2 and 10 μM pargyline to a final tissue concentration of 2.5 mg/mL and added to test tubes containing an incubation buffer, various concentrations of test drug, and [ 3 H]-8-OH-DPAT. Non-specific binding is defined in the presence of a saturating concentration of 5HT. Assay tubes are incubated for 30 minutes at 37° C. to attain equilibrium, and incubations are terminated by rapid filtration through Whatman GF/B filters using a Brandel cell harvester. The membranes are washed three times with 4 mL aliquots of an ice-cold buffer (without CaCl 2 or pargyline). Membrane-bound ligand is determined by liquid scintillation counting of the filters in Ready-Safe scintillation cocktail. The dissociation constant (K d ) for the radioligand, previously determined by saturation analysis, is used to calculate apparent K i 's by means of the Cheng-Prusoff equation (Cheng and Prusoff, 1973). The IC 50 concentrations (concentration of compound required to displace specific binding by 50%) can be calculated by linear regression analysis of the concentration-response curves from competition binding studies. The preferred compounds of this invention bind to the human 5HT 1A receptor with a K 1 less than 5.0 micromolar.
[0118] The agonist and antagonist activities of the therapeutic compounds used in the methods of this invention at 5-HT 1A receptors can be determined using a single saturating concentration according to the following procedure. Male Hartley guinea pigs are decapitated the brain removed and the hippocampus is dissected out. The hippocampus is homogenized in a 5 mM HEPES buffer containing 1 mM EGTA (pH 7.5) using a hand-held glass-Teflon® homogenizer and centrifuged at 35,000×g for 10 minutes at 4° C. The pellets are resuspended in a 100 mM HEPES buffer containing 1 mM EGTA (pH 7.5) to a final protein concentration of 20 ug of protein per tube. The following agents are added so that the reaction mix in each tube contained 2.0 mM MgCl 2 , 0.5 mM ATP, 1.0 mM cAMP, 0.5 mM IBMX, 10 mM phosphocreatine, 0.31 mg/mL creatine phosphokinase, 100 μM GTP and 0.5-1 microcuries of [ 32 P]-ATP (30 Ci/mmol: NEG-003-New England Nuclear). Incubation is initiated by the addition of tissue to siliconized microfuge tubes (in triplicate) at 30° C. for 15 minutes. Each tube receives 20 μL tissue, 10 μL drug or buffer (at 10X final concentration), 10 μL, 32 nM agonist or buffer (at 10X final concentration), 20 μL forskolin (3 μM final concentration) and 40 μL of the preceding reaction mix. Incubation is terminated by the addition of 100 mL 2% SDS, 1.3 mM cAMP, 45 mM ATP solution containing 40,000 dpm [ 3 H]-CAMP (30 Ci/mmol: NET-275-New England Nuclear) to monitor the recovery of cAMP from the columns. The separation of [ 32 P]-ATP and [ 32 P]-cAMP is accomplished using the method of Salomon et al., Analytical Biochemistry, 1974, 58, 541-548. Radioactivity is quantified by liquid scintillation counting. Maximal inhibition is defined by 10 μM (R)-8-OH-DPAT for 5-HT 1A receptors. Percent inhibition by the test compounds is then calculated in relation to the inhibitory effect of (R)-8-OH-DPAT for 5-HT 1A receptors. The reversal of agonist induced inhibition of forskolin-stimulated adenylate cyclase activity is calculated in relation to the 32 nM agonist effect.
[0119] The dopaminergic activity of the compounds of formula I, in particular their D 4 receptor binding ability, can be determined as described in U.S. application Ser. No. 08/809,145, now U.S. Pat. No. 5,852,031, supra.
[0120] The following Examples of therapeutic compounds of formula I useful in the present invention are provided solely for the purposes of illustration and do not limit the invention which is defined by the claims.
EXAMPLE 1
(7R,9aS)-7-(Phenoxy)methyl-(2-pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0121] [0121]
[0122] A solution of 0.385 g (1.55 mmol) of (7R,9aS)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1l-pyrido[1,2-a]pyrazine (Preparation 4), 0.220 g (2.34 mmol) of phenol, and 0.488 g (1.86 mmol) of triphenylphosphine in 30 mL of dry THF was treated with 0.324 g (1.86 mmol) of diethyl azodicarboxylate, and the mixture stirred at 23° C. for 16 h. The solvent was evaporated, the residue dissolved in ethyl ether and treated with HCl(g) in ether. The precipitate was collected on a Buichner funnel, and washed with 1:1 ether:ethyl acetate three times. The solid was dissolved in water, basified with 1 M NaOH and extracted with chloroform. The organic layer was washed with 1 M NaOH (2×) and water (1×), dried (magnesium sulfate), filtered and evaporated to give 0.310 g of (7R,9aS)-7-phenoxymethyl-2,3,4,6,7,8,9,9a-octahydro-2-pyrimidin-2-yl-1H-pyrido[1,2-a]pyrazine. mp (HCI) 203-205° C. 13 C NMR (base, CDCl 3 ): δ 27.0, 29.0, 36.4, 43.6, 49.1, 54.9, 58.8, 60.8, 70.9, 109.8, 114.5, 120.6, 129.4, 157.7, 159.0, 161.5. HRMS calcd for C 19 H 24 N 4 O: 324.195. Found: 324.194.
EXAMPLE 2
7 -(Substituted-phenoxy)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0123] [0123]
[0124] Compounds of the above formula were prepared from isomers of 7-hydroxymethyl-(2 -pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 4, U.S. Pat. No. 5,122,525, and W092/13858) according to Example 1, substituting the appropriate phenol. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixture of chloroform and methanol as the eluting solvent. The stereo-chemical configuration, 7-(optionally substituted phenoxy)methyl substituent, melting point of the monohydrochloride salt, and high resolution mass spectral data are shown. U.S. Pat. No. 5,122,525 is hereby incorporated in its entirety into this application by reference.
Example 2a
[0125] (7SR,9aSR)-7-Phenoxymethyl; mp 119-122° C.; Anal calcd for C 19 H 24 N 4 O.HCl: C, 63.23; H, 6.98; N, 15.53. Found: C, 63.19; H, 7.30; N, 15.66.
Example 2b
[0126] (7R,9aR)-7-Phenoxymethyl; mp 226-231° C.; HRMS calcd for C 19 H 24 N 4 O: 324.1945, found: 324.1920.
Example 2c
[0127] (7RS,9aSR)-7-(4-Fluorophenoxy)methyl; mp 263-266° C.; HRMS calcd for C 19 H 23 FN 4 O: 342.1851, found: 342.1796.
Example 2d
[0128] (7RS,9aSR)-7-((2,4-Difluoro)phenoxymethyl); mp 242.5-244° C.; HRMS calcd for C 19 H 22 F 2 N 4 O: 360.1762, found: 360.1775.
Example 2e
[0129] (7RS,9aSR)-7-(3,4-Difluorophenoxy)methyl; mp 239-240° C.; HRMS calc for C 19 H 22 F 2 N 4 O: 360.1762, found: 360.1745.
Example 2f
[0130] (7RS,9aSR)-7-((3-Fluoro)phenoxymethyl); mp 242-243° C.; HRMS calc for C 19 H 23 FN 4 O: 342.1856, found: 342.1851.
Example 2g
[0131] (7RS,9aSR)-7-(2-Naphthoxymethyl); mp 143-145° C; HRMS calc for C 23 H 26 N 4 O: 374.2107, found: 374.2097.
Example 2h
[0132] (7RS,9aSR)-7-(1-Naphthoxymethyl); mp 243-245° C; HRMS calc for C 23 H 26 N 4 O: 374.2107, found: 374.2098.
Example 2i
[0133] (7RS,9aSR)-7-(4-Fluoro-3-methylphenoxy)methyl; mp 232-233° C.; HRMS calc for C 20 H 25 FN 4 O: 356.2012, found: 356.1992.
Example 2j
[0134] (7RS,9aSR)-7-((3-Carbomethoxy)phenoxymethyl); mp 194-196° C.; HRMS calc for C 21 H 26 N 4 O 3 : 382.2005, found: 382.2010.
Example 2k
[0135] (7RS,9aSR)-7-(5-Fluoroquinolin-8-yloxy)methyl; mp 218-220° C.; HRMS calc for C 22 H 25 FN 5 O (MH+): 394.2043, found: 394.2059
Example 2l
[0136] (7RS,9aSR)-7-((2-Methoxy-5-(1-methyl)ethyl)phenoxy)methyl; mp 94-99° C.; HRMS calcd for C 23 H 32 N 4 O 2 : 396.2518, found: 396.2504.
Example 2m
[0137] (7RS,9aSR)-7-((2-Methoxy-3-(1-methyl)ethyl)phenoxy)methyl; mp 219-221° C.; HRMS calcd for C 23 H 32 N 4 O 2 : 396.2518, found: 396.2522.
Example 2n
[0138] (7RS,9aSR)-7-((2-Methoxy-4-acetyl)phenoxy)methyl; mp 224° C (dec); HRMS calcd for C 22 H28N 4 O 3 : 396.215, found: 396.210.
Example 2o
[0139] (7R,9aS)-7-(3-(1-Methyl)ethylphenoxy)methyl; mp 70-120° C. (dec); HRMS calcd for C 22 H 30 N 4 O: 366.2413, found: 366.2420.
Example 2p
[0140] (7R,9aS)-7-((2-Methoxy)phenoxy)methyl; mp 213-215° C.; HRMS calcd for C 20 H 26 N 4 O 2 : 354.2050, found: 354.2093.
Example 2q
[0141] (7R,9aS)-7-((4-Acetamido)phenoxy)methyl; mp 192° C.; HRMS calcd for C 21 H 27 N 5 O 2 : 381.2159, found: 381.2120.
Example 2r
[0142] (7R,9aS)-7-(4-(1,1-Dimethyl)ethyl-phenoxy)methyl; mp 237-244° C. (dec); HRMS calcd for C 23 H 32 N 4 O: 380.2576, found: 380.2674.
Example 2s
[0143] (7R,9aS)-7-(3-(1,1-Dimethyl)ethyl-phenoxy)methyl; mp 229-230° C.; HRMS calcd for C 23 H 32 N 4 O: 380.2576, found: 380.2577.
Example 2t
[0144] (7R,9aS)-7-(2-(1,1-Dimethyl)ethyl-phenoxy)methyl; mp 240-241° C.; HRMS calcd for C 23 H 32 N 4 O: 380.2576, found: 380.2580.
Example 2u (7R,9aS)-7-(4-Methoxy-phenoxy)methyl; mp 219-222° C.; HRMS calcd for C 20 H 26 N 4 O 2 : 354.2050, found: 354.2063.
Example 2v
[0145] (7R,9aS)-7-(3-Methoxy-phenoxy)methyl; mp 113-115° C.; HRMS calcd for C 20 H 26 N 4 O 2 : 354.2056, found: 354.2041.
Example 2w
[0146] (7R,9aS)-7-(3-Acetamido-phenoxy)methyl; mp 156-158° C.; HRMS calcd for C 21 H 27 N 5 O 2 : 381.2165, found: 381.2160.
Example 2x
[0147] (7R,9aS)-7-(2-Cyano-phenoxy)methyl; mp 250-252° C.; HRMS calcd for C 20 H 23 N 5 O: 349.1903, found: 349.1932.
Example 2y
[0148] (7R,9aS)-7-(3-Cyano-phenoxy)methyl; mp 241.5-243° C.; HRMS calcd for C 20 H 23 N 5 O: 349.1903, found: 349.1897.
Example 2z
[0149] (7R,9aS)-7-(3-Dimethylamino-phenoxy)methyl; mp 80-82° C.; HRMS calcd for C 21 H 29 N 5 O: 367.2372, found: 367.2357.
Example 2aa
[0150] (7R,9aS)-7-(3,4-Difluoro-phenoxy)methyl; mp 252-254° C.; HRMS calcd for C 19 H 22 F 2 N 4 O: 360.1762, found: 360.1763.
Example 2ab
[0151] (7S,9aR)-7-(4-Fluoro-phenoxy)methyl; mp 281-282° C.; HRMS calcd for C 19 H 23 FN 4 O: 342.1856, found: 342.1841.
EXAMPLE 3
(7R,9aS)-7-(Substituted)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0152] [0152]
[0153] Compounds of the above formula were prepared according to Example 1 using (7R,9aS)-7-hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 5) and the appropriate phenol. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixtures of chloroform and methanol as the eluting solvent. The stereochemical configuration, 7-substituent, melting point of the monohydrochloride salt and HRMS or 13 C NMR data are shown.
Example 3a
[0154] (7R,9aS)-7-(3-Cyanophenoxy)methyl; mp 192-194° C.; HRSM calcd for C 20 H 22 FN 5 O: 367.1808, found: 367.1821.
Example 3b
[0155] (7R,9aS)-7-(4-Cyanophenoxy)methyl; mp 256-257° C.; HRSM calcd for C 20 H 22 FN 5 O: 367.1808, found: 367.1793.
Example 3c
[0156] (7R,9aS)-7-(2-Methoxy-3-(1-methyl)ethyl-phenoxy)methyl; mp >286° C.; HRSM calcd for C 23 H 31 FN 4 O 2 : 414.2424, found: 414.2418.
Example 3d
[0157] (7R,9aS)-7-(2-Fluorophenoxy)methyl; mp 209-210° C.; HRSM calcd for C 19 H 22 F 2 N 4 O: 360.1762, found: 360.1767.
Example 3e
[0158] (7R,9aS)-7-(3-Fluorophenoxy)methyl; mp 229-232° C.; HRSM calcd for C 19 H 22 F 2 N 4 O: 360.1767, found: 360.1755.
Example 3f
[0159] (7R,9aS)-7-(4-Fluorophenoxy)methyl; mp 249-254° C.; HRSM calcd for C 19 H 22 F 2 N 4 O: 360.1767, found: 360.1741.
Example 3g
[0160] (7R,9aS)-7-(3,4-Difluorophenoxy)methyl; mp 229-236° C.; HRMS calcd for C 19 H 21 F 3 N 4 O: 378.1667, found: 378.1660.
Example 3h
[0161] (7R,9aS)-7-(3,5-Difluorophenoxy)methyl; mp 248-250° C.; HRSM calcd for C 19 H 21 F 3 N 4 O: 378.1667, found: 378.1680.
Example 3i
[0162] (7R,9aS)-7-(4-lodophenoxy)methyl; mp 284-286° C; HRMS calcd for C 19 H 22 FlN 4 O: 468.0822, found: 468.0785.
EXAMPLE 4
(7RS,9aSR)-7-Phenoxymethyl-2-(5-fluoro-4-thiomethylpyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0163] [0163]
[0164] The title compound was prepared according to Example 1 using phenol and (7RS,9aSR)-7-hydroxymethyl-2-(5-fluoro-4-thiomethyl) pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 6). mp (.HCl) 192-198° C. Anal calcd for C 20 H 25 FN 4 OS: C, 61.82; H, 6.49; N, 14.42. Found: C, 61.52; H, 6.56; N, 14.42.
EXAMPLE 5
(7RS,9aSR)-7-Phenoxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0165] [0165]
[0166] A solution of 3.74 g (9.63 mmol) of (7RS,9aSR)-7-phenoxymethyl-2-(5-fluoro-4-thiomethylpyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 4) in 200 mL of ethanol was treated with 0.3 g of Raney nickle and the mixture was refluxed for 2 h. An additional 0.3 g of catalyst was added and reflux continued for 24 h. A third quantity of catalyst (0.3 g) was added and reflux continued for another 24 h. A fourth quantity of catalyst (0.3 g) was added and refluxed for 4 h. The mixture was cooled to room temperature, filtered through Celite, washing with ethanol and the filtrate was evaporated. Purification by flash silica gel chromatography with methylene chloride and 99:1 methylene chloride:methanol gave 1.30 g (39%) of the title compound. mp (.HCl) 215-217° C. HRMS calcd for C 19 H 23 FN 4 O: 342.1851, found: 342.1853.
EXAMPLE 6
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(5-fluoro-4-thiomethyl-pyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0167] [0167]
[0168] The title compound was prepared according to Example 1 using 4-fluorophenol and (7RS,9aSR)-7-hydroxymethyl-2-(5-fluoro-4-thiomethylpyrimidin-2-yl )-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 6). mp (.HCl) 201-210° C. 13 C NMR (base, CDCl 3 ): δ 11.5, 27.0, 29.0, 36.4, 44.3, 49.8, 54.8, 58.8, 60.7, 71.6, 115.35, 115.45, 115.59, 115.90, 140.4, 140.7, 150.9, 155.1, 158.8. HRSM calcd for C 20 H 24 F 2 N 4 OS: 406.166, found: 406.161.
EXAMPLE 7
(7RS,9aSR)-7-(4-Fluorophenyl)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0169] [0169]
[0170] Using the procedure described in Example 5, 8.23 g (20.3 mmol) of (7RS,9aSR)-7-(4 -fluorophenoxy)methyl-2-(5-fluoro-4-thiomethylpyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine gave 3.4 g of the title compound. mp (.HCl) 249-253° C. Anal calcd for C 19 H 22 F 2 N 4 O.HCl: C, 57.50; H, 5.84; N, 14.12; found: C, 57.40; H, 5.84; N,13.99
EXAMPLE 8
(7SR,9aSR)-7-((4-Fluorophenoxy)methyl)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0171] [0171]
[0172] A solution of 0.600 g (2.43 mmol) of (7SR,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (US Pat. 5,122,525) and 0.34 mL (2.7 mmol) of triethylamine in 10 mL of methylene chloride at 0° C. was treated with 0.20 mL (2.5 mmol) of methanesulfonyl chloride. After 10 min, the mixture was diluted with water, basified with 1 M NaOH, separated, and the mixture was extracted with more methylene chloride (2×). The combined organic layers were washed with water (1×), dried (magnesium sulfate), filtered, and evaporated to give 0.77 g (2.6 mmol) of mesylate.
[0173] A solution of 0.82 g (7.3 mmol) of 4-fluorophenol in 8 mL of DMF was treated with 0.35 g (8.8 mmol) of sodium hydride (60% oil dispersion) and allowed to react for 2 h at 40-50° C. The reaction mixture was cooled to room temperature and a solution of 0.77 g (2.6 mmol) of the above mesylate in 8 mL of DMF was added. The reaction was then heated at 100° C. for 16 h. After cooling to room temperature, the solvent was evaporated, the residue taken up in water, the pH adjusted to 2 with 1 M HCl, and washed with ethyl acetate. The aqueous phase was made basic (pH 11) with 1 M NaOH and extracted with ethyl acetate (3×). The combined organic layers were dried (magnesium sulfate), filtered, and evaported to give 0.430 g of crude product. Purification by silica gel flash chromatography eluting with 90:10 ethyl acetate:hexane gave 0.340 g (38%) of the title compound. A salt was prepared by mixing an ethanol-ethyl acetate solution of 0.29 g free base with a solution of 98 mg of maleic acid in ethanol and evaporating to dryness. The white solid was triturated with ether and dried in vacuo to give 0.35 g of salt. mp (C 4 H 4 O 4 ) 128-139° C. 13 C NMR (base, CDCl 3 ): δ 24.8, 25.2 33.8, 43.6, 49.1, 54.9, 56.6, 61.1, 69.5, 109.7, 115.48, 115.25, 115.58, 115.83, 155.4, 157.7, 161.5. Anal. calcd for C 19 H 23 N 4 OF: C, 66.64; H, 6.77; N, 16.36. Found: C, 66.28; H, 7.02; N, 16.45.
EXAMPLE 9
(7RS,9aSR)-7-Phenoxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro -1H pyrido[1,2-a]pyrazine
[0174] [0174]
[0175] A solution of 1.0 g (4.0 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 3) in 20 mL dry methylene chloride was cooled to 0° C., and treated with 0.57 mL (4.4 mmol) of triethylamine and 0.33 mL(4.2 mmol) of methanesulfonyl chloride dropwise. After 15 min, water was added and the pH adjusted to 11 with IN NaOH. The layers were separated and the aqueous phase was extracted with methylene chloride (2×). The combined organic phase was dried (magnesium sulfate), filtered and evaporated to give 1.0 g (76%) of mesylate.
[0176] A mixture of 10 mL of DMF, 0.90 g (9.6 mmol) of phenol, and 0.45 g (10.2 mmol) of NaH (60% oil dispersion) in a dry flask was stirred for 1.5 h at 40-50° C. After cooling to room temperature, the above mesylate was added in 10 mL of DMF, and the solution was heated at 100-110° C. for 16 h. After cooling to room temperature, water was added, the pH adjusted to 11 with 1 N NaOH, and the mixture extracted with ethyl acetate (3×), dried (magnesium sulfate), filtered and evaportated. The crude product was triturated with a few mL of water redisolved in ethyl acetate, dried (magnesium sulfate), filtered and evaporated. Flash chromatography on silical gel with ethyl acetate gave 0.68 g of the free base as a white solid. mp (·2HCl) 218-223° C. 13 C NMR (base, CDCl 3 ): 6 27.0, 29.0, 36.4, 43.6, 49.1, 54.9, 58.8, 60.8, 70.9, 109.8, 114.5, 120.6, 129.4, 157.7, 159.0, 161.5. Calcd for C 19 H 24 NO 4 .2HCl: C, 57.43; H; 6.60; N, 14.10; found: C, 57.54; H, 6.88; N, 13.83.
EXAMPLE 10
7 -(Substitutedphenoxymethyl)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazines
[0177] [0177]
[0178] Compounds of the above formula were prepared according to Example 8 from (7SR,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2 -a]pyrazines (U.S. Pat. No.5,122,525) and the appropriate phenol. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixture of chloroform and methanol as the eluting solvent. The stereochemical configuration, 7-phenoxymethyl substitutent, melting point of the monohydrochloride salt and HRMS or combustion analysis or 13 C NMR data are shown.
Example 10a
[0179] (7SR,9aSR)-7-(4-Acetamidophenoxy)methyl; mp 123° C. (dec); 13 C NMR (base, CDCl 3 ): δ 24.3, 24.8, 25.1, 33.7, 43.6, 49.1, 54.8, 56.6, 61.1, 69.1, 109.7, 114.9, 121.9, 130.9, 156.2, 157.7, 161.5, 168.3.
Example 10 b
[0180] (7SR,9aSR)-7-((4-Trifluoromethyl)phenoxy)methyl; mp 104-119 ° C.; HRMS calcd for C 20 H 23 F 3 N 4 O: 392.1819, found: 392.1833.
Example 10c
[0181] (7SR,9aSR)-7-((4-Methoxy)phenoxy)methyl; mp 112-114° C.; Anal calcd for C 20 H 26 N 4 O 2 .HCl: C, 61.44; H, 6.96; N, 14.33. Found: C, 61.23; H, 7.29; N, 14.51.
Example 10d
[0182] (7SR,9aSR)-7-((4-Carboethoxy)phenoxy)methyl; mp 189-191° C.; HRMS calcd for C 22 H 28 N 4 O 3 : 396.2162, found: 396.2179.
EXAMPLE 11
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0183] [0183]
[0184] The title compound was prepared according to Preparation 3 with 2-chloropyrimidine and (7R,9aS)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 8). mp (.HCl) 283-285° C. HRMS calcd for C 19 H 23 FN 4 O: 342.1856; found: 342.1867.
EXAMPLE 12
(7R,9aS)-7-(2-Phenyl)ethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0185] [0185]
[0186] A mixture of 3.75 g (14.1 mmol) of (7R,9aS)-7-hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 5), 2.48 g (21.2 mmol) of N-methylmorpholine-N-oxide, 5.0 g of 4 A molecular sieves, 0.495 g (1.41 mmol) of tetrapropylammonium per-ruthenate, and 375 mL of methylene chloride was stirred at ambient temperature for 2 h. The reaction was quenched with saturated sodium thiosulfate and filtered through Celite. The filtrate was washed with brine, dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 95:5 chloroform:methanol gave 2.27 g (61%) of (7R,9aS)-7-formyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0187] A solution of 1.70 g (4.38 mmol) of benzyl triphenyl phosphonium chloride in 20 mL of dry THF was chilled to −78 ° C. and treated with 1.75 mL (4.38 mmol) of n-butyllithium (2.5 M in hexane). After 15 min, 1.05 g (3.98 mmol) of (7R,9aS)-7-formyl-2-(5-fluoropyrimidin-2-yl) 2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 20 mL of dry THF was added dropwise over 30 min, the cooling bath was removed and the solution allowed to warm slowly to ambient temperature overnight (16 h). The solution was concentrated in vacuo and the residue was partitioned between ethyl ether and water. The organic layer was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with petroleum ether:ethyl ether in ratios from 4:1 to 3:1 gave the following isomers of 7-(2-phenyl)ethenyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine: E-(7S,9aS), 0.19 g (Rf=0.75 with 3:1 hexane:ethyl acetate); Z-(7R,9aS), 0.16 g (Rf=0.47 with 3:1 hexane:ethyl acetate); E-(7R,9aS), 0.46 g (Rf=23 with 3:1 hexane:ethyl acetate).
[0188] A mixture of 0.15 g (0.44 mmol) of Z-(7R,9aS)-7-(2-phenyl)ethenyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 0.015 g of 10% palladium on carbon and 25 mL of ethanol was shaken under 40 psig of hydrogen gas in a Parr apparatus for 6 h. The mixture was filtered through Celite, and the filtrate concentrated to give 0.124 g (83%) of (7R,9aS)-7-(2-phenyl)ethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine. mp (.HCl) 250-252 ° C. HRMS calcd for C 20 H 26 FN 4 O (MH+): 341.2142, found: 341.2126.
EXAMPLE 13
(7SR,9aSR)-7-Phenoxymethyl-2-(pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0189] [0189]
[0190] The title compound was prepared according to Example 8 from phenol and (7SR,9aSR)-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-2-pyridin-2-yl-1H-pyrido[1,2-a]pyrazine (U.S. Pat No. 5,122,525). 13 C NMR (base, CDCl 3 ): δ 24.8, 25.3, 33.8, 45.1, 50.7, 54.8, 56.6, 61.0, 68.8, 107.1, 113.1, 114.7, 120.5, 129.4, 137.4, 148.0, 159.3, 159.4. HRMS calcd for C 20 H 25 N 3 O: 323.2000, found: 323.2003
EXAMPLE 14
(7RS,9aSR)-7-Phenoxymethyl-2-(pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0191] [0191]
[0192] The title compound was prepared according to Example 9 from (7RS,9aSR)-hydroxymethyl-2-(pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 11) and phenol. mp (.HCl) 238-241° C. 13C NMR (base, CDCl 3 ): δ 27.0, 29.2, 36.4, 45.2, 50.8, 54.8, 58.8, 60.7, 70.9, 107.0, 113.2, 114.5, 120.7, 113.2, 114.5, 120.7, 129.4, 137.5, 148.0, 159.0, 159.4. Anal. calcd for C 20 H 25 N 3 O C, 74.26; H, 7.79; N, 12.99; found: C, 74.12; H, 7.84; N, 12.86.
EXAMPLE 15
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(3,5-dichloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0193] [0193]
[0194] A mixture of 0.75 g (4.4 mmol) of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 4.02 g (22.1 mmol) of 2,3,5-trichloropyridine, 1.12 g (10.6 mmol) of sodium carbonate and 30 mL of isoamylalcohol was refluxed for 72 h. The mixture was cooled to room temperature, filtered, and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with saturated sodium carbonate. The organic layer was dried (magnesium sulfate), filtered and evaporated, and the crude product was purified by flash chromatography on silica gel eluting with 95:5 chloroform:methanol to give 1.10 g (80%) of (7RS,9aSR)-7-hydroxymethyl-2-(3,5-dichloro-pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0195] A solution of 0.50 g (1.58 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(3,5-dichloro-pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 40 mL of THF with 0.266 g (2.32 mmol) of 4-fluorophenol, 0.498 g (1.90 mmol) of triphenylphosphine, and 0.30 mL (1.90 mmol) of diethyl azodicarboxylate was stirred at room temperature for 16 h. The mixture was diluted with ethyl acetate and treated with excess HCl(g) in ether. The solvent was evaporated and the residue washed repeatedly with 1:1 ethyl acetate:ether. The white powder was dissolved in chloroform, washed with 1M NaOH (2×), dried (magnesium sulfate), filtered and evaporated. The crude product was purified by flash silica gel chromatography with 50:50 ethyl acetate: hexane to give 0.566 g (87%) of title compound. mp (.HCl) 247-248° C. 13 C NMR (base, CDCl 3 ): δ 27.1, 29.0, 36.4, 49.0, 54.4, 54.8, 58.6, 60.7, 71.7, 115.36, 115.47, 115.59, 115.89, 122.3, 124.0, 138.2, 155.1, 155.6, 156.6, 158.8. HRMS calc for C 20 H 22 Cl 2 FN 3 O: 409.1124, found: 409.1141.
EXAMPLE 16
7 -(4-Fluorophenoxy)methyl-2-(substituted-pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0196] [0196]
[0197] Compounds were prepared according to Example 15 from (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874), using the appropriate 2-chloro or 2-bromo pyridine in the first step and 4-fluorophenol in the second step. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixtures of chloroform and methanol as the eluting solvent. The stereochemical configuration, substituted pyridin-2-yl substitutent, melting point of the monohydrochloride salt and HRMS data are shown.
Example 16a
[0198] (7RS,9aSR), 2-(3-Cyanopyridin-2-yl); mp 194-195° C.; HRMS calcd for C 21 H 23 FN 4 O: 366.1855; found: 366.1845.
Example 16b
[0199] (7RS,9aSR), 2-(4-Methylpyridin-2-yl); mp 264-266° C.; HRMS calcd for C 21 H 26 FN 3 O: 355.2060, found: 355.2075.
Example 16c
[0200] (7RS,9aSR), 2-(5-Bromopyridin-2-yl); mp 214-215° C.; HRMS calcd for C 20 H 23 BrFN 3 O: 419.1008, found: 419.1037.
Example 16d
[0201] (7RS,9aSR), 2-(3-Chloropyridin-2-yl); mp 174-175° C.; HRMS calcd for C 20 H 23 ClFN 3 O: 375.1514, found: 375.1528.
EXAMPLE 17
(7RS,9aSR)-7-Phenoxymethyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0202] [0202]
[0203] The title compound was prepared according to Example 15 using 2.5-dichloropyridine, (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874), and phenol. mp (.HCl) 218-224° C. 13 C NMR (base, CDCl 3 ): δ 27.0, 29.1, 36.4, 45.3, 50.9, 54.6, 58.8, 60.5, 70.9, 107.8, 114.5, 120.1, 120.7, 129.4, 137.1, 146.2, 157.6, 159.0. Anal. calcd for C 20 H 24 ClN 3 O C, 67.12; H, 6.76; N, 11.74; found: C, 67.22; H, 6.85; N, 11.49.
EXAMPLE 18
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2-(pyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0204] [0204]
[0205] The title compound was synthesized according to Preparation 11 using 2 -bromopyridine and (7R,9aS)-7-(4-fluorophenoxy)methyl-2,3,4, -6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine (Preparation 8). mp (.HCl) 261-263° C. HRMS calcd for C 20 H 24 FN 3 O: 341.1903; found, 341.1928.
EXAMPLE 19
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0206] [0206]
[0207] The title compound was prepared according to Preparation 11 using 2,5 -dichloropyridine and (7R,9aS)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 8). mp (.HCl) 237-238° C. 13 C NMR (base, CDCl 3 ): δ 27.0, 29.1, 36.4, 45.3, 50.9, 54.6, 58.7, 60.5, 71.6, 107.7, 115.36, 115.47, 115.60, 115.90, 120.1, 137.1, 146.3, 155.1, 155.6, 157.6, 158.8. HRMS calcd for C 20 H 23 ClFN 3 O: 375.1514; found, 375.1544.
EXAMPLE 20
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2-(6-chloropyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0208] [0208]
[0209] The title compound was prepared according to Preparation 3 with 3,6 -dichloropyridazine and (7R,9aS)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine. mp (.HCl) 265-270° C. 13 C NMR (base, CDCl 3 ): δ 26.8, 29.0, 36.4, 45.1, 50.4, 54.4, 58.6, 60.3, 71.5, 115.2, 115.3, 115.4, 115.6, 115.9, 128.7, 146.7, 155.0, 155.6, 158.76, 158.82. HRMS calcd for C 19 H 22 ClFN 4 O: 376.1461; found: 376.1453.
EXAMPLE 21
(7S,9aR)-7-(4-Fluorophenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0210] [0210]
[0211] The title compound was prepared according to Preparation 3 with 2-chloro-5 -fluoropyrimidine and (7S,9R)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 9). mp (.HCl) 251-252° C. 13 C NMR (base, CDCl 3 ): δ 27.0, 29.0, 36.4, 44.3, 49.8, 54.8, 58.8, 60.7, 71.6, 115.35, 115.45, 115.59, 115.89, 145.0, 145.3, 149.9, 153.2, 155.1, 155.6, 158.7, 158.8. HRMS calcd for C 19 H 22 F 2 N 4 O: 360.1762; found: 360.1763.
EXAMPLE 22
(7R,9aR)-7-(4-Fluorophenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0212] [0212]
[0213] The title compound was prepared according to Preparation 3 with 2-chloro-5 -fluoropyrimidine and (7R,9R)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 10). mp (.HCl) 232.5-324° C. 13 C NMR (base, CDCl 3 ): δ 24.8, 25.1, 33.8, 44.3, 49.7, 54.8, 56.6, 61.0, 69.5, 115.48, 115.53, 115.59, 115.83, 145.0, 145.3, 149.9, 153.1, 155.4, 155.5, 158.69, 158.74. HRMS calcd for C 19 H 22 F 2 N 4 O: 360.1762; found: 360.1755.
EXAMPLE 23
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(2-cyano-4-fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0214] [0214]
[0215] A mixture of 1.05 g (6.17 mmol) of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 1.29 g (9.25 mmol) of 2,5 -difluorobenzonitrile in 20 mL of DMSO was heated at 100° C. for 16 h. The mixture was cooled to room temperature, acidified with 1M HCl, washed with ether (3×), made basic with conc. ammonium hydroxide, and extracted with ethyl acetate (3×). The combined organic layers were washed with water (3×), dried (magnesium sulfate), filtered and evaporated. Purification by silica gel MPLC with 90:10 chloroform:methanol gave 0.51 g of (7RS,9aSR)-7 -hydroxymethyl-2-(2-cyano-4-fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2 -a]pyrazine.
[0216] A solution of 0.51 g (1.8 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(2-cyano-4 -fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 0.555 g (2.12 mmol) of triphenylphosphine, and 0.296 g (2.64 mmol) of 4-fluorophenol in 8 mL of dry THF was treated with 0.368 g (2.12 mmol) of diethyl azodicarboxylate and stirred at ambient temperature for 24 h. The mixture was diluted with ether, and 1 M HCl was added until a gummy residue formed. The layers were separated and the aqueous layer was washed with ether (3×). The aqueous layer was combined with the gummy residue and dissolved in a mixture of ethyl acetate and 10% ammonium hydroxide, the layers were separated and the aqueous layer was extracted with more ethyl acetate (2×). The organic layers were evaporated, the residue dissolved in chloroform, washed with 1M NaOH (3×), dried (magnesium sulfate), filtered and evaporated. The product was dissolved in absolute ethanol, filtered and evaporated to give 0.21 g of the title compound. mp (.HCl) 235-240° C. HRMS calcd for C 22 H 23 F 2 N 3 O: 383.1809, found: 383.1796.
EXAMPLE 24
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2-(2-amino-4-fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0217] [0217]
[0218] A solution of 4.38 g (25.8 mmol) of (7R,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (preparation 1), 4.19 mL (38.7 mmol) of 2,5 -difluoronitrobenzene, and 5.46 g (51.5 mmol) of sodium carbonate in 25 mL of DMSO was heated at 95° C. for 16 h. The mixture was cooled to room temperature, acidified with 1M HCl, and washed with ethyl ether (3×). The aqueous layer was made basic with conc. ammonium hydroxide and extracted with ethyl acetate (3×). The combined organic layers were washed with water (3×), dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 90:10 chloroform: methanol gave 6.19 g (78%) of (7R,9aS)-7 -hydroxymethyl-2-(4-fluoro-2-nitrophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0219] A solution of 3.0 g (9.7 mmol) of (7R,9aS)-7-hydroxymethyl-2-(4-fluoro-2-nitrophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 50 mL of methanol and 50 mL of THF was treated with 0.30 g of 10% Pd/C and treated with 30 psi of hydrogen in a Parr apparatus for 1.5 h. The catalyst was removed by filtration and the red solution concentrated to give 2.65 g (98%) of (7R,9aS)-7-hydroxymethyl-2-(2-amino-4-fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0220] A solution of 4.12 g (14.8 mmol) of (7R,9aS)-7-hydroxymethyl-2-(2-amino-4-fluoro-phenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 2.48 g (22.2 mmol) of 4-fluorophenol and 4.65 g (1 7.7 mmol) of triphenylphosphine in 225 mL of THF was treated with 2.79 mL (17.7 mmol) of diethyl azodicarboxylate and stirred at room temperature for 4 days. The solvent was evaporated, the residue dissolved in 1:1 ethyl acetate:ethyl ether and the solution treated with HCl(g) in ether until precipitation ceased. The mixture was filtered and the solid washed repeatedly with ethyl acetate. The solid was dissolved in a mixture of chloroform and 1M sodium hydroxide, the layers separated, and the organic phase was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 60:40 ethyl acetate:hexane gave 1.69 g (30%) of the title compound. mp (.HCl) 144-149° C. HRMS calcd for C 21 H 25 F 2 N 3 O: 373.1966, found: 373.1958.
EXAMPLE 25
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(4-fluorophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0221] [0221]
[0222] A solution of 1.53 g (4.10 mmol) of (7R,9aS)-7-hydroxymethyl-2-(2-amino-4 -fluoro-phenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazine (Example 24) in 160 mL of THF was added to a solution of 1.21 mL (9.02 mmol) of 97% isoamyl nitrite in 100 mL of THF over a 2 h period. After the addition was complete, the solution was heated at reflux for 4 days. The solvent was evaporated, the residue was dissolved in ethyl acetate and washed with 1 M sodium hydroxide (3×). The organic phase was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 50:50 ethyl acetate:hexane gave 0.75 g (52%) of a yellow solid. mp (.HCl) 221-223° C. HRMS calcd for C 21 H 24 F 2 N 2 O: 358.1857, found: 358.1875.
EXAMPLE 26
(7R,9aS)-7-Phenoxymethyl-2-phenyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2 -a]pyrazine
[0223] [0223]
[0224] A mixture of 0.500 g (1.89 mmol) of (7R,9aS)-7-(4-fluorophenoxy) methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 8), 0.400 g (2.84 mmol) of 4-fluoronitrobenzene and 0.401 g (3.78 mmol) of sodium carbonate in 15 mL of DMSO was heated at 95° C. for 16 h. The mixture was cooled to room temperature, acidified with 1M HCl, washed with ethyl ether (3×), basified with conc. ammonium hydroxide and extracted with ethyl acetate (3×). The combined organic layers were washed with water and brine, dried (magnesium sulfate), filtered and evaporated to give 0.614 g of (7R,9aS)-7-(4-fluorophenoxy)-methyl-2-(4-nitrophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0225] A mixture of 0.600 g (1.56 mmol) of (7R,9aS)-7-(4-fluorophenoxy)methyl-2-(4 -nitrophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine and 90 mg of 10% Pd/C in 25 mL of THF was placed in a Parr hydrogenator at 30 psi for 4 h. The catalyst was removed by filtration through Celite and the filtrate was evaporated to give 0.45 g (82%) of (7R,9aS)-7 -(4-fluorophenoxy)methyl-2-(4-aminophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2 -a]pyrazine.
[0226] A solution of 0.400 g (1.13 mmol) of (7R,9aS)-7-(4-fluorophenoxy)methyl-2-(4 -aminophenyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 20 mL of THF was added dropwise to a solution of 0.33 mL (2.48 mmol) of isoamyl nitrite in 15 mL of THF. After the addition was complete, the solution was refluxed for 24 h. The solvent was evaporated, the residue dissolved in ethyl acetate, washed with 1M sodium hydroxide (3×), washed with brine ( 1 x), dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate gave 0.060 g (16%) of the title compound. mp (.HCl) 247-252° C. HRMS calcd for C 21 H 25 FN 2 O: 340.1951, found: 340.1989.
EXAMPLE 27
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(6-methoxypyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-I H-pyrido[1,2-a]pyrazine
[0227] [0227]
[0228] According to the procedure reported by Wynberg ( J. Org. Chem. 1993, 58, 5101), a solution 0.50 g (2.9 mmol) of racemic (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 10 mL of dry THF at 0C was treated with 2.59 mL (6.5 mmol) of n-butyl lithium (2.5 M in hexane). The mixture was kept at 0° C. for 30 min and at room temperature for 1 h, and 0.39 mL (2.94 mmol) of 2,6-dimethoxypyridine was added and the solution refluxed for 16 h. After cooling to room temperature, the mixture was poured into 1 M HCl and washed with toluene (3×). The aqueous layer was basified with 1 M NaOH and extracted with toluene (1×) and ethyl acetate (1×). The combined organic layers were dried (magnesium sulfate), filtered, and evaporated to give a yellow oil. Purification by flash silica gel chromatography with 9:1 chloroform:methanol gave 0.304 g (37%) of (7RS,9aSR)-7 -hydroxymethyl-2-(6-methoxypyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0229] A solution of 0.30 g (1.1 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(6-methoxypyridin-2yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a] pyrazine, 0.182 g (1.62 mmol) of 4-fluorophenol, and 0.340 g (1.30 mmol) of triphenylphosphine, and 0.205 g (1.30 mmol) of diethylazodicarboxylate in 20 mL of THF was stirred at room temperature for 16 h. The solvent was evaporated, the residue dissolved in ether and extracted with 1 M HCl (2×). The combined aqueous layers were basified with conc. ammonium hydroxide and extracted with ethyl acetate (3×). The combined organic layers were dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 50:50 ethyl acetate:hexane gave 0.300 g (75%) of yellow crystals. mp (.HCl) 228-230° C. HRMS calcd for C 21 H 26 FN 3 O 2 : 371.2009, found: 371.2001.
EXAMPLE 28
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-2-(5-fluoropyridin-2-yl)-1H-pyrido[1,2-a]pyrazine
[0230] [0230]
[0231] According to the procedure reported by Schwartz ( J. Am. Chem. Soc. 1986, 108, 2445), a solution of 0.300 g (0.714 mmol) of (7RS,9aSR)-7-(4-fluorophenoxy)methyl-(5-bromopyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 16) in 6.5 mL of THF:hexane:ethyl ether (4:1:1) under nitrogen was cooled to −100° C. n-Butyl lithium (0.57 mL, 2.5 M in hexane) was added dropwise and the mixture stirred for 15 min. N-Fluorodibenzenesulfonamide (0.34 g, 1.07 mmol) in ethyl ether was added, the solution stirred for 20 min, and then allowed to warm to room temperature over 20 h. Water was added and the mixture extracted with ethyl acetate (3×), dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 50:50 ethyl acetate:hexane gave 0.038 g (15%) of the title compound. mp (.HCl) 214-215° C. HRMS calcd for C 20 H 23 F 2 N 3 O: 359.1809, found: 359.1795.
EXAMPLE 29
(7RS,9aSR)-7-Phenoxymethyl-2-(2-chloropyrimidin-4-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0232] [0232]
[0233] A mixture of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 2,4-dichloropyrimidine were combined according to Preparation 3. The product from this reaction was coupled with phenol according to Example 1 to give the title compound. mp (.HCl) 227-233° C. (dec). HRMS calcd for C 19 H 23 ClN 4 O: 358.1560, found: 358.1560.
EXAMPLE 30
(7RS,9aSR)-7-Phenoxymethyl-2-(pyrazin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0234] [0234]
[0235] A mixture of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 2-chloropyrazine were combined according to Preparation 3. The product from this reaction was coupled with phenol according to Example 1 to give the title compound. mp (.HCl) 217-219° C. HRMS calcd for C 19 H 24 N 4 O: 324.1945, found: 324.1981.
EXAMPLE 31
(7RS,9aSR)-7-Phenoxymethyl-2-(6-chloropyrazin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0236] [0236]
[0237] A mixture of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 2,6-dichloropyrazine were combined according to Preparation 3. The product from this reaction was coupled with phenol according to Example 1 to give the title compound. mp (.HCl) 247° C. (dec). HRMS calc for C 19 H 23 ClN 4 O: 358.1560, found: 358.160
EXAMPLE 32
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(6-chloropyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0238] [0238]
[0239] A mixture of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 3,6-di-chloropyridazine were combined according to Preparation 3. The product from this reaction was coupled with 4-fluorophenol according to Example 1 to give the title compound. mp (.HCl) 255° C. (dec). HRMS calc for C 19 H 22 CIFN 4 O: 376.1461, found: 376.1458.
EXAMPLE 33
(7RS,9aSR)-7-Phenoxymethyl-2-(6-chloropyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0240] [0240]
[0241] A mixture of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 3,6-dichloropyridazine were combined according to Preparation 3. The product from this reaction was coupled with phenol according to Example 1 to give the title compound. mp (.HCl) >265° C. (dec). HRMS calcd for C 19 H 23 ClN 4 O: 358.1555, found: 358.1550.
EXAMPLE 34
(7RS,9aSR)-7-Phenoxymethyl-2-(pyrimidin-4-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0242] [0242]
[0243] A mixture of 0.110 g (0.307 mmol) of (7RS,9aSR)-7-phenoxymethyl-2-(2-chloropyrimidin-4-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 29), 20 mg of 10% Pd/C, and several drops of conc. hydrochloric acid in 30 mL of ethanol were shaken under 50 psi of hydrogen gas at room temperature for 6 h. The mixture was filtered through Celite and the filtrate was evaportated. The residue was basified with conc. ammonium hydroxide, extracted with chloroform, dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with a solvent gradient from 100% chloroform to 95:5 chloroform:methanol gave 0.020 g (20%) of the title compound. mp (.HCl) >265° C. (dec). HRMS calc for C 19 H 24 N 4 O: 324.1945, found: 324.1970.
EXAMPLE 35
(7RS,9aSR)-7-(4-Fluorophenoxy)methyl-2-(pyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0244] [0244]
[0245] A mixture of 0.150 g (0.363 mmol) of (7RS,9aSR)-7-(4-fluorophenoxy)methyl-2-(6-chloropyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 32), 0.10 mL (0.72 mmol) of triethylamine, and 20 mg of 10% Pd/C in 10 mL of ethanol were shaken under 50 psi of hydrogen for 18 h. The mixture was filtered through Celite and the filtrate was evaporated. The residue was dissolved in chloroform, washed with water, dried (magenesium sulfate), filtered and evaporated. mp (.HCl) 246-250° C. HRMS calcd for C 19 H 23 FN 4 O: 342.1851, found: 342.1826.
EXAMPLE 36
(7R,9aS)-7-(3,5-Difluorophenoxy)methyl-2-(6-chloropyridazin-3-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0246] [0246]
[0247] A mixture of (7R,9aS)-N-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) and 3,5-difluorophenol were coupled followed by N-BOC deprotection according to Preparation 9. The product from this reaction was coupled with 3,6-dichloropyridazine according to Preparation 3 to give the title compound. mp (.HCl) 254-259° C. 13 C NMR (base, CDCl 3 ): δ 26.7, 28.9, 36.1, 45.1, 50.4, 54.3, 58.4, 60.3, 71.4, 96.3, 95.0, 98.4,115.2, 128.8, 146.8, 158.8.
EXAMPLE 37
(7R,9aS)-7-Phenoxymethyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0248] [0248]
[0249] A mixture of (7R,9aS)-N-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) and 3,5-difluorophenol were coupled followed by N-BOC deprotection according to Preparation 9. The product from this reaction was coupled with 2,5-dichloropyridine according to Preparation 11 to give the title compound. mp (.HCl) 260-261° C. HRMS calcd for C 20 H 22 CIF 2 N 3 O: 393.1419, found: 393.1410.
EXAMPLE 38
3 -[(7R,9aS)-2-Heteroaryl-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazin-7-ylmethyl]-3H-benzoxazol-2-ones
[0250] [0250]
[0251] Compounds of the above formula were synthesized from 3-[(7R,9aS)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzooxazol-2-one (Preparation 12) and the appropriate heteroaryl chloride according to Preparation 5. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixtures of chloroform and methanol as the eluting solvent. The 2-substituent, melting point of the monohydrochloride and high resolution mass spectral data are shown.
Example 38a
[0252] 2-(Pyrimidin-2-yl); mp 165-167° C.; HRMS calcd for C 20 H 23 N 5 O 2 : 365.1852, found: 365.1850.
Example 38b
[0253] 2-(5-Fluoropyrimidin-2-yl); mp 170-171° C.; HRMS calcd for C 20 H 22 FN 5 O 2 : 383.1758, found: 383.1809.
Example 38c
[0254] 2-(6-Chloropyridazin-3-yl); mp 176° C. (dec); HRMS calcd for C 20 H 22 CIN 5 O 2 : 399.1457, found: 399.1519.
EXAMPLE 39
3 -[(7R,9aS)-2-(5-Chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzoxazol-2-one
[0255] [0255]
[0256] The title compound was synthesized according to Preparation 11 from 3-[(7R,9aS)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzoxazol-2-one (Preparation 12) and 2,5-dichloropyridine. mp (.HCl) 247-248° C. HRMS calcd for C 21 H 23 CIN 4 O 2 : 398.1510, found: 398.1484.
EXAMPLE 40
(7RS,9aSR)-7-(5-Fluoroindol-1-ylmethyl)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0257] [0257]
[0258] The title compound was synthesized according to Example 9 from (7RS,9aSR)-7 -hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 3) and 5-fluoroindole. mp (.HCl) 70-72° C. HRMS calcd for C 21 H 25 FN 5 (MH+): 366.2094, found: 366.2104.
EXAMPLE 41
(7RS,9aSR)-7-(4-Fluorophenylsulfanyl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0259] [0259]
[0260] The title compound was prepared according to Example 1 from (7RS,9aSR)-7 -hydroxymethyl-2-(2-pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 3) and 4-fluorothiophenol. mp (.HCl) 99-101° C. HRMS calcd for C 19 H 23 FN 4 S: 358.1627, found: 358.1683.
EXAMPLE 42
(7RS,9aSR)-7-(4-Fluorophenylsulfonyl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0261] [0261]
[0262] A solution of 0.50 g (1.40 mmol) of (7RS,9aSR)-7-(4-fluorophenylsulfanyl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 41) and 1.13 g (5.59 mmol) of 3-chloroperbenzoic acid in 30 mL of chloroform was stirred at room temperature for 20 h. The solution was partitioned with 1 M sodium hydroxide, the layers were separated, the organic phase was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 67:33 chloroform:methanol gave 0.18 g (33%) of the title compound. mp (.HCl) 155-157° C. HRMS calcd for C 19 H 23 FN 4 O 2 S: 390.1526 , found: 390.1483.
EXAMPLE 43
(7R,9aS)-7-(5-Fluoroindol-1-yl)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0263] [0263]
[0264] A solution of 6.0 g (22 mmol) of (7R,9aS)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) and 3.41 mL (24.4 mmol) of triethylamine in 225 mL of dry methylene chloride was chilled to 0° C., and treated with 1.80 mL (23.3 mmol) of methansulfonyl chloride in 75 mL of methylene chloride. After stirring 1 h, water was added and the pH adjusted to 12 with 15% sodium hydroxide. The layers were separated and the aqueous phase extracted with methylene chloride. The combined organic phase was dried (magnesium sulfate), filtered and evaporated to give 7.73 g (100%) of (7R,9aS)-2-BOC-7-(methanesulfonyloxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0265] A solution of 8.41 g (62 mmol) of 5-fluoroindole in 250 mL of DMF was treated with 2.46 g (62 mmol) of sodium hydride (60% oil dispersion) and the mixture stirred at 50° C. for 1.5 h. Heating was stopped temporarily, 7.73 g (22.2 mmol) of (7R,9aS)-2-BOC-7-(methanesulfonyloxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 250 mL of DMF was added, and the mixture stirred at 100° C. for 2 h. The mixture was cooled to room temperature, diluted with water, acidified to pH 2 with 6M hydrochloric acid, and washed with ethyl acetate. The aqueous phase was basified to pH 12 with conc. ammonium hydroxide and extracted with ethyl acetate (3×). The combined organic phase was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate gave 3.09 g (36%) of (7R,9aS)-2-BOC-7-(5-fluoroindol-1-yl)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0266] A solution of 3.0 g (7.75 mmol) of (7R,9aS)-2-BOC-7-(5-fluoroindol-1-yl)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 200 mL of 70:30 trifluoroacetic acid:water was stirred at room temperature for 1h. The mixture was concentrated in vacuo, basified with 15% sodium hydroxide and extracted with ethyl acetate (2×). The combined organics were dried (magnesium sulfate), filtered and evaporated to give 2.0 g (90%) of (7R,9aS)-7-(5-fluoroindol-1-yl)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0267] A mixture of 2.20 g (7.67 mmol) of (7R,9aS)-7-(5-fluoroindol-1-yl)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 1.02 g (7.67 mmol) of 2-chloro-5-fluoropyrimidine and 1.95 g (18.4 mmol) of sodium carbonate in 100 mL of water was stirred at 95° C. for 72 h. The mixture was cooled to room temperature, extracted with chloroform (3×), the combined organic phase was washed with brine, dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 50:50 ethyl acetate:hexane gave 1.17 g (40%) of the title compound. mp (.HCl) 180-182° C. HRMS calc for HRMS calcd for C 21 H 23 F 2 N 5 : 383.1922, found: 383.1924.
EXAMPLE 44
1-[(7R,9aS)-2-(Pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-ylmethyl]-1,3-dihydro-indol-2-one
[0268] [0268]
[0269] A solution of 6.0 g (22 mmol) of (7R,9aS)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) and 3.41 mL (24.4 mmol) of triethylamine in 225 mL of dry methylene chloride was chilled to 0° C., and treated with 1.80 mL (23.3 mmol) of methansulfonyl chloride in 75 mL of methylene chloride. After stirring 1 h, water was added and the pH adjusted to 12 with 15% sodium hydroxide. The layerswere separated and the aqueous phase extracted with methylene chloride. The combined organic phase was dried (magnesium sulfate), filtered and evaporated to give 7.73 g (100%) of (7R,9aS)-2-BOC-7-(methanesulfonyloxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0270] A solution of 2.75 g (10.7 mmol) of oxindole in 85 mL of DMF was treated with 0.82 g (21 mmol) of sodium hydride (60% oil dispersion) and the mixture stirred at 50° C. for 1.5 h. Heating was stopped temporarily, 2.56 g (7.38 mmol) of (7R,9aS)-2-BOC-7-(methanesulfonyloxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 85 mL of DMF was added, and the mixture stirred at 100° C. for 2 h. The mixture was cooled to room temperature, diluted with water, acidified to pH 2 with 6M hydrochloric acid, and washed with ethyl acetate. The aqueous phase was basified to pH 12 with conc. ammonium hydroxide and extracted with ethyl acetate (3×). The combined organic phase was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate gave 0.677 g (24%) of 1-[(7R,9aS)-2-BOC-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-ylmethyl)]-1,3-dihydro-indol-2-one.
[0271] A solution of 0.53 g (1.38 mmol) of 1-[(7R,9aS)-2-BOC-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-ylmethyl]-1,3-dihydro-indol-2-one in 10 mL of chloroform was treated with excess HCl(g) in ethyl ether and stirred at room temperature for 1 h. The solvent was evaporated to give 0.49 g (100%) of 1-[(7R,9aS)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-ylmethyl]-1,3-dihydro-indol-2-one dihydrochloride.
[0272] A mixture of 0.49 g (1.38 mmol) of 1-[(7R,9aS)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-ylmethyl]-1,3-dihydro-indol-2-one dihydrochloride, 0.157 g (1.37 mmol) of 2-chloropyrimidine and 0.64 g (6.02 mmol) of sodium carbonate in 20 mL of water was stirred at 95° C. for 16 h. The mixture was cooled to room temperature, extracted with chloroform (3×), the combined organic phase was washed with brine, dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 95:5 ethyl acetate:methanol gave 0.181 g (30%) of the title compound. mp (.HCl) 174-176° C. HRMS calcd for C 21 H 25 N 5 O: 363.2059, found: 363.2032.
EXAMPLE 45
(7RS,9aSR)-7-Phenoxy-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0273] [0273]
[0274] A solution of 0.600 g (3.03 mmol) of (9aSR)-7-(ethylenedioxy)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Compernolle, F.; Slaeh, M. A.; Toppet, S.; Hoornaert, G. J. Org. Chem., 1991, 56, 5192), 0.35 g (3.0 mmol) of 2-chloropyrimidine and 0.77 g (7.3 mmol) of sodium carbonate in 6 mL of water was refluxed for 21 h. The mixture was cooled to room temperature, extracted with methylene chloride (3×), the combined organic phase was washed with water and brine, dried (magnesium sulfate), filtered and evaporated. Purification by filtration through a 30 g plug of flash silica gel with 95:5 ethyl acetate:ethanol gave 0.624 g (75%) of (9aSR)-7-(ethylenedioxy-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine. mp (base) 121-122° C. Anal calcd for C 14 H 20 N 4 O 2 : C, 60.85; H, 7.29; N, 20.27; found: C, 60.84; H, 7.26; N, 20.42.
[0275] A solution of 0.60 g (2.2 mmol) of (9aSR)-7-(ethylenedioxy)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrimidine was dissolved in 8 mL of 6M HCl and refluxed for 3h. The solution was cooled to room temperature, the solvent was evaportated, the residue dissolved in methylene chloride, mixed with aqueous potassium carbonate, the layers were separated, and the aqueous layer extracted with methylene chloride (2×). The combined organic phase was dried (magnesium sulfate), filtered and evaporated. Filtration through a plug of flash silica gel with 95:5 ethyl acetate:ethanol gave 0.205 g (41%) of 7-keto derivative. The 7-keto derivative was dissolved in 10 mL of methanol and treated with 0.33 g (0.88 mmol) of 10% sodium borohydride on alumina. After stirring for 1 h, the mixture was filtered and evaporated to give 0.156 g (75%) of crude 7-hydroxy derivative. The crude 7-hydroxy derivative, 0.094 g (1.0 mmol) of phenol, and 0.209 g (0.799 mmol) of triphenylphosphine were dissolved in 1.4 mL of dry THF. The mixture was treated with 0.13 mL (0.80 mmol) of diethyl azodicarboxylate and stirred at room temperature for 24 h. The mixture was diluted with ethyl ether, extracted with 0.1M HCl (3×), the combined aqueous phase was washed with ethyl ether (2×), basified with conc. ammonium hydroxide, and extracted with ethyl acetate (3×). The combined ethyl acetate layers were dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 50:50 ethyl acetate:hexane gave 0.036 g (17%) of the title compound. mp (base) 147-148° C. HRMS calcd for C 8 H 22 N 4 O: 310.1794, found: 310.1819.
EXAMPLE 46
(4-Fluoro)phenyl-[(7RS,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazin-7-yl]-methanol
[0276] [0276]
[0277] A flame-dried 3-neck flask was attached to a bleach trap and charged with 20 mL of methylene chloride and 0.77 mL (1.1 mmol) of oxalyl chloride. The solution was chilled to −78° C. and anhydrous DMSO (1.38 mL, 1.93 mmol) was added dropwise at a rate which kept the internal temperature at or below −50° C. A methylene chloride solution of (7RS,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (2.5 g, 9.1 mmol) was added followed by slow addition of 5.2 mL (37 mmol) of triethylamine. After warming to room temperature, 40 mL of water was added, the layers were separated and the aqueous phase extracted with methylene chloride (4×). The combined organic phase was dried (sodium sulfate), filtered and evaporated to give 2.24 g (90%) of aldehyde. 13 C NMR (CDCl 3 ): δ 24.0, 28.5, 43.5, 48.8, 49.0, 55.4, 54.7, 60.3, 109.9, 157.7, 161.3, 202.3. HRMS calcd for C 13 H 18 N 4 O: 246.1481, found: 246.1484.
[0278] A solution of the crude aldehyde (0.44 g, 1.6 mmol) in 45 mL of dry THF was chilled to −10° C. and treated with 8.8 mL (18 mmol, 2M in THF) of 4-fluorophenyl magnesium bromide. The solution was allowed to warm to room temperature and 10 mL of ice water was added carefully followed by 100 mL of saturated ammonium chloride. The aqueous phase was extracted with ethyl ether (1×), dried (sodium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with methylene chloride:methanol:conc. ammonium hydroxide 12:1:0.04 gave 0.037 g (6.7%) of the title compound. 13 C NMR (CDCl 3 ): δ 26.1, 28.8, 43.2, 43.3, 46.1, 48.8, 54.8, 57.8, 58.0, 60.9, 76.4, 109.9, 115.09, 115.38, 127.98, 128.09, 138.7, 157.7, 160.6, 161.4, 163.4. HRMS calcd for C 19 H 24 FN 4 O (MH+): 343.1934, found: 343.1938.
EXAMPLE 47
(4-Fluoro)phenyl-[(7SR,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazin-7-yl]-methanol
[0279] [0279]
[0280] The title compound was prepared according to Example 46 starting with (7SR,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine. HRMS calcd for C 19 H 24 FN 4 O (MH+): 343.1934, found: 343.1934.
EXAMPLE 48
(4-Fluoro)phenyl-[(7RS,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]-methanone
[0281] [0281]
[0282] The title compound was prepared according to the oxalyl chloride/DMSO oxidation step of Example 46 starting with (4-fluoro)phenyl-[(7RS,9aSR)-2-(pyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]-methanol (Example 46). 13 C NMR (CDCl 3 ): δ 27.3, 28.3, 48.6, 54.1, 56.7, 59.9, 110.1, 115.77, 116.05, 131.20, 131.32, 132.4, 158.0, 161.1, 163.4, 166.7. HRMS calcd for C 19 H 21 FN 4 O: 340.1699, found: 340.1539.
EXAMPLE 49
(7S,9aS)-7-(4-Fluorophenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0283] [0283]
[0284] A solution of 0.82 g (3.08 mmol) of (7S,9aS)-7-hydroxymethyl-2-(5-fluoropyrimidin-2-yl) -2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 13), 0.52 g (4.62 mmol) of 4-fluorophenol, 0.97 g (3.70 mmol) of triphenylphosphine in dry THF was treated with 0.64 g (3.70 mmol) of diethyl azodicarboxylate and stirred at room temperature for 72 h. The solvent was evaportated, the residue dissolved in 50:50 ethyl acetate:ethyl ether, and treated with HCl(g) in ethyl ether until precipitation ceased. The solid was collected by filtration, dissolved in chloroform, 1M sodium hydroxide was added, and the layers were separated. The organic layer was dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 90:10 hexane:ethyl acetate gave 0.49 g (44%) of the title compound. mp (.HCl) 225-228° C. 13 C NMR (base, CDCl 3 ): δ 24.8, 25.2, 33.8, 44.3, 49.7, 54.8, 56.6, 61.0, 69.5, 115.48, 115.53, 115.59, 115.83, 144.97, 145.26, 149.85, 153.15, 155.42, 155.54, 158.69, 158.74. HRMS calcd for C 19 H 22 F 2 N 4 O: 360.1762, found: 360.1752.
EXAMPLE 50
(7RS,9aSR)-7-(5-Fluoro-1H-indol-3-yl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0285] [0285]
[0286] A solution of 2.22 g (8.1 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(2-pyrimidinyl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 3) and triethyl amine (1.34 mL, 9.7 mmol) in 15 mL of methylene chloride was chilled to 0° C. and treated with a solution of 0.64 mL (8.3 mmol) of methanesulfonyl chloride in 7 mL of methylene chloride. The solution was stirred at 0° C. for 1 h, and then allowed to warm to room temperature. Water was added (30 mL), and the pH adjusted to 9.5 with 2M sodium hydroxide. The layers were separated and the aqueous phase extracted with methylene chloride (30 mL). The combined organic phase was dried (sodium sulfate), filtered and evaporated to give 2.05 g (78%) of mesylate.
[0287] A flame-dried flask was charged with 0.2 g (1.5 mmol) of 5-fluoroindole, 8 mL of benzene and 0.49 mL (1.5 mmol) of ethyl magenesium bromide (3M in THF). Under vigorous stirring, the above mesylate (0.53 g, 1.6 mmol) was added and the mixture stirred at room temperature for 18 h. Water (15 mL), ethyl acetate (10 mL) and sat. sodium bicarbonate were added, and the layers were separated. The organic phase was dried (sodium sulfate), filtered and evaporated. Initial purification by flash silica gel chromatography with ethyl acetate:methanol 95:5 followed a second purification by flash silica gel chromatography with 30:70:2 ethyl acetate:hexane:methanol gave 80 mg of the title compound. 13 C NMR (CDCl 3 ): δ 29.5, 30.2, 30.8, 37.1, 43.6, 49.1, 54.8, 60.9, 103.8, 104.1, 109.0, 109.4, 109.8, 110.7, 110.9, 114.4, 114.5, 123.7, 132.8, 156.1, 157.7, 159.2, 161.5. HRMS calcd for C 21 H 24 FN 5 : 365.2011, found: 365.1985.
EXAMPLE 51
(7RS,9aSR)-7-(5-Fluoro-1-methyl-1H-indol-3-yl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0288] [0288]
[0289] A flame-dried flask was charged with 0.103 g (0.28 mmol) of (7RS,9aSR)-7-(5-fluoro-1H-indol-3-yl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Example 50), anhydrous DMF (1 mL) and 12 mg (0.30 mmol) of sodium hydride (60% oil dispersion). The suspension was treated with 0.019 mL (0.31 mmol) of methyl iodide and the mixture was heated at 50° C. for 16 h. The mixture was cooled to room temperature, concentrated in vacuo, and diluted with methylene chloride (25 mL) and water (25 mL), and the layers were separated. The organic phase was dried (sodium sulfate), filtered and evaporated to a solid residue. The solid was washed with ethyl acetate (2×), the ethyl acetate was evaporated to give 50 mg of the title compound. 1 H NMR (CDCl 3 ): δ 1.00-1.31 (m, 3H), 1.64-2.23 (m, 6H), 2.54-3.1 (m, 5H), 3.69 (s, 3H), 4.51-4.56 (m, 2H), 6.43 (dd, J=1 Hz, 1H), 6.83 (s, 1H), 6.93 (m, 1H), 7.15 (m, 2H), 8.27 (d, J=1 Hz, 2H). TLC R f : 0.81 (90:10:1 methylene chloride:methanol:ammonium hydroxide).
EXAMPLE 52
(7RS,9aSR)-7-(5-Chloro- and -(6-Chloro-2-methyl-benzoimidazol-1-yl)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0290] [0290]
[0291] A solution of 2.22 g (8.1 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 3) and triethyl amine (1.34 mL, 9.7 mmol) in 15 mL of methylene chloride was chilled to 0° C. and treated with a solution of 0.64 mL (8.3 mmol) of methanesulfonyl chloride in 7 mL of methylene chloride. The solution was stirred at 0° C. for 1 h, and then allowed to warm to room temperature. Water was added (30 mL), and the pH adjusted to 9.5 with 2M sodium hydroxide. The layers were separated and the aqueous phase extracted with methylene chloride (30 mL). The combined organic phase was dried (sodium sulfate), filtered and evaporated to give 2.05 g (78%) of mesylate.
[0292] A flame-dried flask was charged with 0.11 g (0.67 mmol) of 5-chloro-2-methylbenzimidazole, 3 mL of dry DMF, and 29 mg (0.74 mmol) of sodium hydride (60% oil dispersion). The solution heated at 50° C. for 30 min, and then cooled to room temperature. The above mesylate (0.20 g, 0.61 mmol) was added and the mixture was heated at 100° C. for 16 h. The mixture was cooled to room temperature, and concentrated in vacuo. Ethyl acetate (30 mL) and water (30 mL) were added, the layers were separated, and the organic phase was dried (sodium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate gave 130 mg of a mixture of the title compounds. 1 H NMR (CDCl 3 ): δ 1.2 (m, 2H), 1.9 (m, 5H), 2.2 (m,2H), 2.5 (s, 3H), 2.75 (m, 2H), 2.95 (m, 2H), 3.85 (m, 2H), 4.55 (m, 2H), 6.45 (dd, J=1 Hz, 1H), 7.1 (s, 1H), 7.2 (m, 1H), 7.4 (m, 1H), 8.25 (d,J =1 Hz, 2H). TLC R f : 0.32 (90:10 methylene chloride:methanol). HRMS calcd for C 21 H 25 CIN 6 : 396.1829, found: 396.1809.
EXAMPLE 53
1-(4-Fluorophenyl)-2-[(7RS,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]-ethanol
[0293] [0293]
[0294] A solution of 2.2 g (8.1 mmol) of (7RS,9aSR)-7-hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine and 1.3 mL (9.7 mmol) of triethylamine in 15 mL of methylene chloride at 0° C. was treated with a solution of 0.64 mL (8.3 mmol) of methanesulfonyl chloride in 7 mL of methylene chloride, and the solution was stirred for 1 h. Water was added (30 mL) and the pH adjusted to 9.5 with 2M sodium hydroxide. The layers were separated, the aqueous phase was extracted with methylene chloride (30 mL), the combined organic phase was dried (sodium sulfate), filtered and evaporated to give 2.05 g (78%) of mesylate.
[0295] The above mesylate (2.05 g, 6 mmol) was dissolved in 50 mL of dry DMF, 0.31 g (6 mmol) of sodium cyanide was added and the mixture heated at 110° C. under a nitrogen atmosphere for 16 h. The reaction was cooled to room temperature, 1 mL of saturated sodium carbonate solution was added. The solvent was removed in vacuo, the residue was taken up in ethyl acetate (100 mL) and water (50 mL), and the layers were separated. The organic layer was washed with sat. sodium carbonate (2×), dried (sodium sulfate), filtered and evaporated to give 1.4 g (91%) of nitrile. HRMS calcd for C 14 H 19 N 5 : 257.1640, found: 257.1630.
[0296] A flame-dried flask containing 0.350 g (1.36 mmol) of the above nitrile was charged with 1.8 mL (1.8 mmol) of 1M diisobutylaluminum hydride. The solution was stirred for 2 h at room temperature, then stirred at 50° C. for 1 h. The reaction was cooled to room temperature, and 2M hydrochloric acid was added slowly until gas evolution ceased. The pH was adjusted to 8 with 2M sodium hydroxide, and the mixture was diluted with 50 mL of ethyl ether and 50 mL of water. The layers were separated, the organic phase was dried (sodium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 18:1:0.04 methylene chloride:methanol:conc. ammonium hydroxide gave 31 mg (9%) of aldehyde.
[0297] A flame-dried flask containing 30 mg (0.10 mmol) of the above aldehyde in 1 mL of dry THF was chilled to −10° C. and 0.075 mL (0.15 mmol) of 4-fluorophenyl magnesium bromide (2M in THF) was added. The reaction was allowed to warm to room temperature and stirred for 1 h. Water (1 mL), saturated ammonium chloride (1 mL) and ethyl ether (5 mL) were added, and the layers were separated. The organic phase was dried (sodium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 24:1:0.04 methylene chloride:methanol:conc. ammonium hydroxide gave 11 mg (39%) of the title compound. 1 H NMR (CDCl 3 ): δδ0.97-1.05 (m, 1H), 1.23-1.61 (m, 2H), 1.64-1.86 (m 6H), 2.14-2.23 (m, 1H), 2.54-2.78 (m, 1H), 2.81-3.02 (m, 3H), 4.49-4.61 (m, 2H), 4.77-4.71 (m, 1H), 6.45 (t, J=1 Hz, 1H), 6.97-7.03 (m, 2H), 7.25-7.32 (m, 2H), 8.27 (d, J=1 Hz, 2H). HRMS calcd for C 20 H 25 FN 4 O: 356.2012, found: 356.2009.
EXAMPLE 54
1-(4-Fluorophenyl)-2-[(7SR,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]-ethanone
[0298] [0298]
[0299] A solution of 38.1 g (117 mmol) of (7SR,9aSR)-7-(methanesulfonyloxy)methyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (prepared according to U.S. Pat. No. 5,122,525) and 6.01 g (122 mmol) of sodium cyanide in 500 mL of dry DMF was heated at 110° C. for 16 h. The mixture was cooled to room temperature, 10 mL of saturatic sodium bicarbonate was added and the mixture concentrated in vacuo. Water (1000 mL) and ethyl acetate (1000 mL) were added to the solid residue, the pH was adjusted to 11, and the layers were separated. The organic phase was washed with water (2×), dried (sodium sulfate), filtered and evaporated. Recrystalization from ethyl acetate-hexane gave 14.5 g of [(7SR,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]acetonitrile. 13 C NMR (CDCl 3 ): d 19.5, 24.1, 26.9, 31.3, 33.1, 43.6, 48.9, 54.5, 109.8, 119.8, 157.7, 161.4.
[0300] A solution of 0.200 g (0.78 mmol) of [(7SR,9aSR)-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazin-7-yl]acetonitrile in 4 mL of dry THF was treated with 4.3 mg (0.03 mmol) of cuprous bromide and 0.85 mL (0.85 mmol) of 4-fluorophenyl magnesium bromide (1 M in THF), and the mixture was refluxed for 48 h. The mixture was cooled to room temperature, 0.75 mL of water was added carefully followed by 3.5 mL of 15% sulfuric acid. The mixture was refluxed for 24 h. The reaction was cooled to room temperature, and 10% sodium carbonate solution was added until gas evolution ceased. Ethyl ether (10 mL) was added, the layers were separated, and the aqueous phase was extracted with ethyl ether (2×10 mL). The combined organics were dried (sodium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate:hexane:methanol:conc. ammonium hydroxide (1:1:0.01:0.01) gave 30 mg of the title compound. 13 C NMR (CDCl 3 ): d 25.1, 28.3, 29.9, 40.2, 43.7, 49.1, 54.8, 59.1, 61.1, 109.7, 115.4, 115.7, 130.8, 130.9, 134.0, 157.7, 161.5, 164.0, 167.4. HRMS calcd for C 20 H 23 FN 4 O: 354.1856, found: 354.1847.
EXAMPLE 55
(7S,9aS)-7-(Substituted-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0301] [0301]
[0302] Compounds of the above formula were prepared according to Example 49 using (7S,9aS)-7-hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2a]pyrazine (Preparation 13) and the appropriate phenol. Purification was generally accomplished with flash silica gel chromatography using mixtures of ethyl acetate and hexane as the eluting solvent. The stereochemical configuration, 7-(substituted-phenoxy)methyl substituent, melting point of the monohydrochloride salt, and HRMS data are shown.
Example 55a
[0303] (7S,9aS)-7-(4-Fluoro-2-methyl-phenoxy)methyl; mp 237-243 ° C.; HRMS calcd for C 20 H 24 F 2 N 4 O: 374.1913, found: 374.1874.
Example 55b
[0304] (7S,9aS)-7-(3-Cyano-phenoxy)methyl-; mp 209-211 ° C.; HRMS calcd for C 20 H 23 FN 5 O (MH+): 368.1887, found: 368.1884.
Example 55c
[0305] (7S,9aS)-7-(3-(Carbomethoxy)methyl-phenoxy)methyl-; mp 158-161 ° C.; HRMS calcd for C 22 H 28 FN 4 O 3 (MH+): 415.2139, found: 415.2123.
EXAMPLE 56
(7S,9aS)-7-(Substitued-phenoxy)methyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0306] [0306]
[0307] The following compounds were prepared according to Example 8 from (7S,9aS)-7-hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 13) and the appropriate phenol. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixtures of chloroform and methanol as the eluting solvent. The stereochemical configuration, 7-(substituted-phenoxy)methyl substituent, melting point of the monohydrochloride salt and HRMS data are shown.
Example 56a
[0308] (7S,9aS)-7-(4-Fluoro-2-trifluoromethylphenoxy)methyl; mp 205-206° C.; HRMS calcd for C 20 H 21 F 5 N 4 O: 428.1636, found: 428.1633.
Example 56b
[0309] (7S,9aS)-7-(2-Bromo-4-fluorophenoxy)methyl; mp 228-230° C.; HRMS calcd for C 19 H 21 BrF 2 N 4 O: 438.0867, found: 438.0862.
Example 56c
[0310] (7S,9aS)-7-(2-Carbomethoxy-4-fluorophenoxy)methyl; mp 204-205° C.; HRMS calcd for C 21 H 24 F 2 N 4 O 3 : 418.1816, found: 418.1836.
Example 56d
[0311] (7S,9aS)-7-(3,4-Difluorophenoxy)methyl-; mp 226-227 ° C.; HRMS calcd for C 19 H 21 F 3 N 4 O: 378.1667, found: 378.1640.
Example 56e
[0312] (7S,9aS)-7-(3,5-Difluorophenoxy)methyl-; mp 208-211 ° C.; HRMS calcd for C 19 H 21 F 3 N 4 O: 378.1667, found: 378.1703.
Example 56f
[0313] (7S,9aS)-7-(3-Trifluoromethoxyphenoxy)methyl-; mp 180-184 ° C.; HRMS calcd for C 20 H 23 F 4 N 4 O 2 (MH+): 427.1757, found: 427.1776.
Example 56g
[0314] (7S,9aS)-7-(4-Trifluoromethylphenoxy)methyl-; mp 188-193 ° C.; HRMS calcd for C 20 H 23 F 4 N 4 O (MH+): 411.1803, found: 411.1803.
Example 56h
[0315] (7S,9aS)-7-(3-Methoxyphenoxy)methyl-; mp 229-103 ° C.; HRMS calcd for C 20 H 26 FN 4 O 2 (MH+): 373.2040, found: 373.2051.
Example 56i
[0316] (7S,9aS)-7-(4-Methoxyphenoxy)methyl-; mp 220-224 ° C.; HRMS calcd for C 20 H 26 FN 4 O 2 (MH+): 373.2040, found: 373.2055.
Example 56j
[0317] (7S,9aS)-7-(4-Ethylphenoxy)methyl-; mp 227-229 ° C.; HRMS calcd for C 21 H 28 FN 4 O (MH+): 371.2247, found: 371.2228.
Example 56k
[0318] (7S,9aS)-7-(2,4-Difluorophenoxy)methyl-; mp 222-224 ° C.; HRMS calcd for C 19 H 22 F 3 N 4 O (MH+): 379.1746, found: 379.1759.
Example 56l
[0319] (7S,9aS)-7-(4-Carboexthoxy-phenoxy)methyl-; mp 230-232 ° C.; HRMS calcd for C 22 H 28 FN 4 O 3 (MH+): 415.2145, found: 415.2130.
Example 56m
[0320] (7S,9aS)-7-(4-Bromo-2-methoxy-phenoxy)methyl-; mp 214-216 ° C.; HRMS calcd for C 20 H25BrFN 4 O 2 (MH+): 451.1145, found: 451.1108.
Example 56n
[0321] (7S,9aS)-7-(3,4,5-Trifluoro-phenoxy)methyl-; mp 188-191 ° C.; HRMS calcd for C 19 H21F 4 N 4 O (MH+): 397.1651, found: 397.1667.
Example 56o
[0322] (7S,9aS)-7-(3-Nitro-phenoxy)methyl-; mp 114-119 ° C.; HRMS calcd for C 19 H 23 FN 5 O 3 (MH+): 388.1785, found: 388.1799.
Example 56p
[0323] (7S,9aS)-7-(3-Acetamido-phenoxy)methyl-; mp 162-165 ° C.; HRMS calcd for C 21 H 27 FN 5 O 2 (MH+): 400.2149, found: 400.2131.
Example 56q
[0324] (7S,9aS)-7-(3-Trifluoromethyl-phenoxy)methyl-; mp 200-202 ° C.; HRMS calcd for C 20 H23F 4 N 4 O (MH+): 411.1808, found: 411.1781.
Example 56r
[0325] (7S,9aS)-7-(3-Carbomethoxy-phenoxy)methyl-; mp 225-226 ° C.; HRMS calcd for C 21 H 26 FN 4 O 3 (MH+): 401.1989, found: 401.1989.
Example 56s
[0326] (7S,9aS)-7-(3-(4-Morpholino)-phenoxy)methyl-; mp 233-236 ° C.; HRMS calcd for C 23 H 31 FN 5 O 2 (MH+): 428.2462, found: 428.2477.
Example 56t
[0327] (7S,9aS)-7-(3-(1,1-Dimethyl)ethyl-phenoxy)methyl-; mp 252-254 ° C.; HRMS calcd for C 23 H 32 FN 4 O (MH+): 399.2560, found: 399.2528.
Example 56u
[0328] (7S,9aS)-7-(4-Fluoro-2-propyl-phenoxy)methyl-; mp 165-170 ° C.; HRMS calcd for C 22 H 28 F 2 N 4 O: 402.2225, found: 402.2183.
Example 56v
[0329] (7S,9aS)-7-(3-Methyl-phenoxy)methyl-; mp 90-92 ° C.; HRMS calcd for C 20 H 26 FN 4 O (MH+): 357.2091, found: 357.2088.
Example 56w
[0330] (7S,9aS)-7-(3-Dimethylamino-phenoxy)methyl-; mp 216-220 ° C. (dec); HRMS calcd for C 21 H 29 FN 5 O (MH+): 386.2356, found: 386.2368.
Example 56x
[0331] (7S,9aS)-7-(2-Methoxy-3-(1-methyl)ethyl-phenoxy)methyl-; mp 221-223 ° C. (dec); HRMS calcd for C 23 H 32 FN 4 O 2 (MH+): 415.2505, found: 415.2467.
Example 56y
[0332] (7S,9aS)-7-(4-Acetamido-phenoxy)methyl-; mp 220-223 ° C.; HRMS calcd for C 21 H 27 FN 5 O 2 (MH+): 400.2143, found: 400.2136.
EXAMPLE 57
(7S,9aS)-7-(Substitued-phenoxy)methyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazines
[0333] [0333]
[0334] Compounds of the above formula were prepared according to Example 8 from (7S,9aS)-7-hydroxymethyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 14) and the appropriate phenol. Purification was generally accomplished by flash silica gel chromatography using mixtures of ethyl acetate and hexane or mixtures of chloroform and methanol as the eluting solvent. The stereochemical configuration, 7-(substituted-phenoxy)methyl substituent, melting point of the monohydrochloride salt and HRMS data are shown.
Example 57a
[0335] (7S,9aS)-7-(4-Fluorophenoxy)methyl; mp 244-249° C.; HRMS calcd for C 20 H 23 CIFN 3 O: 375.1508, found: 375.1490.
Example 57b
[0336] (7S,9aS)-7-(3,5-Difluorophenoxy)methyl; mp 230-233 ° C.; HRMS calcd for C 20 H 22 CIF 2 N 3 O: 393.1414, found: 393.1389.
PREPARATION 1
(7R,9aS)-7-Hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine 2HCl
[0337] [0337]
[0338] A solution of 4.0 g (15 mmol) (7R,9aS)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) in 40 mL of chloroform was treated with excess HCl(g) in ether. After stirring for 1 h, the solvent was evaporated to give 3.1 g (86%) of the hygroscopic dihyrochloride salt which was used without further purification in subsequent reactions. 13 C NMR (2 HCl, d- 6 DMSO): δ 26.9, 28.8, 30.5, 44.9, 50.6, 54.7, 59.0, 61.1, 64.5. HRMS calcd for C 9 H 18 N 2 O: 170.1419, found: 170.1414.
PREPARATION 2
(7S,9aS)-7-Hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0339] [0339]
[0340] A solution of 5.84 g (21.6 mmol) of (7S,9aS)-N-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) in 140 mL of trifluoroacetic acid and 60 mL of water was stirred at room temperature for 16 h. The mixture was concentrated and the residue dissolved in water. The aqueous phase saturated with solid sodium carbonate and extracted with chloroform (3×). The combined organic layers were dried (magnesium sulfate), filtered and evaporated to give 3.39 g (92%) of the title compound. This material was used without further purification for subsequent reactions. 13 C NMR (base, d- 6 DMSO): δ 24.8, 25.1, 36.0, 45.7, 51.9, 56.1, 56.7, 62.0, 62.7.
PREPARATION 3
(7RS,9aSR)-7-Hydroxymethyl-2-(pyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0341] [0341]
[0342] A mixture of 4.5 g (26 mmol) of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874), 3.0 g (26 mmol) of 2-chloropyrimidine, and 6.7 g (63 mmol) of sodium carbonate in 100 mL of water is heated at 95° C. for 16 h. The mixture was cooled to room temperature, extracted with methylene chloride (3×), the combined organic layers were washed with water and brine, dried, filtered and evaporated to give 4.68 g (72%) of the title compound which was used without purification in subsequent reactions.
PREPARATION 4
(7R,9aS)-7-Hydroxymethyl-2,3,4,6,7,8,9,9a-octahydHro-2-(pyrimidin-2-yl)-1H-pyrido[1,2-a]pyrazine
[0343] [0343]
[0344] A mixture of 2.52 g (14.8 mmol) of (7R,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 1), 1.70 g (14.8 mmol) of 2-chloropyrimidine and 6.91 g (65.2 mmol) of sodium carbonate in 150 mL of water was heated at 90° C. for 16 h.; then cooled and extracted with chloroform (3×). The organic layer was dried (magnesium sulfate), filtered and evaporated to give 3.25 g (89%) of the title compound which was used without purification in subsequent reactions.
PREPARATION 5
(7R,9aS)-7-Hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0345] [0345]
[0346] A solution of 4.41 g (18.2 mmol) of (7R,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine dihyrochloride (Preparation 1), 3.78 g (28.5 mmol) of 2-chloro-5-fluoropyrimidine (B. Baasner, E. Klauke J. Fluroine Chem., 1989, 45, 417-430), and 9.07 g (85.6 mmol) of sodium carbonate in 180 mL of water were heated at 95° C. for 16 h. The mixture was cooled to room temperature, extracted with chloroform (2×), dried (magnesium sulfate), filtered and evaporated. Purification by flash chromatography on silica gel using 95:5 chloroform:methanol gave 5.56 g (81%) of title compound. mp 148-149.5° C. 13 C NMR (CDCl 3 ): δ 26.8, 29.0, 39.1, 44.2, 49.7, 54.8, 58.7, 60.8, 66.2, 145.0, 145.3, 149.9, 153.2, 158.7. Anal calcd for C 13 H 19 FN 4 O: C, 58.63; H, 7.19; N, 21.04; found: C, 58.36; H, 7.18; N, 20.87.
PREPARATION 6
(7RS,9aSR)-7-Hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-2-(5-fluoro-4-thiomethylpyrimidin-2-yl)-1H-pyrido[1,2-a]pyrazine
[0347] [0347]
[0348] The title compound was synthesized according to Preparation 5 from (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874) and 2-chloro-5-fluoro-4-thiomethylpyrimidine (Uchytilova, V.; Holy, A.; Cech, D.; Gut, J. Coll. Czech. Chem. Commun., 1975, 40, 2347. Ueda, T.; Fox, J. J. J. Med. Chem., 1963, 6, 697), and was used for subsequent reactions without purification.
PREPARATION 7
(7R,9aS)-2-BOC-7-(4-Fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1 H-pyrido[1,2-a]pyrazine
[0349] [0349]
[0350] A solution of 12.0 g (44.4 mmol) of (7R,9aS)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552), 7.47 9 (66.7 mmol) of 4-fluorophenol, 14.0 g (53.3 mmol) of triphenylphosphine in 450 mL of THF was treated with 8.40 mL (53.3 mmol) of diethyl azodicarboxylate and stirred at room temperature for 16 h. The mixture was diluted with ethyl acetate and treated with HCl(g) in ethyl ether until precipitation ceased. The solvent was evaporated and the solid residue was repeatedly washed with 1:1 ethyl acetate:ethyl ether. The residue was dissolved in chloroform and washed with 15% NaOH. The organic phase was dried (magnesium sulfate), filtered and evaporated to give 15.9 g of yellow-white crystals. The crude product was dissolved in 1:1 hexane:ethyl acetate and filtered through a plug of silica gel to give 13.3 g (82%) of the title compound. mp 90-92° C. 13 C NMR (CDCl 3 ): δ 26.9, 28.4, 28.8, 54.8, 58.7, 60.8, 71.6, 79.7, 115.33, 115.44, 115.58, 115.89, 154.6, 155.1, 155.6, 158.8. Anal calcd for C 20 H 29 FN 2 O 3 : C, 65.91; H, 8.02; N, 7.69; found: C, 65.90; H, 8.06; N, 7.77.
PREPARATION 8
(7R,9aS)-7-(4-Fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0351] [0351]
[0352] A solution of 44.4 g (122 mmol) of (7R,9aS)-2-BOC-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 7) in 500 mL of trifluroacetic acid and 200 mL of water was stirred at room temperature for 16 h. The mixture was concentrated by evaporation, the residue dissolved in water, basified with 15% NaOH, and extracted with ethyl acetate (2×). The organic layers were dried (magnesium sulfate), filtered and evaporated to give 31.4 g (96%) of (7R,9aS)-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine which was suitable for use in subsequent reactions. Purification of a 0.40 9 sample by flash silica gel chromatography eluting with 90:10 chloroform:methanol gave 0.38 g of colorless crystals. mp (.2 HCl) 200-201° C. 13 C NMR (base, CDCl 3 ): δ 27.2, 29.1, 36.3, 45.9, 51.9, 56.0, 59.1, 62.5, 71.7, 115.4 (d, J CF =8), 115.7 (d, J CF =23). HRMS calcd for C 15 H 21 FN 2 O: 264.1638, found: 264.1660.
PREPARATION 9
(7S,9aR)-7-(4-Fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine 2HCl
[0353] [0353]
[0354] A solution of 0.39 g (1.4 mmol) of (7S,9aR)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 0.24 g (2.2 mmol) of 4-fluorophenol and 0.45 g (1.7 mmol) of triphenyl phosphine in 20 mL of dry THF was treated with 0.27 mL (1.7 mmol) of diethyl azodicarboxylate, and stirred at ambient temperature for 16 h. The solution was diluted with ethyl acetate and treated with excess HCl(g) in ethyl ether. The solvent was evaporated and the white, solid residue was washed with 1:1 ethyl acetate:ethyl ether. The solid remaining was dissolved in chloroform and washed with 1M NaOH, dried (magnesium sulfate), filtered and evaporated to give 0.45 g of (7S,9aR)-2-BOC-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0355] A solution of 0.44 g (1.2 mmol) of (7S,9aR)-2-BOC-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 25 mL of chloroform was treated with excess HCl(g) in ethyl ether and stirred at ambient temperature for 2 h. The solvent was evaporated to give 0.40 g of title compound as the dihydrochloride salt which was used for subsequent reactions without purification.
PREPARATION 10
(7R,9aR)-7-(4-Fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0356] [0356]
[0357] A solution of 0.71 g (2.63 mmol) of (7R,9aR)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine, 0.44 g (3.94 mmol) of 4-fluorophenol and 0.83 g (3.16 mmol) of triphenylphosphine in 25 mL of THF was treated with 0.50 mL (3.16 mmol) of diethyl azodicarboxylate and stirred at ambient temperature for 16 h. The solvent was evaporated, the residue dissolved in ethyl acetate and washed with 1M NaOH (2×). The organic layer was dried (magnesium sulfate), filtered and evaporated. Purification by flash chromatography with 75:25 ethyl acetate:hexane gave 0.5 g of a sticky solid. This material was dissolved in chloroform, washed with 1M NaOH, dried (magnesium sulfate), filtered and evaporated to give 0.20 g of (7R,9aR)-2-BOC-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine.
[0358] A solution of 0.20 g (0.55 mmol) of (7R,9aR)-2-BOC-7-(4-fluorophenoxy)methyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine in 10 mL of trifluoroacetic acid and 3 mL of water was stirred at ambient temperature for 4 h. The mixture was concentrated in vacuo and the residue diluted with water. The solution was adjusted to pH 12 with 15% NaOH, and extracted with ethyl acetate (2×). The organic phase was dried (magnesium sulfate), filtered and evaporated to give 0.149 g of the title compound which was used without further purification for subsequent reactions.
PREPARATION 11
(7RS,9aSR)-7-Hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-2-(pyridin-2-yl)-1 H-pyrido[1,2-a]pyrazine
[0359] [0359]
[0360] A mixture of 1.0 g (5.9 mmol) of (7RS,9aSR)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (U.S. Pat. No. 5,326,874); 4.6 g (29 mmol) of 2-bromopyridine, 1.5 g (14 mmol) of sodium carbonate and 50 mL of isoamyl alcohol were refluxed for 18 h. The mixture was cooled to room temperature, filtered, and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed with saturated sodium carbonate. The organic layer was dried (magnesium sulfate), filtered and evaporated, and the crude product was purified by flash chromatography on silica gel eluting first with chloroform followed by 95:5 chloroform:methanol to give 0.61 g (42%) of the title compound. 13 C NMR (base, CDCl 3 ): δ 26.8, 29.0, 39.0, 45.1, 50.7, 54.8, 58.7, 60.8, 66.0, 107.1, 113.3, 137.5, 147.9, 159.3.
PREPARATION 12
3-[(7R,9aS)-2,3,4,6,7,8,9,9a-Octahydro-1 H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzoxazol-2-one
[0361] [0361]
[0362] A solution of 5.0 g (18.5 mmol) of (7R,9aS)-2-BOC-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (WO 93/25552) and 2.84 mL (20.4 mmol) of triethylamine in 200 mL of dry methylene chloride was chilled to 0C and treated with a solution of 1.50 mL (19.4 mmol) of methanesulfonyl chloride in 75 mL of methylene chloride. After 1 h, the mixture was diluted with water, basified to pH 12 with 15% sodium hydroxide, the layers were separated, and the aqueous layer extracted with methylene chloride. The combined organic phase was washed with brine, dried (magnesium sulfate), filtered and evaporated the give 6.4 g (100%) of mesylate.
[0363] A solution of 7.00 g (51.8 mmol) of 2-benzoxazolinone in 180 mL of DMF was treated with 2.05 g (51.3 mmol) of sodium hydride (60% oil dispersion) and the mixture stirred at 50° C. for 1.5 h. The heat source was temporarily removed, a solution of 6.4 g (18 mmol) of the above mesylate in 180 mL of DMF was added and the mixture heated at 100° C. for 2 h. The reaction was cooled to room temperature, diluted with water, acidified to pH 2 with 6M hydrochloric acid and washed with ethyl acetate (2×). The pH was adjusted to 12 with conc. ammonium hydroxide and the aqueous phase extracted with ethyl acetate (3×). The combined organics were dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with ethyl acetate gave 3.55 g (50%) of 3-[(7R,9aS)-2-BOC-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzooxazol-2-one.
[0364] A solution of 3.1 g (8.01 mmol) of 3-[(7R,9aS)-2-BOC-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]-pyrazin-7-ylmethyl]-3H-benzooxazol-2-one in 40 mL of chloroform was stirred with excess HCl (g) in ethyl ether for 2 h at ambient temperature. The solvent was evaporated to give 2.3 g (100%) of the title compound dihydrochloride which was used for subsequent reactions without further purification.
PREPARATION 13
(7S,9aS)-7-Hydroxymethyl-2-(5-fluoropyrimidin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0365] [0365]
[0366] A mixture of 2.31 g (13.6 mmol) of (7S,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine (Preparation 2), 1.98 g (15.0 mmol) of 2-chloro-5-fluoropyrimidine (B. Baasner, E. Klauke, J. Fluorine Chem., 1989, 45, 417), 4.32 g (40.8 mmol) of sodium carbonate and 50 mL of water was heated at reflux for 16 h. The mixture was cooled to room temperature and extracted with chloroform (3×). The combined organic layers were dried (magnesium sulfate), filtered and evaporated. Purification by flash silica gel chromatography with 95:5 chloroform:methanol gave 2.7 g (75%) of the title compound. mp (base) 111-112° C. 13 C NMR (base, CDCl 3 ): δ 26.5, 27.3, 34.2, 44.3, 49.8, 54.8, 58.8, 60.7, 68.2, 145.0, 145.3, 149.9, 153.2, 158.6. HRMS calcd for C 13 H 19 FN 4 O: 266.1543, found: 266.1530.
PREPARATION 14
(7S,9aS)-7-Hydroxymethyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0367] [0367]
[0368] A mixture of 2.5 g (10.3 mmol) of (7S,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine dihydrochloride, 7.62 g (51.5 mmol) of 2,5-dichloropyridine, 5.45 g (51.5 mmol) of sodium carbonate and 100 mL of isoamyl alcohol was heated at reflux for 72 h. The mixture was cooled, the mixture filtered to remove solids and the solvent evaporated in vacuo. Purification by flash silica gel chromatography using 95:5 chloroform:methanol gave 1.72 g (59%) of the title compound. mp (base) 61-62° C. 13 C NMR (base, CDCl 3 ): δ 26.6, 27.2, 34.3, 45.4, 50.9, 54.6, 58.4, 60.5, 68.0, 107.7, 120.1, 137.1, 146.2, 157.5. HRMS calcd for C 14 H 20 CIN 3 O: 281.1295, found: 281.1298.
PREPARATION 15
(7R,9aS)-7-Hydroxymethyl-2-(5-chloropyridin-2-yl)-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine
[0369] [0369]
[0370] A mixture of 1.35 g (5.56 mmol) of (7R,9aS)-7-hydroxymethyl-2,3,4,6,7,8,9,9a-octahydro-1H-pyrido[1,2-a]pyrazine dihyrochloride (Preparation 1), 4.11 g (27.8 mmol) of 2,5-dichloropyridine, 2.94 g (27.8 mmol) of sodium carbonate and 60 mL of isoamyl alcohol was heated at reflux for 48 h. The mixture was cooled and the solvent removed in vacuo. Purification by flash silica gel chromatography with 95:5 chloroform: methanol gave 1.02 g (65%) of the title compound. mp (base) 139.0-140.5° C. 13 C NMR (CDCl 3 ): δ 26.8, 29.1, 39.1, 45.3, 50.8, 54.6, 58.6, 60.6, 66.2,107.7, 120.1, 137.1, 146.2, 157.6. | Substituted pyrido[1,2-a]pyrazines of general formula I; wherein Ar and Ar 1 represent various carbocyclic and heterocyclic aromatic rings; A represents O, S, SO, SO 2 , CHOH, C═O, or —(CR 3 R 4 ); and n is 0-2, as well as precursors thereto, are ligands for dopamine receptor subtypes and serotonin (5HT) within the body and are therefore useful in the treatment of disorders of the dopamine and serotonin systems: | 2 |
This application is a continuation of application Ser. No. 732,248, filed 05/01/85 now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to slot machines of the type which selects combinations of symbols at random during each game and awards prizes when predetermined prize-winning combinations occur on designated prize-winning rows.
As is well known in this art, slot machines of this type have a plurality of rotatable reels each of which is provided with an annular row of various symbols on the outer surface thereof. During a game, each reel is caused to rotate, and is stopped at random at one of possible stop positions in each of which it displays a corresponding symbol to a player through a window. Recently, there have been proposed slot machines of this type, which use a simulated video display of a plurality of rotating reels. In either case, such slot machines are provided with a starting lever or button for starting the reels to rotate all at once, stop buttons for selectively individually stopping the respective reels preferably at mutually different moments of time after the start of the reels, and detector means for detecting the occurrence of the prize-winning combinations on the designated prize-winning rows.
In general, slot machines are prepared for playing a game only by inserting a coin or coins into a slot thereof after a previous game has ended. Because, in such slot machines, it is usual to play the same game repeatedly, it is a nuisance for the player to have to insert coins into the slot for every game. In order to avoid this, there have been developed slot machines of the type which allows inserting a number of coins at one time before playing games and which counts down the number of coins used every game. Such slot machines are convenient to operate, because a game can be repeated many times without inserting coins before every game.
In order to increase the player's interest in the game, there have been provided slot machines of the type which allows players to select prize-winning rows. Slot machines of this type have, for example, three reels each of which, during a game, is stopped at random at one of the possible stop positions in each of which it displays a corresponding set of three symbols arranged in a vertical row in a window. Therefore, the slot machine selects three combinations of symbols arranged in three horizontal or transverse or even diagonal rows in the window and awards prize coins when predetermined prize-winning combinations occur on any of the selected rows as a prize-winning row. In slot machines of this type, the number of prize-winning rows is selected corresponding to the number of coins inserted into the slot machine. For example, the slot machine assigns the center row as the prize-winning row for one coin, the upper two rows for two coins and all three horizontal rows for three coins. After the completion of the step of assigning prize-winning rows, the operation of the starting lever or button is made possible, permitting the player thereafter to start the reels.
However, a slot machine of the type which allows inserting a number of coins at once as well as selectively assigning prize-winning rows, does not permit assigning prize-winning rows corresponding to the number of coins inserted immediately before each game. Such slot machines, therefore, require the provision of means which is operated selectively to assign prize-winning rows before the operation of starting lever or button for starting the rotation of reels.
The provision of assigning means, which obliges a player to operate a starting lever or button for starting the rotation of the reels every time the assignment of prize-winning rows is made, encumbers the game, because the starting lever or button has to be operated a number of times corresponding to the number of games repeatedly tried.
OBJECTS OF THE INVENTION
It is therefore a primary object of the present invention to provide a slot machine of the type having means for selectively assigning prize-winning rows, in which the operation of starting the rotation of reels is simplified.
It is another object of the present invention to Provide a slot machine of the type having means for selectively assigning prize-winning rows, in which a starting mechanism for the rotation of reels comprises a reduced number of parts and the facilitated operatiOn Of playing a game is realized.
SUMMARY OF THE INVENTION
To accomplish the above objects, the present invention provides that the rotation of the reels is caused as a result of the operation of means for selectively assigning prize-winning rows.
According to the present invention there is provided a slot machine in which the reels are simultaneously started to rotate by the operation of one of a plurality of manually operable means for selectively assigning prize-winning rows.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features and advantages of the invention will be described in more detail in the following, by way of an example, reference being made to the accompanying drawings, in which:
FIG. 1 is a front view showing an embodiment of the slot machine according to the present invention; and
FIG. 2 is a block diagram showing a game circuit applied to the slot machine of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1, shown therein is a slot machine 1 which comprises a set of rotary reels 5, 6 and 7 mounted side by side on a common shaft so as to be individually rotatable. Each one of the reels, 5, 6 and 7 is provided with an annular row of various symbols on the outer surface thereof and, during a game, is stopped at random at one of the possible stop positions in each of which it displays corresponding symbols to a player in one of windows 8, 9 and 10 formed in the front panel. As seen in FIG. 1, each rectangular window has a height sufficient to display three symbols in a vertical row therein.
The slot machine 1 is adapted to allow inserting a number of coins, medals or tokens (which are hereafter referred to as coins) thereinto through a slot 11 prior to playing games. The number of the coins inserted is indicated on a digital display unit 12, each elemental digit comprising seven segments of light emitting diodes. Three transverse rows of combinations of symbols on the reels 5, 6 and 7 which are visible through the windows 8, 9 and 10 win prizes when any combination of symbols occurs corresponding to any of a plurality of predetermined prize-winning combinations. In practice, a player can select the prize-winning row or rows. For this selection, the slot machine 1 is provided on its operation, panel with push buttons 16, 17 and 18 for assigning the middle transverse row 13, the upper and middle transverse rows 13 and 14 and all three horizontal transverse rows 13 to 15 as the prize-winning row or rows, respectively.
The number of coins spent per game corresponds to the number of transverse rows designated as prize-winning rows, for example, three coins for three transverse rows, two coins for two transverse rows and one coin for a single transverse row. Consequently, in response to the pushing of one of the buttons 16 to 18, the number of coins is reduced by the number of coins to be spent and the number of remaining coins is indicated on the digital display unit 12.
When pushing one of the buttons 16 to 18 for designating prize-winning rows, the reels 5 to 7 are started to rotate simultaneously with the reduction of the remaining number of coins. After a certain time has elapsed, the reels 5 to 7 are stopped at random based on random programmed numbers, each at one of the possible stop positions, and so display corresponding symbols to the player through the associated windows.
Referring now to FIG. 2, there is shown therein, in a block diagram, a control circuit for the slot machine described above with reference to FIG. 1. In FIG. 2, the section 21 enclosed with the dotted line is a microcomputer.
Upon inserting a number of coins into slot 11 prior to playing games, sensing means 19 senses the coins inserted so as to provide pulse signals, corresponding to the number of the coins, which are transmitted to and counted by a pulse counter 20. The counted value by the counter 20 is indicated on the digital display unit 12. To designate prize-winning rows, the button 17, for example, is pushed to provide pulse signals which in turn are directed toward the counter 20. The counter 20 counts down two counts and causes the digital display unit 12 to indicate the number of remaining coins. Simultaneously with the operation of the push button 17 for actuating the counter 20, the motor control 22 is actuated by receiving a signal gated by the OR gate 25' to derive a clock pulse signal from a clock pulse generating circuit 24 and deliver it to motor driving circuits 25 to 27 so as to cause pulse motors 28 to 30 to rotate. Counters 34 to 36 commence counting up at the clock pulse rate from the clock pulse generating circuit 24. The pulse motors 28 to 30 thus caused to rotate cause the respective reels 5 to 7 to rotate and to occupy positions corresponding to counts of the respective counters 34 to 36.
The reels 5 to 7 are provided on their periphery with projections 5a to 7a which cooperate with photosensors 37 to 39, respectively, so as to provide, every time the projections pass the photosensors, signals each of which in turn is directed to the respective counter 34 to 36 to reset its content to an initial value, for example zero.
It should be noted that the numbers of pulses counted by each counter have one-to-one correspondence to the respective symbols arranged on the peripheral surface of each reel associated with the counter. Thus, it can be detected based on the content of the counter, which symbols are displayed in the window.
When a certain time has elapsed after starting the rotation of the reels, a random number generator 23 is actuated to provide signals which in turn are directed to the motor control 22 and shut it off to stop the rotation of the respective pulse motors 28 to 30. At this time, symbol discriminating circuits 40 to 41 derive the contents of the respective counters 34 to 36 as signals to determine which symbols are displayed in the respective windows 8 to 10. A set of the signals which represent a combination of symbols is transmitted to a judging means 32 wherein various prize-winning combinations of symbols are memorized as combinations of signals and compared therein with each of the combinations of signals. The decision that there has occurred a prize-winning combination of symbols is made, based on the correspondence between these signals. When the upper and middle transverse rows 13 and 14 are designated as prize-winning rows by pushing the button 17, a signal is delivered to the judging unit 32 and causes it to compare two sets of signals with each prize-winning combination of signals memorized therein. The second set of signals is made based on the first set of signals which consist of the signals from the symbol discriminating circuits 40 to 42 because the counted numbers of pulses have one-to-one correspondence to the respective symbols arranged on the peripheral surface of each related reel.
When a predetermined prize-winning combination occurs on a prize-winning line, a prize signal is applied to a controller 44 which causes a coin hopper 45 to pay out coins of a corresponding number.
Instead of applying the prize signal to the coin pay-out controller for paying out coins every game, pulses of the numbers corresponding to the prize signal may be directed to the counter 20 for counting up. In this case, coins corresponding to the counted number of pulses are paid out by operating a pay out button (not shown) when the player is through.
Although the invention has been described in detail with particular reference to a preferred embodiment thereof, the invention is not limited to that embodiment, but various variations and modifications thereof may be made without departing from the scope of the invention. For example, it is possible to designate diagonal rows as prize-winning rows and to provide stop buttons for the respective reels. The push buttons 16 to 18 may also be used for stopping the reels. The present invention is, of course, applicable to slot machines of the type which allows using a particular card instead of coins. | A slot machine of the type having a plurality of rotatable reels, each bearing an annular row of various symbols on the outer surface thereof, which selects combinations of symbols at random during each game, and which awards prize coins when predetermined prize-winning combinations of symbols occur on prize-winning rows previously selected. For selectively designating prize-winning rows, the slot machine is provided with push buttons which also start the rotation of the reels. | 6 |
The present application is a division of U.S. patent application Ser. No. 08/432,657, filed May 2, 1995, now U.S. Pat. No. 5,733,428; which is a continuation of application Ser. No. 08/185,667 filed Jan. 21, 1994, now abandoned; which is a continuation-in-part of application Ser. No. 07/909,543 filed Jul. 6, 1992, now abandoned.
BACKGROUND OF THE INVENTION
The use of urethane polymers has been proposed for golf ball cover compositions. One patent teaches initially forming two urethane shell blanks from which cover halves are made (U.S. Pat. No. 3,989,568). Another patent suggests forming a smooth cover and thereafter impressing dimples in the smooth cover (U.S. Pat. No. 5,006,297). Still another patent describes a sequence of filling first half of a mold with urethane, inserting a ball center therein and later adding more urethane to a second half and uniting the second with the first half (U.S. Pat. No. 3,147,324).
SUMMARY OF THE INVENTION
Broadly, the present invention is a method and apparatus for making a golf ball comprising treating a core as described herein, placing a polyurethane cover of selected composition thereon in which the treated core is positioned in a mold using a controlled alignment device for centering the core during cover formation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is plan view of the core treating apparatus;
FIG. 2 is an elevational view of such apparatus;
FIG. 3 is an elevational view of alignable device for placing a treated core in a mold half;
FIG. 3a is a partial side elevational view of the alignable device;
FIG. 4 is a sectional view along line 4--4 of FIG. 3;
FIG. 5 is a plan view showing a mold being positioned in the alignment device;
FIG. 6 shows apparatus for mixing polyurethane, dispensing it in a mold half and shows one mold half being inverted before mating with a second mold half.
FIG. 7 shows a plan view of set-up mold;
FIG. 7a shows a side view of set-up core with alignment holes;
FIG. 8 is a graph plotting voltage vs. cps;
FIG. 9 is a graph plotting voltage vs. time;
FIG. 10 is a table of process steps in a timed sequence;
FIG. 11 is a graph plotting hardness vs. spin rate;
FIG. 12 is a graph plotting initial velocity vs. wound ball size;
FIG. 13 is a front elevational view of an alternative embodiment of the core alignment device;
FIG. 13a is a side elevational view of the alignment device;
FIG. 14 is a sectional view along line 14--14 of FIG. 3; and
FIG. 15 is a plan view of a mold half with a horizontal aligning rail unit.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning to the Figures, and in particular to FIGS. 1 and 2, dipping apparatus 10 includes a dip tank 12 filled to level 12a and agitated by electric mixer 12m. Apparatus 10 also includes oval conveying rack 13 with ball core carriers 16. Dip tank 12 is filled with latex bath 12b to level 12a and, if latex has been in tank 12 for a substantial length of time, initial mixing of bath 12b in tank 12 should be carried out until uniformity of bath 12b is reached. After such mixing golf ball cores 14 are loaded at loading station 15 into holding carriers 16 each comprising a stem 16a and a holder ring 16b. During normal operation tank 12 is agitated by electric mixer 12m. Loaded carriers 16 are carried by conveying rack 13 along and down to dip cores 14 for 1 to 60 seconds into latex bath 12b. Rack 13 moves through a descending portion 20, dipping portion 22 and ascending portion 24 of the carrier circuit to accomplish the latex dip core treatment. In wound cores the latex encapsulates the core with penetrate to a depth of about 0.050 inch and in solid cores the latex forms an encapsulating coating on the core of 0.001-0.010 inches thick.
After the ball cores 14 exit dip tank 12, they pass into a curing chamber 25 in which heat, ultraviolet rays, or other means for accelerating cure may be applied. It will be understood that some latex bath materials cure sufficiently under ambient conditions that curing chamber 25 is not required. Cores are unloaded at unload station 21.
In accordance with this invention, wound cores 14 preferably are latex dipped while dipping of solid cores 14 is optional. Depending on the nature of the latex material applied, the golf ball dip-treated cores 14 can then be stored for a period of time for additional cure, or, if the latex material is sufficiently cured at this point, the wound cores with the latex dip encapsulate can be transported directly to the molding area for molding of the cover material.
Since the latex material generates low levels of ammonia fumes in the dip tank 12, it is preferred to have a vacuum hood 23 positioned above the dip tank 12. The vacuum hood 23 is preferably provided with means (not shown) for generating a clean air curtain about the periphery of the dip tank 12 to prevent escape of undesirable gasses. The curing chamber 25 can also be provided with suitable gas removal means.
As described above, the initial step of the process of the present invention is the dipping of the core in a latex bath. The preferred core is a wound core but any core, molded or wound, may be treated by the present process. With a molded core the advantage of such latex dip treatment is the increased velocity attainable to golf balls made with such cores. With a wound core the advantages are increased velocity, reduction of flow of air into the cover material during cover formation and prevention of rubber strand unravelling.
It is important that a thermosetting, not a thermoplastic, latex be employed so that the arrangement of the cover material to the core encapsulated will not soften the encapsulating envelope and permit air to pass through it into the interstices in the windings of the wound core or allow the rubber strands to unravel.
The thermosetting latex materials which are useful in the present invention are any materials which will withstand the temperatures at which the cover material is to be applied. This temperature will, of course, depend upon the particular fluidization temperature of the selected cover material. Typical thermosetting latex materials which can be used are: low ammonia, natural latex or pre-vulcanized natural latex with or without penetrant. When using a polyurethane cover material, it has been found that pre-vulcanized natural latex is particularly suitable.
The preferred latex material, Heveatex brand Model H1704 pre-vulcanized natural latex, is a partially pre-vulcanized material which has a 60%-30% water dilution solids content. The preferred penetrant material is Niaproof #4 (tetra decyl sulfate) sold by Niacet Corp. It is understood that non-latex encapsulating materials may also be used.
After latex coating, the cover is formed around the coated core by mixing and introducing the material in mold halves. Once mixed, an exothermic reaction commences and continues. It is important that the viscosity be measured over time, so that the subsequent steps of filling each mold half, introducing the core into one half and closing the mold can be properly timed for accomplishing centering of the core cover halves fusion and achieving overall uniformity.
The increase in the viscosity of the urethane mix over time is measured by Vibrating Needle Curemeter (VNC) manufactured by Rapra Technology Limited. It is achieved by suspending a steel needle in the curing formulation. The needle is vibrated vertically by a small electrodynamic vibrator driven by a signal generator. Resistance to its movement is ultimately recorded as the voltage output. Suitable viscosity range of the curing urethane mix for introducing cores 14 into the mold halves 51, 59 is determined to be approximately between 2,000 cps-30,000 cps or between 60 mv-98 mv voltage output with the preferred range of 8,000 to 15,000 cps (see FIG. 8). The time (gel time) at which the desired viscosity range occurs for mold mating is measured from first introduction of mix into the top half mold 51a.
The dip coating of latex penetrates the interstices, crevices and openings between the wound core threads to a depth of a fraction of an inch preferable about 0.050 inches and, as solidified, prevents a substantial quantity of air from flowing from the interior of the core into the cover during its formation. A negligible amount of the latex remains on the outside of the wound core. With solid cores about 0.001-0.010 inches is coated on the surface thus reducing the cover thickness by that amount. Small amounts of air passing through or around the latex coating are not large enough to create noticeable imperfections in the cover as determined by visual inspection.
Turning to FIGS. 3 and 3a, another step of the process is the formation of the cover on the wound core 12. To accomplish this step a centering fixture is used. Fixture unit 30 includes box frame 32, stationary central guide mount 34 comprising fixed cylinder 35 and stationary guide block 37. Guide block 37 has two (2) parallel passageways 37a, 37b therethrough for receiving movable rods 41, 42 in sliding vertical movement. Rods 41, 42 are fixed to slide ball cup frame unit 44, through back piece 40, which unit 44 carries ball cup 46 mounted on cup plate 44b as described (see FIG. 3a). Ball cup 46 holds ball core 14 through reduced pressure (or partial vacuum) in hose 46a . Ball cup frame unit 44 includes base plate 44b, central opening 44a and upstanding back plate 44c. Back support 40 is secured to back plate 44c. Ball cup 46 is adjustably secured to cup plate 44b through adjustable fasteners 49a, b which ride in slots 44s and 44t (FIG. 4). Cup 46 can be adjusted vis-a-vis plate 44b front and back along arrow A (FIG. 4).
To initially align ball core cup 46 in the proper position for molding of cover material, a machined metal set-up mold 50 is used. Set-up mold 50 is positioned by lowering unit 44 to permit pins 72, 73 to pass through alignment holes 71a, 71b in mold 50. Rails 53 and 56 serve only to assist in placing the mold 50 under unit 44 and after mold 50 is properly aligned it is spaced a few thousandths of an inch from each rail 53, 56 (FIG. 7). With ball cup 46 free through loosened fasteners 49a, b, alignment of cup 46 is accomplished by lowering ball cup 46 until it sits on and contacts set-up core 70. Fasteners 49a, b are tightened when flush contact with ball cup 46 and set-up core 70 has been made. Next, mechanical stop 39b is tightened in this position. Frame unit 44 is then raised from set-up mold 50 and set-up mold 50 is removed from fixture 30.
More than one fixture unit 30 is used in the practice of this invention. With fixture unit 30 so aligned, the set-up mold 50 is removed and is ready to be replaced with a ball core 14 and a series of regular mold halves 51b, 51c, etc.
The core is centered by fixture unit 30 in the top mold half, as then inverted, to a tolerance of about 0.010 of an inch. Such tolerance is described by determining the theoretical center of the core in the mold half and tolerating the actual core center, as fixtured, to be located up to 0.005 of an inch in any direction for the theoretical center. Since the actual center is tolerated to move 0.005 inch in any direction from the theoretical center, it can move over a range of 0.010 of an inch.
Turning to FIGS. 13-15, prime numbered elements correspond to elements on FIGS. 3-5. This alternative embodiment aligns each mold half 51, 59 with respect to the fixture frame base 30b of frame 30' using a horizontal rail alignment unit 66 which includes stationary mount block 66m, positioned on fixture base 30b, a raised horizontal cross piece 66c which carries two (2) parallel alignment rails 66a , 66b having square cross sections which rails 66a , 66b lie in mold end-to-end indentations 67, 68. Each mold indentation 67 and 68 includes a horizontal wall 67a, 68a and a vertical wall 67b, 68b. Rails 66a , 66b have tapered tips 66d, 66e to assist in guiding and positioning mold halves 51', as each is slid in direction D to the position of FIG. 15. As a mold half 51' is moved back against block 66m it is aligned and the mold half 51' is thereafter accurately positioned as pins 72' and 73' engage and move, as necessary, the mold half 51' during fixture descent. The spacings between block 66m and rails 66a , 66b and mold 51 are exaggerated in FIG. 15. These tolerances are small enough to achieve the centering tolerances set out below.
Vertical position of core 14 in ball cup 46' is accomplished using machined collars 84, 85 which slip over pins 72', 73' as shown. Set screws 82 are used to hold collars 84, 85. The length of collars 84, 85 determines the distance between cup plate 44b and mold halves 51', 59' and thereafter the position of core 14 (not shown) in cup 46'. Cup 46' is not adjustable in this embodiment but is held in fixed relationship to plate 44b' with fasteners 83a-c.
As in the other fixture embodiment, core 14 can, using this embodiment, be located up to 0.005 of an inch in any direction from the theoretical center.
Prior to proceeding with cover formation regular mold halves 51b, 51c are preheated to 140-180° F., the prepolymer is preheated and degassed at 140-160° F. and the curative is also preheated and degassed at a temperature of 140-160° F. As so preheated, the prepolymer and curative both have approximately viscosities of 2000 cps.
The cover material used in the present method is polyurethane which is the product of a reaction between a polyurethane prepolymer and a curing agent. The polyurethane prepolymer is a product formed by a reaction between a polyol and a diisocyanate. The curing agent is either a polyamine or glycol. A catalyst may be employed to promote the reaction between the curing agent and the polyurethane prepolymer.
Suitable polyurethane prepolymers for use in the present invention are made from a polyol, such as polyether, polyester or polylactone, and a diisocyanate. Suitable diisocyanates for use in the present invention include 4,4'-diphenylmethane diisocyanate (MDI) and 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI) and toluene diisocyanate (TDI).
Suitable polyether polyols include polytetramethylene ether glycol; poly(oxypropylene) glycol; and polybutadiene glycol. Suitable polyester polyols include polyethylene adipate glycol; polyethylene propylene adipate glycol; and polybutylene adipate glycol. Suitable polylactone polyols include diethylene glycol initiated caprolactone; 1,4-butanediol initiated caprolactone; trimethylol propane initiated caprolactone; and neopentyl glycol initiated caprolactone. The preferred polyols are polytetramethylene ether glycol; polyethylene adipate glycol; polybutylene adipate glycol; and diethylene glycol initiated caprolactone.
Suitable curatives for use in the present invention are selected from the slow-reacting polyamine group consisting of 3,5-dimethylthio-2,4-toluenediamine; 3,5-dimethylthio-2,6-toluenediamine; N,N'-dialkyldiamino diphenyl methane; trimethylene-glycol-di-p-aminobenzoate; polytetramethyleneoxide-di-p-aminobenzoate; or a difunctional glycol; and mixtures thereof. 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine are isomers and are sold under the trade name ETHACURE® 300 by Ethyl Corporation. Trimethylene glycol-di-p-aminobenzoate is sold under the trade name POLACURE 740M and polytetramethyleneoxide-di-p-aminobenzoates are sold under the trade name Polamine by Polaroid Corporation. N,N'-dialkyldiamino diphenyl methane is sold under the trade name UNILINK® by UOP.
Suitable difunctional glycols are 1,4-butanediol; 1,3-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; dipropylene glycol; and ethylene glycol. Difunctional glycols are inherently slow-reacting.
To start the cover formation, mixing of the prepolymer and curative is accomplished in motorized mixer 60 (FIG. 6) including mixing head 61 by feeding through lines 63 and 64 metered amounts of curative and prepolymer. The mixer 60 is cooled by cooling jacket 66. Due to the exothermic reaction of prepolymer and curative as mixed, the mixing head temperature will tend to rise. To control such a rise, the mixing head temperature is maintained by cooling in a range appropriate for the specific urethane material and to attain a workable gel time. From the time mixing commences until the reacting material is fed into each top mold 51a, b, c, etc. or bottom mold half 59a, b, c etc. is about 4-7 seconds. Top preheated mold halves 51a, b, c etc. are filled and placed in fixture unit 30 using pins 72, 73 moving into holes 71a, 71b in each mold 51a, b, c etc. After the reacting materials have resided in top mold halves 51a, b, c, etc. for about 50-80 seconds, a core 14 is lowered at a controlled speed into the gelling reacting mixture by lowering frame unit 44 using an pneumatic powered arrangement not shown. Alternatively, electric or hydraulic systems may be used. Controlled lowering is accomplished by adjustment of the powered arrangement and by use of pneumatic controls not shown to lessen and preferably prevent air bubbles. Stop 39b limits movement downward. The amount of mixture introduced into each mold half 51a is 5.4-5.7 g. At a later time a bottom mold half 59 of a series of bottom mold halves 59a, 59b, etc. has similar mixture amounts introduced into its cavity 58 through nozzle 74 (FIG. 6).
Upon location of the coated core 14 in halves mold 51a, b, c after gelling for 50-80 seconds, the vacuum is released in line 46a allowing core 14 to be released. Mold halves 51a, b, c with core 14 and solidified cover half 80 thereon is removed from the centering fixture unit 30, inverted by invertor 65 (see FIG. 6) and mated with other mold halves 59a, b, c which, at an appropriate time earlier have had a selected quantity of reacting polyurethane prepolymer and curing agent introduced therein to commence gelling.
When a plurality of mold halves 51a, b, c etc. and 59a, b, c etc. are filled and clamped at one time, the following time sequence is preferred.
The sequence of introducing the polyurethane mix into the top mold half 51a (1T) and its mate the bottom mold half 59a (1B) is as follows: Introduction of the mixed prepolymer and curative into the top mold 51a starts the time sequence which start is referred to herein as time zero. The top half mold 51a receives the mix first at time zero and shortly mold half is placed in fixture unit 30. The core is initially inserted in the mix located in top mold 51a at time 60 seconds (see FIG. 10). At time 72 seconds, bottom mold half 59a (1B) is filled and at time 132 seconds, the mold halves 51a, 59a (1T-1B) are mated and clamped. At time 126 seconds, the mix has been in top half 5a 126 seconds and mix has been in bottom half 50a for 60 seconds. The sequence of filling other mold halves 51b (2T) and 59b (2T) and so forth follows a similar pattern. Within this sequence of mixing and dispensing of the prepolymer and curative commences at -4 to -7 seconds.
The thorough mixing that takes place in mixer 60 for the period of time described provides an improved cover material. Mold halves 51, 53 are pre-heated to 160-190° F. The core is held in its fully-down position for 30-40 seconds and the vacuum is then released. Following clamping of mold halves, the clamped mold is put in a curing oven for approximately 10 minutes to reach a mold temperature of 140-180° F. followed by cooling for approximately 10 minutes to reach a mold temperature of 50-70° F.
The mold halves are clamped together under 400-600 psi pressure. The mold halves each contains sufficient reacting material to form hemispherical portions of the cover. Mold halves are held together for 10-15 minutes and thereafter cooled from 140° F.-180° F. to 50° F.-70° F. and then opened to demold the ball. Excess polyurethane is extruded from the mold cavity into sprue channels 51s forming solidified sprues not shown.
EXAMPLE I
A wound center was dipped in a 30% pre-vulcanized latex solution, drained and partially dried in a current of warm air. Remainder of drying was accomplished at room temperature. Latex penetration was approximately 50 mils. A mold half was preheated to approximately 160° F.
A mixture of 100 parts of Betathane 23.711, an MDI-based polyether prepolymer, 5.19 parts of titanium dioxide dispersion and 48.27 parts of Polamine 250 was prepared. Approximately 5.6 g of this mixture was dispensed into a heated mold cavity and allowed to thicken for approximately one minute. A dipped wound core with a diameter of 1.580" was placed in the bottom mold cavity by means of the centering fixture shown in FIG. 3. The core was held in a concentric position for approximately 40 seconds to allow the material to thicken further to support the core. The top heated mold half was then filled and the material allowed to thicken for approximately 1 minute. The top and bottom mold halves were then assembled and clamped by bolts or any conventional manner. The assembled mold was introduced into a curing oven and cured for 10 minutes at approximately 160° F. The assembled mold was then introduced into a cooling chamber for approximately 10 minutes to reach a mold temperature of 50-70° F.
The resulting cover was approximately 50 mils thick on a side and had a Shore D durometer of approximately 58-60 when measured after a two-day waiting period. Subsequently, the ball was painted and the cover was observed to be highly abrasion and cut resistant. Spin rate of this ball was approximately 100-200 rpm lower than a balata covered ball(Tour 100) with an acceptable velocity of 252.7 ft/sec.
EXAMPLE II
The steps of Example I were carried out except that the wound core was not dipped in a latex solution.
EXAMPLE III
The steps of Example I were carried out except that a solid core was used.
EXAMPLE IV
The steps of Example I were carried out with a solid core without a latex dip.
A range of core sizes that can be employed in this invention, whether dipped or non-dipped, is 1.560" to 1.610" was determined by previous testing that as core size of the ball increases, ball velocity increases (FIG. 11). However, if the durometer of the cover remains the same, spin rate of the ball was materially unaffected. Spin rate can be changed by modifying the durometer of the cover by selecting different ratios of materials or combining other materials. Cover durometers of 48 Shore D to 72 Shore D are attainable with the preferred range of 58-62 for this type of ball.
The relationship between durometer and spin rate was determined to be linear with harder durometer covers producing lower spin rates (FIG. 12). | A method and apparatus for making a golf ball of selected instruction having an encapsulated core or a non-treated core and a polyurethane cover of selected composition in which equipment is employed for aligning, centering and locating the core in relationship with the molding of the cover thereon. | 0 |
BACKGROUND
1. Field of Invention
This invention relates to the production, purification, and isolation of hydroxyamides, which are useful as chemical intermediates and chemical crosslinkers.
2. Description of Prior Art
Hydroxyamides have been synthesized by the aminolysis of dimethyl esters by alkanolamines. Isolation and purification of solid hydroxyamide products is done conventionally either by recrystallization (J. Coat. Tech., 50 (643), 49-55 (1978); U.S. Pat. Nos. 4,032,460; 4,076,917; 4,493,909; 4,727,111; Japanese Patent 56-062895) or by prilling/flaking. Using recrystallization, relatively pure product is obtained but product losses due to dissolution in the solvents used and the complexity of removing residual solvent from the product as well as recovering solvents for reuse pose significant disadvantages to this approach. Recrystallization is typically performed by dissolving the crude hydroxyamide in solvent, such as methanol/acetone, cooling to grow the crystals, filtering the product away from the mother liquors, and drying the product free of residual solvent. Alternatively, recrystallization may entail adding solvent to melted hydroxyamide, followed by crystal growth, filtration, and drying as described above.
Prilling/flaking requires that the hydroxyamide be maintained in a fluid state for several hours until the operation is complete. During this time in the molten state some of the product degrades to undesirable byproducts.
The physical state of the crude hydroxyamides of interest is that of a soft, sticky, waxy solid, which typically renders the materials unsuitable for use in powder coatings, such use requiring free-flowing powders. Certain hydroxyamides are useful as crosslinkers in powder coatings based on polyester or acrylate chemistries.
SUMMARY OF INVENTION
A process for producing solid hydroxyamides of the formula (I): ##STR1## wherein A is a bond, a polyvalent organic radical or when n' is zero, A may be hydrogen or a monovalent organic radical selected from a saturated or unsaturated alkyl, aryl, carboxy lower alkenyl, lower alkoxycarbonyl lower alkenyl; R 1 is selected from the group consisting of hydrogen, lower alkyl, or hydroxy lower alkyl; n is an integer having a value of 1 to 10; and n' is an integer having a value of 0 to 2; which comprises reacting carboxylic alkyl esters with alkanolamines at a certain reaction temperature, removing the alcohol byproduct compound at atmospheric or reduced pressure, controlling the temperature of the crude reaction mixture until the hydroxyamide crystallizes to form a slurry, maintaining the slurry in the reaction mixture by temperature control (25° to 200° C., preferably 80° to 115° C.) for from about 15 minutes to about 12 hours (preferably 1 to 3 hours), followed by isolation of the hydroxyamide.
This invention involves a process for producing high purity solid hydroxyamides by first forming a slurry of the solid hydroxyamide in a liquid melt mixture of said hydroxyamide, amine precursors, and other minor process impurities, followed by flaking, prilling, casting, spray drying or other means of solidification to isolate the high purity solid hydroxyamide. In another aspect, this invention is used to produce solid hydroxyamides having the consistency of a free-flowing powder suitable for direct use as a crosslinker in powder coating formulations.
The invention may be practiced by cooling the crude mixture resulting from the base catalyzed aminolysis of a diester and an alkanolamine until a thick slurry develops. The temperature of the mixture is then varied to maintain slurry characteristics during the subsequent steps used for solidification (casting, prilling, flaking, and the like).
Solid hydroxyamides produced by this invention are superior to products produced by prior art methods of recrystallization in that physical form (free-flowing powder) characteristics equal or exceed that obtained from recrystallization and no solvents are involved, thus eliminating the additional steps of solvent removal/recovery. In contrast to prior art recrystallization methods (which "separates" impurities from the desired product), the invention uses the slurry environment (solid hydroxyamide in the presence of precursors and byproducts) to "convert" some of the byproduct impurities to the desired hydroxyamide product; the slurry conditions drive the chemical reaction towards completion. The invention may be used to produce hydroxyamides that are solids at room temperature, i.e., those having melting points above about 25° C. In comparison to the prior art methods of casting, prilling, or flaking, use of the invention results in an hydroxyamide product of much higher overall quality in that fewer impurities are present, since the process of the invention does not subject the hydroxyamides to long hold times at elevated temperatures in the molten state (non-slurry conditions) during which undesirable byproducts form. Also, the operations of filtration and drying, usually associated with recrystallization routes, are eliminated by use of the invention.
DETAILED DESCRIPTION OF INVENTION
Hydroxamides which may be produced by the process of the invention include those represented by formula I: ##STR2## wherein A is a bond, a polyvalent organic radical or when n' is zero, A may be hydrogen or a monovalent organic radical where the organic radical is derived from a saturated or unsaturated alkyl radical wherein the alkyl radical contains from 1-60 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, eicosyl, triacontyl, tetracontyl, pentacontyl, hexylcontyl and the like; aryl, for example, mono- and dinuclear aryl such as phenyl, naphthyl and the like; or an unsaturated radical containing one or more ethylenic groups [>C═C<] such as ethenyl, 1-methylethenyl, 3-butenyl-1,3-diyl, 2-propenyl-1,2-diyl, carboxy lower alkenyl, such as 3-carboxy-2-propenyl and the like, lower alkoxy carbonyl lower alkenyl such as 3-methoxycarbonyl-2-propenyl and the like; tri-lower alkyleneamino such as trimethyleneamino, triethyleneamino and the like; R 1 is hydrogen, lower alkyl of from 1-5 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl and the like or hydroxy lower alkyl of from 1-5 carbon atoms such as hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxy-2-methylpropyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl and the isomers of pentyl; n is an integer having a value of 1 to 10, preferably 1 or 2, and n' is an integer of 0 to 2 or when n' is 0, a polymer or copolymer (i.e., n has a value greater than 1 preferably 2-10) formed from the β-hydroxy-alkylamide when A is an unsaturated radical.
Examples of preferred compounds fall within formula I where A is an alkylene group, preferably (C 2 -C 8 )alkylene.
Examples of the most preferred compounds fall within the formula: ##STR3## wherein m is 0-10, preferably 2-8.
Specific examples falling within Formula Ib are bis[N,N-di(β-hydroxyethyl)]adipamide, bis[N,N-di(β-hydroxyethyl)]azelamide.
The β-hydroxyalkylamides (I, supra) may be prepared by aminolysis of an ester of Formula II (infra) with an amine of Formula III (infra) at a temperature in the range of from about ambient up to about 200° C. The aminolysis reaction is typically carried out using a molar ratio of amine to ester of 2.0/1, preferably 1.95-2.05/1, and most preferably 1.98-2.02/1. In addition, the water content of the aminolysis reactants is typically controlled to less than 0.5% moisture and preferably to less than 0.1% moisture in order to maintain the activity of any basic catalyst that may be used and to minimize unwanted hydrolysis of ester reactants. Control of reactant mole ratio and moisture level is typically practiced in aminolysis reactions in order to maximize product yield and purity. Optionally, a basic catalyst may be employed, for example, potassium methoxide or butoxide; quaternary ammonium alkoxides, such as tetramethylammonium methoxide and the like; or alkali metal or quaternary ammonium hydroxides at an amount in the range of from 0.1 to 1.0 wt. % based on the weight of the ester. The reaction is preferably conducted at elevated temperatures. The following equation illustrates this process: ##STR4## wherein A, R 1 , n and n' are as defined above and R 2 is lower alkyl of from 1-5 carbon atoms such as methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl and the like.
The esters (II, supra) employed above are either known compounds or are prepared by esterifying the corresponding acid by standard esterifying procedures well-known to those skilled in the art. Among the preferred acids and mixtures thereof which can be employed are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, 1,4-cyclohexane dicarboxylic and the like and alkyl derivatives thereof. Also, there may be employed dimer and trimer acids and mixtures thereof prepared by the polymerization of C 18 fatty acids such as a dimer acid with 2 carboxy groups, 36 carbon atoms and an approximate molecular weight of 565 of a trimer acid with 3 carboxy groups, 54 carbon atoms and an approximate molecular weight of 850.
Some representative examples of the amines which can be employed include 2-aminoethanol; 2-methylaminoethanol; 2-n-butylaminoethanol.
The crude reaction mixture from the aminolysis (reaction of II with III) is maintained at a temperature of 25°-200° C., preferably 80°-115° C., until a thick slurry is formed. By manipulating the temperature, the mixture is then maintained in slurry form during subsequent isolation steps (flaking, spray drying, casting, and the like). It is important that the maximum "thickness" of the slurry be maintained during the final isolation steps, and it is important to maintain good agitation of the slurry during these steps. We have found that maximizing slurry "thickness" (as measured by bulk viscosity of the fluid mixture) unexpectedly maximizes the purity of the final product hydroxyamide.
Control of in-process viscosity may be attained by continuous monitoring via on-line viscometer instrumentation. In large-scale reactors (300-gallons and larger) relative viscosity changes have been found to be most useful; typical changes in bulk viscosity upon formation of a slurry range from 2 to 200 times the bulk viscosity of the reaction mixture prior to formation of the slurry. Specific viscosities of 300-2,500 cps (Brookfield Viscometer, 100 rpm, 34 sec -1 ) are suitable for producing high purity hydroxyamides, with 600-2,000 cps being a preferred viscosity range, when lab-scale equipment, e.g., 1-liter reactor, is used. In-process pressure is not critical to the use of the invention and vacuum or elevated pressures may be used to satisfy individual process requirements; however, it is preferable to use a slight vacuum (50-300 mm Hg) to remove residual methanol (or other alcohol byproducts) from the aminolysis reaction. Hold times may vary widely depending on the vacuum conditions and temperatures employed for the aminolysis; thereafter the temperature of the crude liquid reaction mixture is controlled in such a way to form the thick slurry. The thick slurry condition is maintained with good agitation and temperature control from about 15 minutes up to at least about 12 hours, preferably 1-3 hours, in order to achieve maximum purity of the hydroxyamide. The aminolysis may also be carried out in a solvent, in which case the solvent should be removed prior to formation of the slurry; moreover, solvent may enable the aminolysis to be conducted at lower temperatures, resulting in less byproduct formation in some cases. Practice of the process of the invention may be by batch, continuous or semicontinuous modes.
Scheme I presents an outline of the postulated chemistry of the process steps involved in the use of the invention. The reaction of dimethyladipate (DMAd) and diethanolamine (DEA) is used for illustrative purposes. The initial base-catalyzed (KOH, or other strong bases) transesterification (Equation IV) rapidly forms the theoretical diester intermediate (DE) along with methanol. DE is then believed to convert to the desired hydroxyamide (HAm) product (Equation V) or the amide-ester dimer, AED (Equation VI); the latter (in the presence of DEA) subsequently establishes an equilibrium with HAm (Equation VII). The formation of AED is a primary source of impurity in final product HAm and also the main cause of low HAm yield.
During the aminolysis reaction, all of the Scheme I components are present simultaneously in solution. As the methanol is stripped off, the HAm may begin to "crystallize" from the mixture, i.e., to form a solid in liquid (slurry), due to its lesser solubility in the reaction medium in the absence of methanol. As additional HAm crystallizes from the molten slurry mixture, the equilibrium is shifted toward HAm at the expense of DEA, DE, and AED, all of which are undesirable components in the HAm product. The crystallization of HAm is relatively slow; therefore, extended hold times tend to produce purer product and more viscous slurries. The viscosities of the slurries should be maintained as high as possible to maximize the purity and yield of the HAm, but the viscosities should not be so high that the reaction mixture completely solidifies ("sets up"), e.g., above 2,500 cps absolute viscosity at 80° C. in small-scale lab reactors. ##STR5##
EXAMPLE 1
A mixture of diethanolamine (DEA), 131 g, and potassium hydroxide (KOH), 0.5 g, is placed in a 500-ml glass reactor and blanketed with nitrogen. This mixture is heated to 100° C. under 205 mm Hg vacuum with stirring, at which point dimethyladipate (DMAd) is introduced into the mixture dropwise; the DMAd (106 g) is added over a 4 hour period during which methanol is simultaneously distilled from the reaction mixture. Within one hour after completion of the DMAd addition, the reaction mixture develops the appearance of a thick, white slurry. The slurry is maintained at 100°-103° C. for an additional 1.75 hours; the HAm product is isolated by pouring the slurry into an aluminum dish at 20°-25° C.
EXAMPLE 2 (COMPARATIVE)
In a manner similar to Example 1, the aminolysis is repeated and the reactor temperature is maintained at 93° C. such that the reaction mixture maintains its homogeneous character without forming a slurry after the DMAd addition. The reaction solution is then poured into an aluminum dish at 20°-25° C. to isolate the HAm product. Analytical data on the HAm products obtained by the processes of Examples 1 (invention) and 2 (prior art) are presented in Table I.
TABLE I______________________________________ Example 1 Example 2 Present Invention Control______________________________________Physical Appearance: free-flowing, white sticky, chalky solid white solid% Residual DEA: 5.3 9.0M.P. (°C.): 124 117______________________________________
EXAMPLE 3
In a manner similar to Example 1, a mixture of diethanolamine (DEA), 129 g, and potassium t-butoxide, 2.4 g, is placed in a 500-ml glass reactor and blanketed with nitrogen. After DMAd (106 g) is added and methanol distilled off, the reaction temperature is then increased to 108°-110° C. and held for 30 minutes to slowly convert the HAm to its molten state; the temperature is then lowered to 87° C. over a period of 25 minutes at which point a thick slurry state is obtained again. Samples are withdrawn from the reactor at each stage of this process, allowed to cool and solidify to produce product HAm. Experimental conditions and analytical data obtained from on-line sampling are presented in Table 2.
TABLE 2______________________________________Time Temp Operation/ % % AED/(min) (°C.) Comments HAm DEA HAm______________________________________ 0 84 Start DMAd addition30 79 Reaction mixture cloudy50 84 Formation of slurry, temp increased60 108 DMAd addition complete75 110 Thick slurry (A) 90.4 1.7 0.04390 109 Thick slurry (B) 90.8 1.6 0.044120 109 Thinner slurry (C) 90.0 1.9 0.056150 108 Cloudy, no slurry (D) 84.8 2.4 0.064180 108 Cloudy, no slurry (E), 83.1 3.1 0.085 temp lowered205 87 Slurry (F) 90.0 1.6 0.042______________________________________
HAm and AED/HAm ratios are determined by HPLC analyses. The data indicate that "slurry" conditions (samples A, B, C, and F) are conducive to high purity product (90+% HAm, <2% DEA, lower AED/HAm ratio), whereas "molten" conditions (samples D and E), representing the prior art, are conducive to low purity product (<85% HAm, >2% DEA, higher AED/HAm ratio). | A method of preparing solid hydroxyalkylamides by reacting carboxylic alkyl esters with alkanolamines at controlled reaction temperatures, removing the alcohol byproduct, controlling the temperature of the reaction mixture to form a slurry, maintaining the slurry and recovering the solid hydroxyalkylamides. | 2 |
[0001] This application is a continuation of co-pending U.S. application Ser. No. 13/610,400, filed Sep. 11, 2012, and issuing as U.S. Pat. No. 8,776,430 on Jul. 15, 2014, which was a continuation of U.S. application Ser. No. 12/585,803, filed on Sep. 24, 2009, which issued as U.S. Pat. No. 8,359,783 on Jan. 29, 2013, which claimed the priority of U.S. provisional application, Ser. No. 61/136,676, filed Sep. 24, 2008, the priority of which is hereby claimed.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to cage-type animal traps of the kind generally used outdoors for trapping small to medium sized animals without harming the trapped animal.
[0004] 2. Description of the Prior Art
[0005] Cage-type traps generally include a cage of metal wire mesh or the like with a door held open by a trigger mechanism until an animal is lured into the trap by suitable pre-inserted bait. After the animal enters the interior of the trap, the animal's weight pressed against the trigger actuates a trip which releases and closes the door, thereby trapping the animal inside the cage. A locking device serves to prevent the animal from opening the door from the inside.
[0006] To release the trapped animal, the locking device must be disengaged and the door must be opened. These steps generally require the use of two hands and involve close contact with the animal.
[0007] One solution to the problem of close contact with the trapped animal is set forth in copending application, U.S. Ser. No. 11/600,085, filed Nov. 16, 2006 (“the '085 application”), and published as U.S. Publ. No. US2008/0115405 on May 22, 2008, which is commonly owned by the assignee of the present application. The disclosure of the '085 application is hereby expressly incorporated by reference in its entirety as if fully set forth herein.
[0008] In the '085 application, the door at the front of a cage-type trap is held in the open position by an over-center set mechanism mounted on the roof of the trap. A cable assembly extends from the set mechanism to a point of connection on the door and a torsion spring, operatively connected to a locking yoke that engages the door, urges the door toward its closed position when the trap is triggered by an animal.
[0009] In addition to the cable assembly, the over-center set mechanism further includes a set mechanism platform attached to the roof with a transversely extending set lever bracket mounted thereon. A generally U-shaped set lever is pivotally coupled to both ends of the bracket so as to be movable through slightly less than 180 degrees from one side of the bracket nearest the rear of the trap in the set position to the other side of the bracket nearest the front of the trap in the tripped position. Generally centered on the set lever is a lever grip that can be grasped by a user when setting the trap to facilitate placement of the set lever in the set position.
[0010] The over-center set mechanism disclosed in the '085 application can be set using only one hand. Accordingly, opening the door of the trap to release a trapped animal requires only one hand, allowing the user to maintain a greater distance from the front of the trap than is possible with traps requiring two hands to place the trap door in the open position. Nonetheless, the user must grasp the lever grip and move it manually, necessitating that the user be immediately adjacent the trapped animal. When releasing a potentially dangerous animal, this may subject the user to an unacceptably close encounter when the animal exits the trap.
[0011] Similar concerns arise as well with other trap designs which require that the user physically open the trap to release the animal.
[0012] There is thus a need for a mechanism by which an over-center type cage trap such as that disclosed in the '085 application, or other style traps, may be remotely activated to open an escape door from a distance so that the user can easily release a trapped animal without subjecting the user to close contact with the trapped animal.
SUMMARY OF THE INVENTION
[0013] The present invention is therefore directed to a remotely activated cage door opening device for use with a cage-type animal trap that has a wire mesh animal enclosure made up of a base, a pair of opposed sidewalls emanating from the base, a rear wall secured to the sidewalls and the base, a roof secured to the tops of the sidewalls and the rear wall, and a front end provided with an animal access opening defined by the base, sidewalls, and roof.
[0014] According to a first embodiment, a single door is movably mounted at the front end and operates in an opened position to reveal the animal access opening and in a closed position to block the animal access opening. The door is held in its open position by an over-center set mechanism as disclosed in the '085 application which has a set handle mounted on the roof and a cable assembly that extends from the set handle to a point of connection on the door.
[0015] The remotely activated cage door opening device includes an infrared (IR) receiver and associated circuitry, a rotatable spool and cable, and a latch pawl at least partly enclosed within a housing. One end of the spool has a toothed sprocket that ratchets against the latch pawl and the other end of the spool engages a torsion/clock spring in the housing. The cable is wound on the spool with at least one free end thereof coupled to a fastening element that is secured to the set handle of the trap. The door opening device also includes an attachment element to secure the housing to the trap enclosure.
[0016] When the device is secured to the trap by the attachment element and the trap has been tripped so as to trap an animal inside, the cable is pulled off the spool against the tension of the torsion/clock spring until the fastening element can be clipped onto the set handle. The ratcheting of the sprocket against the pawl allows the extracted cable to remain extended without a retraction force.
[0017] The IR receiver includes a solenoid which is operative to release the latch pawl from the sprocket when actuated by a remote wireless IR transmitter. Once released, the cable is retracted onto the spool by the stored energy in the wound tension spring, automatically opening the door to which the cable is attached.
[0018] According to a second embodiment, the entry door is as already described in connection with the door of the first embodiment but, in addition thereto, a secondary escape door is provided at another location in the trap body, preferably at the rear end of the trap opposite the entry door at the front end. The secondary escape door operates independently from the entry door and is movable between closed and opened positions to either cover or uncover an escape opening formed in the side or end wall of the trap. A door release unit secures the secondary escape door in the closed position until activated, either by remote control or other release mechanism. Once activated, the escape door is free to move to the opened position at which time an animal inside the trap can escape through the escape opening while the entry door remains closed.
[0019] It is thus an object of the present invention to provide a remotely activated door-opening mechanism for a cage trap demonstrating mechanical and electronic simplicity for ease of opening the trap's door without requiring the user to have physical contact with the trap.
[0020] It is a further object of the present invention to provide a door-opening mechanism for a cage trap that is remotely controlled by a wireless IR transmitter to allow the user to maintain a safe distance from the trap when releasing a trapped animal.
[0021] It is another object of the present invention to provide a cage trap door-opening mechanism in accordance with the preceding objects and a first embodiment that can be retrofit onto existing cage traps equipped with an over-center set mechanism.
[0022] It is yet another object of the present invention to provide a door-opening mechanism for a cage trap in accordance with the preceding objects and the first embodiment that can be easily attached to and then removed from the cage trap as an accessory, allowing the same mechanism to be moved from one trap to another for opening the respective doors thereof.
[0023] It is still another object of the present invention to provide a door-opening mechanism for a cage trap in accordance with the preceding objects that is relatively simple in electronic design while providing robust mechanical operation to open the trap door.
[0024] It is a further object of the present invention to provide a cage trap in accordance with a second embodiment having a main entry door through which an animal enters the trap and a secondary escape door that operates independently of the entry door such that, once the animal has been trapped inside the cage, the user can remotely release the animal by triggering the opening of the secondary escape door while the entry door remains closed.
[0025] It is yet another object of the present invention to provide a cage trap in accordance with the preceding object in which opening of the secondary escape door is controlled by a door release unit that can be activated either using a remote control unit or with a mechanical time release.
[0026] Additional objects of the invention include, for example, the provision of a door-opening mechanism for a cage trap which is durable, reliable and user friendly, and which can be manufactured from readily available components and in a cost-effective manner.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Other objects, features and advantages of the present invention will be apparent to those skilled in the art upon a reading of this specification including the accompanying drawings. While intending to illustrate the invention, the drawings are not necessarily to scale.
[0028] FIG. 1 is a perspective view of a preferred embodiment of the present inventive door-opening mechanism as mounted on a cage trap in a tripped position with the door of the trap closed.
[0029] FIG. 2 is an exploded perspective view of the components of the door-opening mechanism shown in FIG. 1 .
[0030] FIG. 3 shows a left side view of the front end of the housing to illustrate the sliding clip for securing the housing of the door-opening mechanism to the trap roof at the rear of the trap enclosure as shown in FIG. 1 .
[0031] FIG. 4 shows an alternative embodiment to the clamp of FIG. 3 , in which the door-opening mechanism includes clips on both ends of the cable, one clip for securing the mechanism to the trap enclosure and the other clip for securing the cable to the door.
[0032] FIG. 5A shows a cage trap having a secondary escape door in accordance with a further embodiment of the door release mechanism of the present invention, the secondary escape door being shown in a closed position.
[0033] FIG. 5B shows a partial view of the cage trap of FIG. 5A with the secondary escape door being shown in an opened position.
[0034] FIG. 5C shows a user activating the trap of FIGS. 5A and 5B from a safe distance using a remote control unit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] In describing preferred embodiments of the present invention illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
[0036] As shown in FIGS. 1 and 2 , the remotely activated cage trap door-opening mechanism according to a first embodiment of the present invention is generally designated by reference numeral 10 and is mounted at the top rear of a cage trap as disclosed in the aforesaid '085 application. The door opening mechanism 10 includes a mechanical assembly, generally designated by reference numeral 12 , and an activating assembly, generally designated by reference numeral 14 . The activating assembly and portions of the mechanical assembly are contained within a housing 16 which is mounted to the trap 18 .
[0037] The mechanical assembly 12 includes a rotatable spool 20 , a toothed sprocket 22 , a latch pawl 24 , a torsion/clock spring and a cable 28 with a fastening element 30 . The toothed sprocket 22 is mounted on one end of the spool 20 so as to ratchet against the latch pawl 24 within the housing. The torsion/clock spring 26 is mounted on the opposite end of the spool 20 . The cable is wound on the spool 20 with the extendible end thereof coupled to the fastening element 30 . The fastening element 30 may be embodied as a clip, such as a carbineer style clamp, by which the extendible end of the cable 28 is secured to the set lever 40 of the trap 18 .
[0038] The mechanical assembly 12 also includes an attachment element 32 to secure the housing 16 to the trap 18 . This attachment element 32 may be embodied as a sliding clip element 34 (see FIG. 3 ), as a carbineer style clamp 33 (see FIG. 4 ), or as any other suitable clamp or fastening mechanism as would be understood by persons of ordinary skill in the art.
[0039] According to one preferred embodiment, the activating assembly 14 includes an IR receiver generally designated by reference numeral 50 and a remote IR transmitter 52 . The receiver 50 includes a circuit board 54 , a power source such as a battery 56 , and a solenoid 58 operative to release the latch pawl 24 from the sprocket 22 when actuated by the remote IR transmitter 52 . Alternatively, the receiver may be configured for RF communication with a remote RF transmitter.
[0040] To use the door-opening mechanism, the housing 16 is secured to the upper rear edge 44 of the trap enclosure 42 by the attachment element 32 . The housing 16 may be secured to the trap prior to use, i.e., prior to setting the trap, or may be attached to the trap after an animal has been trapped. If the housing 16 is secured to the trap prior to use, according to a preferred method of use, the extendible end of the cable 28 is not attached to the set lever 40 of the trap 18 until after the trap has been tripped and the animal is to be released.
[0041] The trap 18 is set by moving the set lever 40 toward the rear of the trap 13 in the manner described in the '085 application. When the trap 18 is tripped by an animal, the set lever 40 moves toward the front of the trap under the urging of the weight of the door 46 as conveyed through the trap cable assembly 48 . Once the door is closed, the animal is trapped inside.
[0042] To release the animal, the housing is secured to the upper rear edge 44 of the trap enclosure 42 , if not already secured thereto. The free end of the cable 28 is pulled out of the housing to extract the cable 28 from the spool 20 against the tension of the torsion/clock spring 26 until the fastening element 30 is positioned to be clipped onto the set lever 40 . The ratcheting of the sprocket 22 against the pawl 24 allows the extracted cable 28 to remain extended without a retraction force.
[0043] With the end of the cable 28 attached to the set lever, the user may withdraw a desired distance away from the trap. Once the user is at a safe distance, the user or another individual having the remotely located IR transmitter 52 , actuates the IR receiver 50 . Actuation of the IR receiver 50 activates the solenoid 58 which, in turn, releases the latch pawl 24 from the sprocket 22 . Once the pawl 24 is released, the spool 20 is free to spin and thereby retract the cable 28 onto the spool 20 by the stored energy in the wound tension spring 26 . The retraction of the cable 28 pulls the set lever 40 toward the rear of the trap to automatically open the door 46 .
[0044] To soften any abruptness in the rapid cable retraction, a rotary dampener 60 may be added to the mechanical assembly in a manner known to those skilled in the art.
[0045] As described herein, the cage trap door-opening mechanism is an independent accessory that can be easily attached to and then removed from any existing cage trap equipped with an over-center set mechanism to remotely open the door thereof.
[0046] Other mechanical assemblies suitable for the operation of the present invention could also be used as would be understood by persons of ordinary skill in the art. For example, the cable spool and cable could be operated by an electric motor or a hand-wound crank. Retraction of the cable could also be effected by a pneumatic cylinder.
[0047] Similarly, as alternatives to the IR transmitter and receiver, or to an RF transmitter and receiver, other remote means of conveying a signal and of receiving the signal by a receiver or comparable device on the activating assembly are also intended to be included within the present invention. The door-opening mechanism could also be mechanical or electrically timed. Activation of the door-opening mechanism could also be accomplished through the use of a wired remote or by a remote mechanical mechanism.
[0048] Any of the above-described assemblies for operation and activation of a remote door-opening mechanism may also be used in conjunction with a trap having a separate escape door such as that illustrated in FIGS. 5A and 5B and generally designated by reference numeral 62 , in accordance with a second embodiment of the present invention. The separate escape door 62 is preferably positioned at the opposite end of the trap relative to the entry door 46 . Since the entry door 46 of the trap shown in FIG. 1 is described herein as being at the trap front end, then the separate escape door 62 is preferably at the rear end of the trap. Alternatively, the separate escape door could be positioned on the side of the trap, preferably near the rear end. Wherever its location, the separate escape door 62 may be more simply designed than the entry door, requiring only a movable panel that can be positioned and held in a closed position, as shown in FIG. 5A , to cover an escape opening 64 , and then moved to an opened position to uncover the escape opening, as shown in FIG. 5B .
[0049] In the embodiment shown in FIGS. 5A and 5B , the escape door 62 is pivotally mounted to the end wall 66 of the trap by a hinge 68 positioned at the bottom of the escape opening 64 . When the trap is in a set condition for trapping an animal as shown in FIG. 5A , the escape door 62 is held vertically in a closed or secured position by a door release unit generally designated by reference numeral 70 .
[0050] The door release unit 70 , in the embodiment shown, includes a control assembly 72 mounted on the trap body, preferably on the roof 76 , and a catch 74 mounted on the escape door 62 so as to be adjacent the control assembly 72 when the escape door is in the closed position. Alternatively, the control assembly 72 may be mounted adjacent one side of the escape door with the catch then being placed on the escape door in generally horizontal alignment with the control assembly. With this alternative placement of the release unit, the escape door may be secured to the trap by a vertical hinge (not shown) positioned on the opposite side of the door so that the escape door is configured to swing between opened and closed positions while remaining in a vertical orientation.
[0051] The control assembly 72 includes a latching mechanism (not shown) for securing the catch 74 to keep the escape door in the closed or secured position until the control assembly 72 is activated. The latching mechanism can use mechanical, electrical, magnetic, or other means to keep the catch 74 engaged with the control assembly. When this engagement is released by the control assembly, the door and catch are allowed to pivot downwardly away from the control assembly to uncover the escape opening 64 .
[0052] According to one preferred embodiment, the door release unit 70 is battery powered and remotely activated by a user 78 using a remote control unit 80 as shown in FIG. 5C . Alternatively, the door release unit 70 can be designed to operate using a mechanical time release, such as that described in U.S. Pat. No. 3,638,346, by which a manually set timing device triggers the opening of the escape door after the manually set time period has elapsed. In conjunction with such a mechanical time release, the escape door may be spring loaded so as to be ready to swing open when the door release unit is triggered by the timer.
[0053] However configured, the present invention provides a door-opening mechanism that is easy to use and which, through the remote control activation capability, allows the user to maintain a safe distance from the trap when releasing a trapped animal.
[0054] It is to be understood that the present invention is not limited to the illustrated embodiments described herein. Modifications and variations of the above described embodiments of the present invention are possible as appreciated by those skilled in the art in light of the above teachings. | A remotely activated door-opening mechanism is provided for a cage trap having an animal enclosure, preferably a cage trap as disclosed in U.S. Publ. No. US 2008/0115405. The mechanism is mounted outside the enclosure of the trap and is preferably remotely activated by an IR or RF transmitter to open a door of the trap and release a trapped animal when the operator is at a safe distance away. The mechanism may also be manually set with a time delay and may be associated with either a main entry door to the trap or with a secondary escape door located at an opposite end of the trap. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to tanks designed to hold gas or volatile liquids, and more particularly, is designed to improve tanks which store pressurized gas, either in conjunction with a natural gas supply system, or an anaerobic wastewater treatment digester.
In the case of anaerobic digesters, gases, typically methane and carbon dioxide, are given off and collected to be used as the fuel for heating the sludge mixture. Traditional storage tanks employ a floating gas holder positioned above the sludge which collects the gas and provides a controllable downward force thereon, pressurizing the gas and making it immediately usable by the sludge heating equipment.
These tank facilities must meet environmental limitations concerning the discharge of gases into the atmosphere. Careful monitoring and control of the gases produced during the anaerobic process is essential, since the gases frequently are explosive when mixed with ambient atmospheric air. The conventional floating gas holder, while workable in theory, is subject to corrosion, freezing, tipping and gas leakages, all of which substantially interfere with its effective operation to properly control the gas within the tank.
Attempts have been made to solve the deficiencies of the common floating gas holder by providing the digester with a fixed outer cover and a flexible, pressurized gas retention membrane underneath. U.S. Pat. No. 4,060,175 to Rysgaard, discloses such a membrane connected to a vertically slidable stack equipped with pressure release and flame arrester system. A flowable granular ballast material placed upon the membrane near the tank wall serves as the pressure regulating mechanism.
In operation, the Rysgaard systems have proved to be impractical, largely due to the unwieldy nature of the ballast used to exert pressure on the membrane, as well as the inability of the flexible membrane to retain the ballast and simultaneously maintain a gas-proof seal.
Commonly-assigned U.S. Pat. No. 4,437,987 to Thornton, et al. discloses a digester cover with a fixed outer cover and a fixed center gas well, to which inner and outer flexible membranes are affixed. The inner membrane collects the digester gas. The cavity between the inner and outer membranes is filled with pressurized air as the gas pressure regulating means. The Thornton, et al. system has overcome most of the drawbacks of the Rysgaard and floating gas well designs, but the cost of constructing the fixed outer dome has rendered the system noncompetitive as compared to conventional floating gas holder designs.
The fixed cover and gas well assembly is necessary to provide the following features: a means of mounting pressure/vacuum release systems; a support means to prevent a deflated membrane from falling into the sludge or being impaled upon an internal projection such as a pipe; a means of introducing air between the membranes without penetrating either membrane; and the provision of access to the interior of the tank for periodic cleaning.
Thus, it is an object of the present invention to provide a digester gas collection system with a low-cost, yet structurally sound gas well support structure and a flotaing gas well with maintenance access means.
It is a further object of the present invention to provide a flexible membrane gas collection system which exerts minimal loading on the gas well support structure.
SUMMARY OF THE INVENTION
A gas collection and storage system including dual storage membranes and a supported gas well is provided for use in conjunction with a tank and is designed to prevent the transmission to the gas well support structure of excessive and potentially damaging stress loads exerted by stored gas.
More specifically, the present invention comprises a gas storage tank, preferably circular in shape and having a peripheral support wall. A rigid gas well support structure is provided. A gas well is floatably seated on the support structure and is provided with a downwardly depending concentric portion. A plurality of flexible support members such as cables emanate radially from the concentric portion, and are pivotally connected thereto. The free ends of the cables are pivotally secured to the tank wall.
Two flexible gas retention membranes are sealingly secured at one end to the downwardly extending concentric portion of the well at a location below that of the cable attachment points. The free ends of the membranes are sealingly secured to the tank wall.
When the tank is free of gas, the gas well rests on the support structure. As gas is introduced into the tank, and begins to exert pressure on the retention membrane, the resulting stress is transmitted via the cables to the tank wall. The cables are designed to have a length which, under pressurized conditions, permits free lateral movement of the gas well but limits its vertical movement. In this manner, stress loading on the gas well support structure is substantially reduced, allowing for cost effective reductions in gas well support structure configuration and materials.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and its many attendant objects and advantages will become better understood by reference to the following drawings, wherein:
FIG. 1 is a side elevation in partial section of a gas storage tank equipped with the gas collection system of the present invention;
FIG. 2 is a plan view of the gas well support structure framework of the tank shown in FIG. 1;
FIG. 3 is a detailed view of the gas well of the present invention;
FIG. 4 is a detailed view of the gas well shown in FIG. 1;
FIG. 5 is a detailed view of the top of the tank wall shown in FIG. 1;
FIG. 6 is a side elevation in partial section of an alternate embodiment of the present invention; and
FIG. 7 is a detailed side elevation in partial section of the gas well depicted in FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, wherein like reference characters designate identical or corresponding parts, an anaerobic digester tank for the treatment of wastewater is depicted, although the present invention may be employed in various types of tanks adapted to store specific gases or volatile liquids. Digester tank 10 is comprised of an annular wall 12 having a top 13 and a sloped floor 14 to facilitate the removal of settled waste solids, as well as the periodic draining of tank contents through conduit 16 for cleaning or maintenance. The position of conduit 16 may be varied to comport with industry practice. An inlet 18 is provided for the access of wastewater influent into tank 10. To be consistent with industry practice, additional inlets and outlets may be provided. A gas-impervious seal 20 is secured to the interior of tank wall 12 to provide protection for the variable volume of gas to be contained therein.
Tank 10 is provided with a gas well support structure 22, which in the preferred embodiment is dome-shaped, but may take other forms without betraying the spirit of the present invention. For purposes of cost reduction, the preferred structure 22 is not closed, but is essentially an open latticework of tubular segments 24 arranged in a pattern for efficient strength maximization. In the present invention, each segment 24 is fabricated of a material having properties similar to anodized aluminum or galvanized steel. The segments are assembled by any suitable means, such as bolting or welding.
Support structure 22 is also provided with a plurality of base plates 26 which are secured to the top 13 of wall 12 by anchor bolts 15. Selected segments 24 are adapted to lockingly engage base plates 26 at point 27 using conventional locking means.
Structure 22 is further provided with an access stairway 28 and railing 30 which leads to the central access aperture 32, circumscribed by rim 34 of structure 22.
Inserted into access aperture 32 is floating gas well 40, preferrably comprising a top plate 42 adequately overlapping rim 34, and a vertically depending, substantially cylindrical frame ring 44. If the top plate 42 is designed to not overlap rim 34, the gas well 40 may engage support structure 22 by means of a plurality of outwardly projecting support members (not shown). Frame ring 44 is secured to top plate 42 via `L`-bracket 46 or by welding. Top plate 42 is also provided with a detachable manhole cover 48, gasket 49 and access port 50, and at least one pressure/vacuum release valve 52 and gas takeoff 53. Railing 31 facilitates access to manhole cover 48.
In order to adequately adapt to variations in internal tank pressure, gas well 40 should be capable of relatively free lateral movement in any direction. This goal is achieved by the installation of a resilient support cushion 54 between the outer edge of the top plate 42 or equivalent structural member and rim 34. Cushion 54 may be secured either to top plate 42 or rim 34, and, once secured, protects both surfaces from potentially damaging abrasion.
Frame ring 44 is provided with an annular tension ring 45 to which is attached a plurality of radially positioned lugs 56, each having an aperture 58. Because of the large number of lugs and the relatively small diameter of the tension ring 44, the lugs 56 may be provided in two alternating lengths (not shown) to stagger their distance from frame ring 44. This facilitates the installation of cables 60 by allowing room to manipulate the mounting bolts 70. Lugs 56 and tension ring 45 are preferably located low enough on frame ring 44 to allow gas well 40 to rise vertically an acceptable distance without incurring potentially damaging contact between lugs 56 and rim 34. In practice, however, it has been observed that under normal operational conditions, when tank 10 is filled with pressurized gas, the vertical movement of gas well 40 is negligible.
A plurality of radially-positioned flexible support members 60 connect gas well 40 with tank wall 12. Support members may be chains, ropes, tie bars or other suitable equivalent, but are preferably comprised of steel cables, each having a gas well end 62 and a base end 64. Gas well end 62 is provided with an open clevis socket 66 and an eyelet 68 which is pivotally secured to mounting lug 56 by bolt or pin 70. The base end 64 of each cable 60 is also provided with an open clevis socket 66 and an eyelet 68 which is secured to anchor plate 26 at lug 72.
Frame ring 44 is also provided with an outwardly projecting annular flange 76, which serves as a mounting point for flexible outer air retention membrane 78. Any reinforced polymeric material which is gas-impervious and chemical resistant may be used to manufacture membrane 78. Membrane 78 is essentially donut-shaped, having a central aperture and inner and outer peripheral margins, 80 and 82, respectively. Each margin 80, 82 is provided with an annular bead 84 of rope-like material.
Membrane 78 is sealingly secured to gas well 40 in the following manner. The inner margin 80 is sandwiched between two resilient annular gaskets, designated as upper gasket 86 and lower gasket 88. Lower gasket 88 rests upon flange 76, and upper gasket 86 is covered by annular plate 90. A plurality of mounting bolts or studs 92 secure the assembly comprised of plate 90, gaskets 86, 88, membrane 78 and flange 76 in a sealingly secure fashion.
The outer margin 82 of membrane 78 is sealingly secured to the top 13 of wall 12 in a similar fashion, employing gaskets 94 and 96, annular plate 98, and anchor bolts or studs 100.
Gas well 40 is further provided with at least one air intake 102 for filling the pressure cavity 104. Air intakes 102 are routed through holes in top plate 42 and a port 106 in frame ring 44, the latter directly below flange 76, and may be connected to an external blower assembly (not shown).
Directly beneath air intake port 106, and at the lower edge of ring 44, a second annular flange 108 is secured. Inner gas storage membrane 110 may be mounted to flange 108 in a fashion similar to that described for membrane 78 and flange 76. To enable the two membranes to be installed or replaced separately, an annular `L`-bracket 112 may be secured to flange 108, which orients the supplemental membrane attachment 90° from that of membrane 78. As was described above, a pair of gaskets 86, 88, a separate annular clamping bar 114 and additional mounting bolts 116 will be employed. The outer margin 82 of membrane 110 is secured to wall 12 directly beneath membrane 78, being separated therefrom only by a sealing gasket 118.
In operation, when tank 10 is empty or has been relieved of evolved gas through takeoff 53, gas well 40 rests upon the rim 34 of support structure 22, being cushioned by pads 54. The cables 60 and membranes 78 and 110 are in a slackened condition. The combined weight of the gas well 40, cables 60 and membranes 78 and 110 are not sufficient to place undue strain upon support structure 22.
As gas is evolved, and/or as stored gas is fed into tank 10, cavity 104 will be pressurized to exert pressure upon the incoming gas. As the gas volume in the tank 10 increases, membrane 78 exerts tension upon cables 60. Until this tension equalizes throughout the tank, some cables may be subject to more stress than others. Thus, the gas well will shift laterally in response to this tension equalization process. Since the gas well 40 is not connected to the support structure, the stress loading experienced by the gas well is transmitted through the cables to wall 12, and not through structure 22.
Referring now to FIGS. 6 and 7, an alternate embodiment of the present invention is disclosed wherein the support structure consists of a centrally located vertical support pier 120. Pier 120 may be comprised of a tubular center section 122 to which are fixed three legs 124 in tripod arrangement. Legs 124 are secured to tank floor 14 by means of load bearing plates 126. Referring to FIG. 7, gas well 40 is floatably mounted to the top of center section 122. In similar fashion to pads 54, resilient pads 128 are positioned at the top of section 122 to prevent abrasion between top plates 42 and section 122. Also, pads 128 may be secured either to top plate 42 or section 122. Manhole cover 48 is located over access aperture 130 which in turn leads to the interior of center section 122.
Thus, the present invention discloses a gas collection and storage system comprised of a tank having a gas well support structure and a free-floating gas well suspended by cables so that the outwardly directed loads exerted by pressurized gas will be transmitted to the tank wall and not to the support structure.
Although a particular embodiment of this process has been described, it will be obvious to persons skilled in the art that changes and modifications might be made without departing from the invention in its broader aspects. | A floating as well for a covered gas storage tank is provided which rests on the tank cover until enough gas is introduced into the tank to inflate a gas collection membrane. The stress loads created by an increasing volume of stored gas on the gas collection membrane are diverted from the tank cover and through a series of cables attached to the floating gas well. The stress load is ultimately transmitted to the tank wall. | 5 |
The present invention relates to devices used for removing concrete from concrete mixing containers and a method for removing concrete from such containers.
Containers for mixing concrete have their most predominant application in what are commonly known as "cement trucks," used in the construction industry. Such concrete mixing containers are typically made from metal, such as steel, and are mounted for rotation on a truck. The containers are provided with internal mixing fins for mixing or agitating concrete contained therein during rotation thereof. Such agitation and mixing maintains the consistency of the concrete and inhibits the concrete from hardening within the container.
Premixing containers or drums are also known in the concrete industry and are used to premix concrete (which is typically a mixture of cement, sand, stone, water and hardening agents) with rotatable blades mounted for rotation within the container. The premixing containers are also typically made from steel and have similar volumes to the cement truck type containers. Smaller concrete containers are also typically made from steel and serve, for example, as a household appliance for use in paving driveways and other similar applications. These smaller containers are also mounted for rotation or provided with other means of agitating concrete placed therein.
It can be appreciated that there are significant problems and costs associated with maintaining such mixing containers. For example, if a container containing concrete sits for an extended period of time without mixing or agitating the concrete contained therein, the concrete will harden or "cure." Most of the hardened concrete will adhere to the inner walls of the mixing container. Hardening of concrete within the container can be inhibited to some extent if the concrete within the container is continuously agitated until the container is emptied and cleaned with water or solvent. It can be appreciated, however, that it is quite difficult to prevent concrete from ever hardening within the container. In actual use, it is almost inevitable that some appreciable amount of hardened concrete will accumulate within the mixing container during its useful life. This build-up must be removed, or the mixer loses its efficiency and load carrying capacity. In fact, in some cases, an inordinate accumulation of concrete within the mixing container results in the need to dispose of the container. Disposal is normally a last resort, as containers of this nature are relatively expensive.
While different methods of removing hardened concrete from concrete mixing containers are currently employed, none are cost effective or convenient. The predominant method of concrete removal is for an individual to use a jackhammer, sledge hammer, or hammer and chisel, to mechanically break apart the concrete and then manually remove the concrete fragments from the container. In the instance in which it is necessary to remove hardened concrete from a large mixing container, such as those mounted on a cement truck, it is necessary for the individual to climb into the container and to mechanically break the hardened concrete while inside. In the instances in which large amounts of concrete must be removed, explosives may be used as a preliminary step in loosening the concrete.
While removal of concrete can be accomplished in such fashion, there are a number of drawbacks associated with it. For example, because of the inherent strength of hardened concrete, mechanical breakage is quite difficult, and requires a substantial number of man-hours when a typical amount of concrete must be removed. Additionally, because a substantial amount of force must be applied to the hardened concrete in order to break it apart (by explosion or by use of an appropriate tool), substantial damage to the container may be caused. For example, puncture holes or cracks can be formed in the container, thereby rendering it unusable. At this point, the container must either be discarded or repaired at a substantial expense.
The patent literature, such as U.S. Pat. Nos. 5,003,144, 3,443,051, 3,430,021, 3,614,163, and 3,601,448 has proposed to utilize microwave radiation energy to assist cracking of concrete or rock material in an open environment, such as in a rock field or on pavement. However, use of microwave energy in such fashion has had limited success. More specifically, in order to weaken the chemical structure of concrete sufficiently to facilitate breakage, it is necessary for microwaves to penetrate deeply into the concrete, and be absorbed by water molecules throughout the thickness of the concrete. In an open environment, microwaves must be projected at highly localized portions of concrete to enable any cracking of the concrete to be accomplished. For example, U.S. Pat. No. 3,4430,021, discloses the need to employ a microwave waveguide to direct a microwave beam at a small area of a concrete surface for a sufficient amount of time to cause localized cracking. Even with the application of microwave energy in such tedious fashion, the transmission losses of the microwave energy remain significant. As a result, the effectiveness and efficiency of these types of devices are lacking and commercially deficient.
The present invention stems from extensive experimentation in which microwave radiation energy was used to remove hardened concrete from the closed environment of a metal container. The experimentation revealed that generation of microwave energy into a metal container is an extremely effective and efficient way to separate concrete from the inner walls of the container and to make the concrete sufficiently brittle that it will crack. Because the container is made from metal, it effectively contains not only the concrete but also the microwave radiation energy. The metal fabric of the container will continue to reflect microwaves tuned to the natural resonant frequency of water molecules until the microwaves impact upon, and are absorbed by, water molecules in the concrete. The absorbed energy is released as thermal energy, and, eventually, the water molecules are liberated from the concrete as water vapor.
It has been found that operation of the microwave energy generation device of the present invention for a relatively short period of time (e.g., on the order of an hour, depending on the power of microwave energy generated and the amount of concrete which is to be removed), will cause a sufficient amount of water removal from the concrete to cause the concrete to become brittle and crack. In many areas, the concrete actually separates from the inner walls of the container. As a result, the force required to break apart the concrete is significantly reduced and can be applied relatively easily and quickly, without the likelihood of container damage. For example, an ordinary hammer or pry bar can be used to dislodge the concrete from the container walls. Even more significantly, it has been found that after applying microwave energy for a greater period of time (e.g., after a few hours), the hardened concrete will actually weaken sufficiently that it breaks free from the container wall at areas at which the adhesion forces no longer can support the weight of the concrete. Moreover, it has been found that application of microwave radiation energy for an even longer period of time (e.g., several hours) will actually cause the cement to explode into fragments. More specifically, as water vapor is liberated from the concrete, significant amounts of the vapor accumulates in small pockets within the concrete. As more water vapor is generated, the vapor pressure within the pockets increases. This, combined with the weakened chemical structure of the concrete, eventually causes the hardened concrete to explode. Thus, removal of hardened concrete can be accomplished simply be emptying the concrete fragments from the metal container, without the need for additional mechanical breakage, or for personnel to enter the confines of the container.
In one test, approximately one-half (1/2) yard (one yard of concrete is one cubic yard by volume) was removed from a commercial cement truck container. Approximately one cubic foot of the material was found broken free of the walls, some of which exploded free. Most of the remaining concrete had visibly separated from the mixing fins and walls of the container, and was sufficiently brittle that a two pound hammer and a twelve inch pry bar could be used to leverage the concrete from the fins and walls. In most areas, the separation space between the concrete and the inner surfaces of the container was large enough to insert the pry bar. In other areas, simple hammering caused the concrete to shatter and fall.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an apparatus for mixing concrete that is adapted to facilitate removal of hardened concrete therefrom. The apparatus includes a metal container and a microwave energy generation device. The metal container is adapted to contain concrete to enable concrete placed therein to be mixed or agitated, the container having inner walls to which the concrete may adhere when the concrete hardens. The microwave energy generation device generates microwave radiation energy into the metal container and is capable of liberating water molecules from the concrete placed in the container so as to weaken the chemical structure of the concrete to thereby facilitate breakage of the hardened concrete and removal of the concrete from the container.
It is a further object of the present invention to provide a microwave energy generation device used to facilitate removal of concrete from a metal container utilized in mixing concrete. The microwave energy generation device includes a rigid base adapted to be mounted over an opening in the metal container, and at least one microwave energy generation source mounted on the base. The microwave energy generation source is capable of generating microwave radiation energy into the metal container to liberate water molecules from concrete in the metal container so as to weaken the chemical structure of the concrete. In addition, circuitry is operably connected with the at least one microwave energy generation source to enable the at least one microwave energy generation source to generate microwave energy.
In accordance with the principles of the present invention, it is a further object of the invention to provide a method for removing hardened concrete from a metal container. The method includes covering an opening in the metal container; generating microwave radiation energy into the metal container to liberate water molecules from the hardened concrete in the metal container so as to weaken the chemical structure of the concrete; uncovering the opening in the metal container; and removing the concrete from the metal container.
The preferred embodiment of the present invention will be better understood with reference to the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view, partly in section, showing a cement truck incorporating a metal mixing-container in accordance with the principles of the present invention.
FIG. 2 is a partial sectional view showing the interface between the microwave energy generation device and the metal container of the present invention.
FIG. 3 is a perspective view, with certain portions removed to better reveal others, of a shield structure in accordance with the principles of the present invention.
FIG. 4 is a perspective view showing a fan for drawing heated air with high water vapor content outwardly from the metal mixing-container in accordance with the principles of the present invention.
FIG. 5 is a plan view showing the main opening of the metal mixing-container of the present invention.
FIG. 6 is a plan view showing one side of the microwave energy generation device manufactured in accordance with the principles of the present invention.
FIG. 7 is a block diagram showing the system used to operate the apparatus of the present invention.
FIG. 8 is a perspective view showing another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
For convenience, the present invention is shown and described as it applies specifically to the type of metal mixing-container which is rotatably mounted on a cement truck. It is understood, however, that the present invention has applications in other types of metal mixing-containers for mixing concrete.
Shown generally in FIG. 1 is a cement truck 10, which incorporates a metallic mixing-container 12 in accordance with the principles of the present invention. The metal container 12 has a forward end 14 thereof rotatably mounted on a rotating apparatus 16 of the truck 10. A rearward portion 18 of the container 12 is supported by a truck bearing mount 20, which facilitates rotation of the container through the rotating torque of apparatus 16.
The container 12 is somewhat tubular, and the rearward portion 18 thereof has a major opening, generally indicated at 22. The opening 22 is defined by an annular flange 24. While the forward end 14 is typically provided with a similar opening, such opening is closed off by its interface with the rotating apparatus 16.
It can be appreciated that the container 12 is adapted to have a concrete slurry, dry mix ingredients, or suspension placed therein through opening 22. As the mixing-container 12 is rotated via the apparatus 16, internal mixing fins 26 mix or agitate the concrete. The mixing fins 26 are welded to the inner surface 28 of the container 12, and extend radially inwardly into the container 12 toward the axis of rotation "a" indicated by dashed lines.
In FIG. 2, the interface between the metal container 12 and a microwave energy generation device, generally indicated at 30, is shown. The microwave energy generation device 30 includes a rigid base 32, made from a metallic material such as aluminum, and has a plate-like, circular configuration. The base 32 functions as a cover that closes off the major opening 22 in the container.
The microwave energy generation device 30 also includes at least one microwave energy generation source mounted on the base. In FIG. 2, the microwave energy generation source is in the form of a plurality of magnetrons 34. The microwave energy generation device 30 also includes circuitry operably connected with the magnetrons 34, as is shown in FIG. 7, and which will be described in greater detail later.
The magnetrons 34 are commercially available, and each utilizes power in the 0.5-1 kilowatt range. Preferably, anywhere between fifteen to forty 1-kilowatt magnetrons are used, for a total of 15-40 kilowatts of power. It is understood that, as more power is used, the time required to evaporate a predetermined amount of water decreases. It is also understood that a single microwave energy generation source can be used. For example, it is possible to use a single magnetron of approximately 20 kilowatts. While a single magnetron with less power can also be used, the amount of time required to liberate the required amount of water will be longer than the time considered desirable for commercial application. It should also be noted that other types of microwave energy generation sources can be used, such as travelling wave tubes, klystrons, solid state amplifiers, and others. Preferably, the microwave generation source is tuned to a resonant frequency of the water molecule, which is approximately 2450 mHz. However, excitation of any molecular component, such that the bulk concrete rises in temperature beyond the boiling point of water, would provide an appropriate method for fracturing the concrete without using a water resonant frequency.
As shown in FIG. 2, each of the magnetrons 34 mounted on rigid base 32 includes an antenna 36 from which microwave energy is emitted, and a main housing 38. The housing 38 houses components used to generate the microwave energy. As shown, each of the main housings 38 are secured to an outer surface 40 of the rigid base 32 by appropriate fasteners 42. The antennas 36 extend through openings in the rigid base 32, past an inner surface 44 of the rigid base, and into the confines of the container. Omitted from FIG. 2, for clarity, are electrical cables and cooling fans for the magnetrons.
The annular flange 24 of container 12 engages an annular peripheral surface 46 of the rigid base 32, when the base 32 is mounted over the opening in the container 12. Fasteners 48 extend through the flange 24 and through openings 45 in the base 32 at circumferentially spaced locations to secure the base 32 to the container 12. Disposed between the flange 24 and annular surface 46 is an annular sealant 50. The sealant 50 is preferably in the form of a metal gasket, or a metallic resin. In addition to, or instead of, sealant 50, an exterior sealant 52 can be provided. Shown in FIG. 2, sealant 52 is in the form of metallic tape at the juncture between flange 24 and rigid base 32. The provision of such sealants is desirable in order to prevent leakage of microwave radiation into the environment.
During one seventeen hour test the microwave leak rate was measured at the interface of the annular flange 24 with the annular peripheral surface 46 of the rigid base 32. For sealant 52, metallic tape was used. C-shaped clamps were used as fasteners to peripherally secure the rigid base 32 to the annular flange 24. The measured leak rate was less than 1 milli-watt per centimeter squared (1 mw/cm 2 ).
Also provided between the container flange 24 and the annular surface 46 of the base, are contact sensors 56 mounted at circumferentially spaced positions on annular surface 46. The contact sensors 56 are connected with the circuitry shown in FIG. 7, and are operable to detect whether the annular surface 46 is in proper circumferential engagement with the annular flange 24. The contact sensors 56 serve as a precautionary measure, to ensure that microwave energy does not leak into the environment.
As also shown in FIG. 2, handles 58 are provided to enable a user to easily place the microwave energy generation device 30 over the opening in the container 12. In this regard, it is preferable for fasteners 48 to be captive bolts, which remain with the rigid base 32 at all times, and which can be easily aligned with the openings in flange 24.
Shown in FIG. 3 is a protective shield 60 manufactured in accordance with the principles of the present invention. The shield 60 is omitted from FIG. 2 for the sake of convenience. It is preferable for the protective shield 60 to be mounted on the inner surface 44 of the rigid base. The protective shield 60 has a protective wall 62 mounted directly over the antenna 36 in order to reduce the likelihood of exploding concrete fragments from impacting the antenna 36. The protective shield 60 is formed from a metallic material, and also functions to provide an impedance match for the antenna to free space. The shield 60 functions also to disperse the microwave energy through opening 66, after at least a portion of the microwaves are reflected within the confines of the shield 60. Such dispersion of microwaves is desirable because it reduces the time in which they will find and be absorbed by water molecules in concrete located in corners and crevices within the container.
It can be appreciated that providing a microwave energy generation device with a plate-like base is a preferred construction. The are other constructions which are also advantageous. For example, the microwave energy generation device may include an encasing mounting structure having an opening. Such an encasing mounting structure may have, for example, a cylindrical or box-like configuration. A cylindrical mounting structure would include a sleeve portion, one closed-off end, and one opened end mounted over the container 12 opening. The magnetrons would then be mounted on the exterior of the cylindrical encasing, with the antennas projecting inwardly into the confines of the encased area. By providing such a configuration, more mounting surface area is provided so that more magnetrons can be used. In other words, since the surface area of an encasing structure is larger than a plate-like base, more magnetrons can be mounted, thereby enabling more microwave energy to be generated. This expedites the liberation of water molecules from concrete.
In another configuration, as shown in FIG. 8, the microwave generation device includes a cover 200 for the container opening. While the cover may be similar to rigid base 32, it will not have any magnetrons mounted thereon. Rather, the cover 200 will be provided with one or more large openings 202 (only one opening being shown in the embodiment of FIG. 8) therethrough, each for receiving a metallic flexible tube 204. For example, the tube may be made from a corrugated aluminum, and have a diameter of approximately two to four feet. A microwave energy generation source 206, such as a plurality of magnetrons, is provided remotely from the cover. The microwave energy generation device may also include a mobile box 212 or enclosure into which the microwave energy is generated by the microwave energy generation source. In any event, the microwave energy is guided from the remote generation source by the metallic flexible tube 204 into the confines of the container. The tube is peripherally sealed at both ends 208 and 210 so that microwave energy cannot escape into the environment. This configuration is advantageous because no magnetrons are mounted on the cover, and as a result, the weight of the unit which is mounted over the container opening is greatly reduced. In addition, the circuitry and electrical cables that are connected with each magnetron (or other microwave generation source) can be harnessed more neatly. As a result, the apparatus can be made more user friendly.
FIG. 4 illustrates a ventilation device generally indicated at 70. The ventilation device is also shown in FIG. 1 mounted on the container 12. The ventilation device includes a fan 72 and a rigid metal plate 74. The plate 74 is secured over an opening in the side of the container 12 by appropriate fasteners 76. A sealant similar to the sealant 50 and/or 52 shown in FIG. 2 is used between the outer surface of the container about the side opening and the periphery of plate 74. Ventilation holes 78 extend through the plate 74, and enable the fan 72 to aspirate water vapor from the container as water is liberated from the hardened concrete by the microwave energy generation device. The plate 74 may be mounted over an opening within the container 12 which is normally provided to enable individuals cleaning the container 12 to climb into the container 12. When the container 12 is used to mix concrete, a plate similar to plate 74, but without ventilation holes, covers the side opening in the container.
It is preferable for vent holes 78 in the plate 74 to be sufficiently small, so that microwaves are not permitted to escape therethrough. For example, it is preferred that such openings be less than 1/4" in diameter for a microwave frequency of 2450 mHz, since microwaves of this frequency have a wavelength of sufficient length, that they will not be permitted to traverse holes of this size.
Contact sensors 75 are preferably provided at spaced locations between the peripheral interface of the inner surface of the plate 74 and the exterior surface of the container 12. The contact sensors 75 are connected with the circuitry shown in FIG. 7, and are operable to provide an appropriate indication when proper peripheral contact between the plate 74 and the exterior surface of container 12 is not obtained. The contact sensors 75 are provided to warn a user of potential microwave leakage between the plate 74 and container 12.
FIG. 5 is a plan view showing the inner confines of container 12 as seen through opening 22. As shown, the peripheral flange 24 is provided with a plurality of openings 80, which serve to receive the fasteners 48 shown in FIG. 2. As can also be appreciated from FIG. 5, the fins 26 extend radially inwardly towards the axis of rotation of the container, and terminate a predetermined distance "r" therefrom. This distance "r" is shown by dashed lines in FIG. 5, and represents the radius of a circle generally defined by the inner edges of fins 26. The dashed line "D" represents the diameter of this circle.
FIG. 6 is a plan view of the microwave energy generating device 30 showing outer surface 40, and main housings 38. Not shown are wiring cables electrically connecting the magnetrons with appropriate circuitry, and forced air cooling fans for cooling the magnetrons. The antennas 36 of each of the magnetrons 34 are represented by circular dashed lines in FIG. 6. As also shown in FIGURE 6, vent holes 84 are provided at spaced locations through the rigid base 32. These vent holes permit outside air to enter the confines of the container 12 as air with high water vapor content is exhausted through vent holes 78 in the plate 74. The vent holes 84 provide cross-ventilation through the container and expedite the rate at which water molecules are forced from the container by fan 72. It is preferable for vent holes 84 in the rigid plate 32 to be sufficiently small so that microwaves are not permitted to escape therethrough. For example, it is preferred for such openings to be less than 1/4" in diameter, as described hereinbefore with respect to openings 78 in plate 74.
As can also be discerned from FIG. 6, it is preferable for the majority of the magnetrons 34 to be concentrated towards the center of the rigid base 32, so that the antennas 36 are disposed within radius "r" from the center of the base. As noted hereinbefore, the circle formed by the inner edges of fins 26 defines radius "r" as shown in FIG. 5 The positioning of magnetrons 34 in this fashion decreases the time required for dispersion of microwaves towards the rearward portion of the container to facilitate liberation of water molecules from concrete thereat.
Shown in FIG. 7 is the circuitry forming part of the microwave energy generation device of the present invention. The circuitry includes a 240 VAC, 60 Hz voltage supply 90. The voltage supply 90 provides power for the entire apparatus, including the ventilation fan 72, high voltage/filament transformer 92, magnetrons 34, contact sensors 56, contact sensors 75, a fan 94 for cooling the transformer 92, and a fan 93 for cooling the magnetrons. Thermal cutouts 95 are used to protect the magnetrons and transformers. The circuitry also includes a capacitor 96 and diode 98. The diode, capacitor, and high voltage transformer function to provide electrical energy to the magnetrons 34, which convert the electrical energy to microwave energy. An on/off switch 102 is connected with a relay 104, and controls the operation of the microwave energy generation device 30. Indicator lights 106 are provided to indicate the proper functioning and/or status of the magnetrons 34, transformers 92, contact sensors 56, and contact sensor 75. For example, such indicator lights 106 might indicate whether power is being provided to each magnetron, and whether each of the contact sensors is making proper contact with the respective surface which it is to contact. It can also be appreciated that while only one on/off switch 102 may be provided, an independent switch may be provided for each magnetron. This may be beneficial, for example, when the same microwave energy generation device of the present invention is to be sequentially used in conjunction with many different containers of different sizes. With a larger sized container, it may be preferable to utilize more microwave radiation energy than with a smaller container.
With respect to the manner in which the microwave energy generation device is secured to the container, fasteners other than the bolts disclosed can be used. For example, the aforementioned C-shaped clamps may be used to clamp the peripheral outer portion of the rigid base 32 to the flange 24. Use of this type of clamp may facilitate the ability to adapt the microwave energy generation device to containers having flanges 24 of different diameters.
While premixing-containers typically have a major opening that is rectangular in shape, and which is generally larger that the opening in a container for a cement truck, the microwave generation device can be easily adapted by customizing the size and shape of the rigid base according to the size and shape of the opening over which it is to be mounted. The same holds true where the microwave generation device is to be used together with a smaller mixing-container.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not limiting in character. It is to be understood that the preferred embodiment has been shown and described and that all changes and modifications that come within the spirit and scope of the appended claims are to be protected. | An apparatus for mixing concrete adapted to facilitate removal of hardened concrete therefrom includes a metal container and a microwave energy generation device. The metal container is adapted to contain concrete and to enable concrete placed therein to be mixed or agitated, the container having inner walls to which the concrete may adhere when the concrete hardens. The microwave energy generation device generates microwave radiation energy into the metal container and is capable of liberating water molecules from the concrete placed in the container so as to weaken the chemical structure of the concrete to thereby facilitate breakage of the hardened concrete and removal of the concrete from the container. | 7 |
FIELD OF THE INVENTION
The present invention relates generally to composite materials containing high strength fibers in a matrix of a refractory carbide, boride or nitride, and more particularly to a rapid low-cost process for fabricating carbon fiber-ceramic matrix composites.
BACKGROUND OF THE INVENTION
Ceramic matrix composites (CMCS) are a class of structural materials for service at very high temperatures that have a variety of applications in the aerospace, aircraft propulsion, and power generation industries. Among these applications are rocket nozzles, turbine engine components, and heat exchangers.
Processes for making CMCs start with a preform of high strength fibers that retain their strength at high temperatures (for example carbon, a metal carbide, or a metal oxide). The preform may be prepared by a variety of processes similar to those used in the textile industry that either directly yield useful shapes or produce material, such as woven fabric, that may be subsequently shaped.
The fiber preform is consolidated by emplacing therein a matrix of ceramic material by one of several methods such as chemical vapor infiltration (CVI), gas phase reaction bonding, liquid phase reaction bonding, or slurry infiltration followed by hot pressing.
In the CVI process, illustrated by U.S. Pat. No. 5,079,039 to Heraud et. al., a reactive gas or mixture of gases simultaneously infiltrates the preform and pyrolyzes to form a ceramic matrix. CVI requires sophisticated and expensive equipment and, due to the necessity for operating under conditions where the deposition rate is low, is a slow and inefficient process when used as the sole process to fabricate CMCs.
The gas phase reaction bonding process has been developed primarily for silicon nitride matrix CMCs, where a green body made with silicon powder is nitrided with nitrogen gas. This process is illustrated by U.S. Pat. No. 5,510,303 to Kameda et al., which discloses a CMC material manufactured by forming a matrix containing reaction sintered silicon carbide as the primary component and nitriding the free metal silicon produced in the sintering process to convert it to silicon nitride. Gas phase reaction bonding has been developed only for silicon nitride and silicon carbide matrices.
Liquid phase reaction bonding has been used primarily for the production of silicon carbide matrix composites by infiltrating a preform containing carbon particles with liquid silicon. After reaction, the matrix consists of SiC and usually some free silicon. This process is illustrated by U.S. Pat. No. 5,552,352 to Brun et al., which discloses a composite fabricated from coated reinforcement fibers admixed with a carbonaceous material which is infiltrated with molten silicon. Liquid phase reaction bonding has been developed only for silicon carbide and silicon matrices.
In the slurry infiltration process, typically a tow is passed through a slurry containing matrix material, wound onto a drum, dried, laid up in the desired configuration, and hot pressed, as illustrated by U.S. Pat. No. 5,407,734 to Singh et al. Processes that use slurry infiltration followed by hot pressing require equipment operating at high pressures and temperatures in excess of 1800° C. to 2000° C.
Other methods of preparation involving fluid precursors have been suggested which involve the use of oxygen-free organometallic precursors. In general, however, the precursor materials employed are extremely air and moisture sensitive and require expensive inert environment fabrication.
In addition to the basic techniques for fabricating CMCs as summarized above, various additional processing steps can be integrated into the fabrication process to enhance various properties. The use of such additional steps obviously depend upon the intended use of the final CMC product. One such well-known step is the use of an interface coating to enhance the mechanical properties of a CMC, as exemplified by the teaching in U.S. Pat. No. 4,752,503 to Thebault. Such a coating consists of carbon or boron nitride applied by a CVI process. Other techniques are disclosed in U.S. Pat. No. 5,110,771 to Carpenter et al., U.S. Pat. No. 5,455,106 to Steffier, and U.S. Pat. No. 5,422,319 to Stempin et al.
U.S. Pat. No. 4,576,836 to Colmet et al. discloses a process for making oxide matrix CMCs by vapor phase in-situ hydrolysis of halide vapor, and includes a preliminary rigidization step of repeated liquid phase impregnation with a hydroxide, alkoxide, or organometallic, with intermediate drying/calcination.
One potentially low-cost fabrication route for carbide matrix CMCs is infiltration of a porous carbonaceous preform with a liquid containing a compound of a carbide-forming metal in solution or suspension and then heat treating the infiltrated body to form metal carbide in the interstices of the preform. The application of this method to form two-phase carbon-metal carbide bodies from porous monolithic graphite has been known and practiced for many years, as illustrated by U.S. Pat. No. 3,432,336 to Langrod et al. Other processes directed to the production of metallic carbide composites are described in U.S. Pat. No. 4,576,836, to Colmet et al., U.S. Pat. No. 4,196,230 to Gibson et al, and U.S. Pat. No. 5,759,620 to Wilson et al.
All the fabrication processes and additional steps summarized above require specialized equipment, long processing times, complex processing steps, high processing temperatures, and, in some cases, high processing pressures. They also are applicable with only a limited number of matrix and reinforcement compositions. These and other factors contribute to the high cost of CMCs, which in turn has limited their commercial acceptance.
Therefore, what is needed is a process for fabricating ceramic matrix composites that has advantages of lower cost, greater simplicity, shorter production times, and utilization for a wider range of matrix compounds.
SUMMARY OF THE INVENTION
This invention is an improved process for producing low-cost CMCs by the steps of fluid infiltration followed by pyrolysis. The process generally includes three simple process steps that may be carried out directly after one another without any intermediate steps. First, a fiber preform is infiltrated with a metalloid or metal-containing compound together with other constituents as detailed below. Next, the infiltrated preform is given repeated cycles of infiltration and low temperature heat treatment to evaporate the fluid vehicle or solvent, if used, and to convert the infused compound to an oxide matrix. Finally, after several infiltration-drying cycles, the preform is given a high temperature heat treatment at an appropriate temperature and in an appropriate atmosphere to convert the infused metal-containing compound in the matrix to metal carbide, boride or nitride. Repeated cycles of infiltration, drying, and high temperature conversion may be used to increase the matrix density. Further increases in matrix density may be achieved by additional CVI treatment.
DETAILED DESCRIPTION OF THE INVENTION
As noted above, this invention is a simple process for producing ceramic matrix composites. By “ceramic matrix composite” we mean a fibrous preform infiltrated with a single, binary, ternary, or complex non-oxide compound or mixture of compounds which is produced in situ.
In general, the procedure encompasses the steps of first infusing a fluid containing a metallic or metalloid compound one or more times into a fibrous preform. Second, the thus-infused preform is given repeated cycles of infiltration and low temperature heat treatment to evaporate the fluid vehicle and convert the infused metal-containing compound to an oxide matrix. Finally, the infused preform is then pyrolyzed, with or without additional infiltration steps, in an appropriate reduced pressure or inert atmosphere to convert the oxide matrix to a carbide, boride or nitride matrix, which together with the fibrous preform then constitutes the desired ceramic (matrix) composite. If desired, one infiltration step can be accomplished so to coat the fibers or the fibrous preform prior to application or infiltration of additional or other matrix precursor material. It is understood that the invention can be preferably and fully accomplished by practicing each of these process steps directly after one another, without the need for any intermediate steps, e.g., separation, hydration, conversion, reaction, or the like.
The fibrous preform used in this present invention is preferably made from carbon fibers, although any continuous high temperature fiber is within the scope of the invention. The fiber preform is preferably highly porous and has a low fiber volume. It is formed by methods known in the art such as, for example, air-laying, braiding, or weaving. Preform mats typically have a thickness of about 0.5 mm and about 10 mm.
The carbon or other high-temperature fibers, when used singly or as part of the preform, typically have a diameter as small as about 5 μm and as large as about 200 μm, though they may have diameters smaller or larger than these dimensions. Fiber lengths can range from about 1 mm to the maximum dimension of the preform. Although a wide variety of carbon fibers is contemplated for use in the present invention, HM carbon fibers, manufactured by Hercules, Inc. and having a diameter of about 8 μm, are preferred. Silicon carbide fibers, more preferably NICALON silicon carbide fibers, manufactured by Dow Corning and having a diameter of about 10 μm, are preferred for use in composites having silicon carbide matrices. Silicon carbide fibers may also be used in other matrices without departing from the scope of the invention.
This invention desirably employs ceramic matrix phase precursor materials that are neither extremely air- nor moisture-sensitive. For example, the precursor impregnation step can potentially be performed in the presence of water. The precursor material may be an oxide, or other pyrolyzeable or reactive compound, of the metal or metalloid constituents of the non-oxide refractories sought. For instance, it may be an alkoxide or salt, such as an isopropoxide, butoxide, acetate, nitrate, or dichloride oxide; a colloidal dispersion of an oxide, such as a nitrate-, chloride-, or acetate-stabilized aqueous sol or colloidal suspension; or a low melting point compound for melt-infiltration, such as an ethoxide or pentanedionate. It also may be an inorganic or organic metalloid-containing compound. It is understood that these and other various precursor materials may be used singly or in multiple combinations and be within the scope of the present invention if the precursor composition contains sufficient combined carbon.
Any metal or metalloid that suitably forms a refractory compound is within the scope of the present invention and is designated as M in the following description. Preferably, M is silicon or like metalloid or a member of Group IVB, VB, VIB or VIIB of the periodic table of elements. More preferably, M is silicon, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, or manganese. Most preferably, M is silicon, zirconium, hafnium, titanium, or tantalum.
For conversion to a carbide or nitride matrix, carbon may be added to the original infiltrant if the metal compound does not contain sufficient combined carbon for the high temperature reaction step, as calculated from the reaction stochiometry and elemental analysis of the starting materials, allowing for any loss of carbon as volatiles evolved during the pyrolysis step. The carbon may be in the form of dispersed finely divided carbon-containing powder or carbon powder, such as carbon black, or as a miscible carbon-rich liquid, such as a phenolic resin, a furfuryl alcohol-based resin, or a sugar.
For conversion to a boride matrix, boron may be added in the form of dispersed finely divided boron-containing or boron powder or as a solution of boric acid in water or an alcohol such as methanol, together with finely divided carbon powder, such as carbon black.
For conversion to a carbide or boride matrix, the high temperature conversion step generally may be carried out at a temperature of about 1400° C. or higher in an inert atmosphere or, preferably, in a vacuum. A preferred temperature range is between about 1400° C. and about 1800° C.; more preferred is between about 1400° C. and about 1600° C. Generally, if a vacuum is used, a vacuum level of less than about 1 torr is within the scope of the present invention; a vacuum level of less than about 10 −3 torr is preferred. If an inert atmosphere is used, the total impurity level should be less than about 0.1%; an impurity level of less than about 0.001% is preferred.
For conversion to a nitride matrix, the high temperature conversion step is carried out at a temperature between about 1300° C. and about 1700° C. in desirably an atmosphere of nitrogen or ammonia and possibly containing carbon monoxide. A preferred temperature range is between about 1400° C. and about 1500° C.
A key feature of the present invention is that the large negative free energy of formation of carbon monoxide or boric oxide at high temperature, when combined with the large negative free energies of formation of the desired non-oxide refractories, are such that non-oxide refractories may be formed under conditions where reduction of the oxide using carbon alone to metal otherwise could not be achieved. This principle may be applied to similar systems where the non-oxide product has a sufficiently negative free energy of formation.
For the production of carbides, the overall chemical equation for this variation of the inventive process may generally be written
MO 2 +3C→MC+3CO.
Even at temperatures in the neighborhood 1500° C., the carbon monoxide partial pressure is sufficient that this reaction may occur if the carbon monoxide is removed, for example by a stream of inert gas or in a vacuum chamber.
In addition to the precursor materials recited above, the metalloid oxide or metal oxide and carbon may be directly incorporated through fluid impregnation using metalloid oxide or metal oxide sols mixed with carbon black. The metals or metalloids may also be present in the form of alkoxides or salts of organic acids, for which either melt impregnation or solution impregnation may be appropriate. For organic materials containing oxygen, it is believed that the metallic oxide forms an intermediate product.
The final volume of the non-oxide refractory ceramic composite is less than the volume of the preform precursors. A single process cycle can produce a fiber coating but densification of a fiber-reinforced body requires multiple process cycles. Most of the volume reduction occurs at lower temperatures than required for the carbon reduction step. It is advantageous to carry out multiple impregnation, intermediate temperature thermal treatment cycles before carrying out the high temperature conversion step.
The method can be employed to produce boride or nitride as well as carbide products. For zirconium and hafnium, if elemental boron is incorporated with the oxide and carbon, the overall reaction
MO 2 +2B+2C→MB 2 +2CO
is a more favorable reaction than the carbide formation reaction at all temperatures. Below 1100° C. the formation of boric oxide is predicted, but above 1200° C. this is reduced by carbon, allowing the formation of additional boride. A preferred temperature range is between 1400° C. and 1800° C.; more preferred is between 1500° C. and 1600° C.
It is possible to use boric oxide rather than the element as the boron source. This proceeds by the overall reaction
MO 2 +B 2 O 3 +5C→MB 2 +5CO.
Borides may also be prepared using boron as the reducing agent in place of carbon, according to the overall reaction
3MO 2 +10B→3 MB 2 +2B 2 O 3
This reaction is thermodynamically favored at lower temperatures than reactions using carbon as the reducing agent. Excess B 2 O 3 may be removed by evaporation or by heating in steam to remove the B 2 O 3 as volatile boric acid.
If the reaction of the metal oxide and carbon is carried out in the presence of nitrogen, it is possible to form the nitride. The overall reaction is
MO 2 +½N 2 +2C→MN+2CO.
For this reaction the temperature must be carefully controlled, e.g., below about 1700° C., because at higher temperatures carbon can react with the nitride to form the carbide and release nitrogen.
The method characterized by the above reactions, for example, can be illustrated by substitution of zirconium, hafnium and silicon as the metal or metalloid (M), but it can be extended to other candidate fiber coating or matrix materials for which the combined thermodynamic stability of the non-oxide ceramic product and the coproduct carbon monoxide is sufficient to balance the thermodynamic stability of the oxide of the metal or metalloid component. The formation of other than carbide non-oxide ceramics further requires that the non-metal constituent form a more stable combination with the metal than carbon does.
Reference will now be made in detail to the present invention by means of examples.
EXAMPLE 1
This example shows the production of a zirconium carbide matrix composite using zirconium acetate as the metal compound for solution infiltration into the fibrous preform.
A braided carbon fiber preform 1.6 mm thick containing 56% by volume HM fiber was vacuum-infiltrated at room temperature with zirconium acetate solution in acetic acid containing 15-16% zirconium to which 6% by weight carbon black had been added. After each infiltration the coupon was dried at 60° C. for a minimum of 2 hours to remove the solvent and heated in argon to 500° C. for 2 hours. Fifteen infiltration-heat treatment cycles were made. Heat treatments at 1400° C. for 2 hours in an atmosphere of argon were made after the 11th and 15th infiltration cycles. The weight of the final product was 262% that of the original carbon fiber preform. Micrographic examination showed that matrix material had penetrated throughout the preform and into the fiber bundles. Analysis of selected areas by energy dispersive x-ray spectrometry (EDX) and wavelength dispersive spectrometry (WDS) showed that the matrix material contained zirconium, carbon, and oxygen with the carbon peaks 1.5 to 5 times larger that the oxygen peaks.
EXAMPLE 2
This example shows the production of a zirconium carbide matrix composite using pentanedionate for melt-infiltration of the fibrous preform.
A braided carbon fiber preform 1.6 mm thick containing 56% by volume HM fiber was melt-infiltrated by placing the preform specimen in an aluminum foil pan and completely covering it with zirconium pentanedionate powder. The pan was placed in a tube furnace, the furnace was evacuated, and the temperature was raised to 190° C. The pressure was raised to 1 atmosphere and the specimen was furnace cooled to room temperature. The specimen was heat treated in argon at 500° C. for 2 hours. Ten melt infiltration-heat treatment cycles were made. The weight of the final product was 235% that of the original carbon fiber preform. Micrographic examination showed that matrix material had penetrated throughout the preform and into the fiber bundles. Analysis of selected areas by EDX and WDS showed that the matrix material consisted of zirconium, carbon, and oxygen with the carbon peaks 0.7 to 1.7 times larger than the oxygen peaks.
EXAMPLE 3
This example shows the production of a hafnium carbide matrix composite using an acetate-stabilized acetate sol containing carbon black for slurry-infiltration of the fibrous preform.
A braided carbon fiber preform 1.6 mm thick containing 56% by volume HM fiber was vacuum-infiltrated at room temperature with a hafnium oxide sol consisting of 20% hafnium oxide in a chloride-stabilized aqueous suspension to which 3.4% by weight carbon black had been added. After each infiltration the coupon was dried at 60° C. for a minimum of 2 hours to remove the solvent. Nine infiltration-drying cycles were made. The specimen was heated in argon to 500° C. for 2 hours after the seventh cycle and at 1500° C. for 2 hours in vacuum after the ninth cycle. The weight of the final product was 231% that of the original carbon fiber preform. X-ray diffraction analysis of the matrix material made on a companion specimen heat treated at 1400° C. for 4 hours in vacuum showed that it was composed of hafnium carbide with a minor amount of hafnium oxide, with the strongest hafnium carbide peaks 6.5 times larger than the strongest hafnium oxide peaks.
EXAMPLE 4
This example shows the production of a hafnium boride matrix composite using an acetate-stabilized acetate hafnium oxide sol containing boron powder for slurry-infiltration of the fibrous preform.
A braided carbon fiber preform 1.6 mm thick containing 56% by volume HM fiber was vacuum-infiltrated at room temperature with a hafnium oxide sol consisting of 20% hafnium oxide in a chloride-stabilized aqueous suspension to which 3.3% by weight boron powder had been added. The preform was repeatedly vacuum-infiltrated at room temperature and dried at 200° C. in air between infiltrations, then heated in vacuum at 1400° C. for 4 hours after the final infiltration-drying cycle. X-ray diffraction analysis of the matrix material made on a companion specimen heat treated at 1400° C. for 4 hours in vacuum showed that it was composed of hafnium boride with a minor amount of hafnium oxide, with the strongest hafnium carbide peaks 6.4 times larger than the strongest hafnium oxide peaks.
EXAMPLE 5
This example shows the production of a hafnium nitride matrix composite using an acetate-stabilized acetate hafnium oxide sol containing carbon black heated in nitrogen.
A braided carbon fiber preform 1.6 mm thick containing 56% by volume HM fiber was vacuum-infiltrated at room temperature with a hafnium oxide sol consisting of 20% hafnium oxide in a chloride-stabilized aqueous suspension to which 2.5% by weight carbon black had been added. The preform was repeatedly vacuum infiltrated at room temperature and dried at 200° C. in air between infiltrations, then heated in nitrogen at 1400° C. for 4 hours after the final infiltration-drying cycle. X-ray diffraction analysis of the matrix material made on a companion sample heat treated at 1400° C. for 4 hours in nitrogen showed that it was composed mainly of hafnium nitride and hafnium oxynitride with a minor amount of hafnium oxide. The strongest hafnium nitride peaks were 3.2 times larger than the strongest hafnium oxide peaks, and the strongest hafnium oxynitride peaks were 14 times larger than the strongest hafnium oxide peaks.
EXAMPLE 6
This example shows the production of a hafnium nitride matrix composite using hafnium pentanedionate.
A braided carbon preform was melt-infiltrated with hafnium pentanedionate using the procedure described in Example 2 and heat treated at 1400° C. for 4 hours in nitrogen after the final infiltration cycle. X-ray diffraction analysis of the matrix material made on a companion sample heat treated at 1400° C. for 4 hours in nitrogen showed that it was composed mainly of hafnium nitride with minor amounts of hafnium oxynitride and hafnium oxide. The strongest hafnium nitride peaks were 3.5 times larger than the strongest hafnium oxide peaks, and the strongest hafnium oxynitride peaks were 0.7 times larger than the strongest hafnium oxide peaks.
EXAMPLE 7
This example shows the production of a hafnium carbide matrix composite using an chloride-stabilized hafnium oxide sol containing carbon black and additional CVI treatment to enhance the density of the final product.
A 2 in. long section from a 2 in. diameter braided HM carbon fiber preform was vacuum-infiltrated at room temperature with a hafnium oxide sol consisting of 20% hafnium oxide in a chloride-stabilized aqueous suspension to which 3.4% by weight carbon black had been added. The preform was vacuum-infiltrated at room temperature for 13 cycles and dried at 200° C. in air between infiltrations. It was heat treated in vacuum at 1600° C. for 2 hours after the 4th, 8th, and 13th cycles. The weight after the final heat treatment was 84% that of the original carbon fiber preform. The preform was then subjected to additional CVI densification using a mixture of HfCl 4 , propane, and argon and a deposition temperature of 1000° C. The HfCl 4 was generated in situ by flowing chlorine over hafnium sponge.
EXAMPLE 8
This example shows the synthesis of a silicon carbide matrix using SiO 2 as the metalloid compound.
A mixture of 20 gm of LUDOX, a 40% by weight colloidal dispersion of SiO 2 in water manufactured by DuPont Aerospace, and 4.8 grams of carbon black was prepared. The mixture was dried at 95° C. and divided into four portions for heat treatment in vacuum to convert the SiO 2 to SiC according to the equation
SiO 2 +3C→SiC+2CO
and under the temperature schedule illustrated in the following table:
TABLE 1
Sample
Temperature Range
Duration
Relative Principal
Number
(° C.)
(hours)
X-ray Count
1
1200
1.42
225
1300
1.25
1400
0.25
2
1400
4.25
>500
3
1500-1598
2.83
>1000
4
1570-1580
2.00
>1000
X-ray diffraction analysis of the matrix material in test sample 1 revealed the presence of a small amount of SiC as a reaction product along with some residual SiO 2 . This is evidenced in a low relative count of approximately 225 obtained at the β-SiC Bragg angle of approximately 36 degrees. These results indicate that the reaction to SiC at these temperatures was largely confined to the surface of the test sample.
X-ray diffraction results for sample 2 (1400° C.) yielded a SiC reaction that proceeded much further and the presence of a higher amount of SiC. This is confirmed by a relative β-SiC count that exceeded 500.
Finally, at the higher temperatures of the experiments associated with samples 3 and 4, the x-ray diffraction test results showed a complete reaction to SiC, as confirmed by a relative β-SiC count that exceeded 1000. There was no evidence of any residual SiO 2 .
Many alterations and modifications may be made by those having ordinary skill in the art without departing from the spirit and scope of the invention. The illustrated variations have been used only for the purposes of clarity and should not be taken as limiting the invention as defined by the following claims. | This invention is a fiber-reinforced ceramic matrix composite and a method for their fabrication. The precursors of the ceramic matrix phase are impregnated into the fibrous preform or-applied to the surface of the fiber as fluids. The preform or fibers are then thermally processed to convert the precursor compounds to the desired refractory materials, e.g., carbides, borides, or nitrides. The density and other properties of the composites may be enhanced further by using a hybrid process that combines fluid infiltration and thermal treatment with chemical vapor infiltration. | 2 |
TECHNICAL FIELD
[0001] The present invention relates to earth-boring shoes configured for attachment to a section of wellbore casing, to methods of manufacturing such earth-boring shoes, and to methods of adapting such earth-boring shoes for attachment to a section of wellbore casing.
BACKGROUND
[0002] The drilling of wells for oil and gas production conventionally employs longitudinally extending sections or so-called “strings” of drill pipe to which, at one end, is secured a drill bit of a larger diameter. After a selected portion of the borehole has been drilled, the borehole is usually lined or cased with a string or section of casing. Such a casing or liner usually exhibits a larger diameter than the drill pipe and a smaller diameter than the drill bit. Therefore, drilling and casing according to the conventional process typically requires sequentially drilling the borehole using drill string with a drill bit attached thereto, removing the drill string and drill bit from the borehole, and disposing casing into the borehole. Further, often after a section of the borehole is lined with casing, which is usually cemented into place, additional drilling beyond the end of the casing may be desired.
[0003] Unfortunately, sequential drilling and casing may be time consuming because, as may be appreciated, at the considerable depths reached during oil and gas production, the time required to implement complex retrieval procedures to recover the drill string may be considerable. Thus, such operations may be costly as well, since, for example, the beginning of profitable production can be greatly delayed. Moreover, control of the well may be difficult during the period of time that the drill pipe is being removed and the casing is being disposed into the borehole.
[0004] Some approaches have been developed to address the difficulties associated with conventional drilling and casing operations. Of initial interest is an apparatus which is known as a reamer shoe that has been used in conventional drilling operations. Reamer shoes have become available relatively recently and are devices that are able to drill through modest obstructions within a borehole that has been previously drilled. In addition, the reamer shoe may include an inner section manufactured from a material which is drillable by rotary drill bits. Accordingly, when cemented into place, reamer shoes usually pose no difficulty to a subsequent drill bit. For instance, U.S. Pat. No. 6,062,326 to Strong et al. discloses a casing shoe or reamer shoe in which the central portion thereof may be configured to be drilled through. In addition, U.S. Pat. No. 6,062,326 to Strong et al. discloses a casing shoe that may include diamond cutters over the entire face thereof, if it is not desired to drill therethrough. Such reamers that are configured for attachment to a casing string are referred to hereinafter as “reamer shoes.”
[0005] As a further extension of the reamer shoe concept, in order to address the problems with sequential drilling and casing, drilling with casing is gaining popularity as a method for initially drilling a borehole, wherein the casing is used as the drilling conduit and, after drilling, the casing is cemented into and remains within the wellbore to act as the wellbore casing. Drilling with casing employs a drill bit that is configured for attachment to the casing string instead of a drill string, so that the drill bit functions not only to drill the earth formation, but also to guide the casing into the wellbore. This may be advantageous as the casing is disposed into the borehole as it is formed by the drill bit, and therefore eliminates the necessity of retrieving the drill string and drill bit after reaching a target depth where cementing is desired. Such drill bits that are configured for attachment to a casing string are referred to hereinafter as “drill shoes.”
[0006] As used herein, the terms “earth-boring shoes” and “boring shoes” mean and include any device that is configured for attachment to an end of a section of casing and used for at least one of drilling a wellbore, reaming a previously drilled wellbore, and guiding casing through a previously drilled wellbore, as the section of casing to which the device is attached is advanced into a subterranean formation. Earth-boring shoes and boring shoes include, for example, drill shoes, reamer shoes, casing shoes configured to merely guide casing through a wellbore and ensure that the wellbore diameter remains as drilled (i.e., has not decreased as sometimes occurs in reactive or sloughing formations), and shoes that both drill and ream as casing to which they are attached is advanced into a subterranean formation.
[0007] Commercially available casing sections are sold in a variety of different diameters and with a variety of different coupling configurations. As a result, when an earth-boring shoe is manufactured for a particular customer, a conventional boring shoe must be manufactured for the particular diameter of casing to which the boring shoe is to be attached. Furthermore, the boring shoe must be provided with a connection portion that is configured (e.g., with threads) to complimentarily engage the particular connection portion of the casing string to which the boring shoe is to be attached.
[0008] There is a need in the art for improved methods of coupling boring shoes to casing strings, and for improved methods of adapting boring shoes for attachment to casing strings having different connection configurations.
BRIEF SUMMARY
[0009] In some embodiments, the present invention includes methods of attaching a crown of a boring shoe to a section of casing. A first end of an adaptable shank may be attached to the crown of a boring shoe, and an opposite, second end of the adaptable shank may be machined to configure the second end of the adaptable shank for attachment to a section of casing after attaching the first end of the adaptable shank to the crown.
[0010] In additional embodiments, the present invention includes methods of attaching boring shoes to sections of casing. A first end of an adaptable shank is welded to a crown to form a boring shoe. The adaptable shank is selected to have an average wall thickness greater than about five percent (5%) of a maximum diameter of the crown. An opposite, second end of the adaptable shank is configured for attachment to a particular type of casing section after welding the first end of the adaptable shank to the crown.
[0011] Yet further embodiments of the present invention include boring shoes having an adaptable shank attached to a crown, wherein the adaptable shank comprises a generally cylindrical wall having an average wall thickness greater than about five percent (5%) of a maximum diameter of the crown.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0012] While the specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the present invention, the advantages of embodiments of this invention may be more readily ascertained from the following description of certain embodiments of the invention when read in conjunction with the accompanying drawings, in which:
[0013] FIG. 1 is a perspective view of an embodiment of a shoe tool of the present invention that includes a crown attached to an adaptable shank;
[0014] FIG. 2 is a schematic illustration showing the shoe tool of FIG. 1 attached to a section of casing and disposed within a subterranean formation;
[0015] FIG. 3 is a longitudinal cross-sectional view of an embodiment of a shoe tool like that of FIG. 1 including a crown attached to an adaptable shank;
[0016] FIG. 4 is an enlarged cross-sectional view of an interface between the crown and the adaptable shank shown in FIG. 3 ;
[0017] FIG. 5 is a longitudinal cross-sectional view of the shoe tool shown in FIGS. 3 and 4 after adapting the shank for connection to casing in accordance with embodiments of methods of the present invention; and
[0018] FIG. 6 is a longitudinal cross-sectional view of the shoe tool shown in FIG. 5 , further illustrating a section of casing coupled to the shank of the shoe tool.
DETAILED DESCRIPTION
[0019] Illustrations presented herein are not meant to be actual views of any particular device or system, but are merely idealized representations which are employed to describe embodiments of the present invention. Additionally, elements common between figures may retain the same numerical designation.
[0020] An embodiment of a boring shoe 10 of the present invention is shown in FIG. 1 . The boring shoe 10 shown in FIG. 1 is an intermediate structure that has not yet been adapted for attachment to any particular section of casing. After formation of the intermediate boring shoe 10 shown in FIG. 1 , the boring shoe 10 may be adapted for attachment to a particular section of casing, as described in further detail herein below.
[0021] The boring shoe 10 shown in FIG. 1 may be a reamer shoe or a drill shoe configured for attachment to a section of casing for use in forming a wellbore in a subterranean formation. As shown in FIG. 1 , the boring shoe 10 includes a crown 20 and an adaptable shank 30 that is attached to the crown 20 .
[0022] In some embodiments, the crown 20 may be configured to drill a wellbore in a subterranean formation. In other embodiments, the crown 20 may be configured to ream (i.e., enlarge the diameter of) a previously drilled wellbore. In yet other embodiments, the crown 20 may be configured to merely guide casing through a wellbore and ensure that the wellbore diameter remains as previously drilled and has not decreased as sometimes occurs in reactive or sloughing formations. In other words, the crown 20 may only ream sections of the wellbore that have an undersized diameter due, for example, to encroachment of the formation material into the wellbore.
[0023] The crown 20 includes a body 21 that may be formed of and comprise, for example, a metal or metal alloy (e.g., steel, aluminum, brass, or bronze), or a composite material including particles of a relatively harder material (e.g., tungsten carbide) embedded within a relatively softer metal or metal alloy (e.g., steel, aluminum, brass, or bronze). The material of the body 21 may be selected to exhibit physical properties that allow the body 21 to be drilled through by another drill bit after the boring shoe 10 has been used to advance a section of casing attached thereto into a subterranean formation, as known in the art.
[0024] Drilling and/or reaming structures may be provided on exterior surfaces of the body 21 of the crown 20 . For example, the crown 20 may comprise a plurality of blades 22 that define fluid courses 24 therebetween. Apertures 25 may be formed through the crown 20 for allowing fluid (e.g., drilling fluid and/or cement) to be pumped through the interior of the boring shoe 10 , out through the apertures 25 in the crown 20 , and into the annular space between the walls of the formation in which the wellbore is formed and the exterior surfaces of the boring shoe 10 and the casing sections to which the boring shoe 10 may be attached. For example, the apertures 25 may comprise fluid passageways extending through the body 21 of the crown 20 . Optionally, nozzles (not shown) may be secured to the crown 20 within the fluid passageways to selectively tailor the hydraulic characteristics of the boring shoe 10 . Cutting element pockets may be formed in the blades 22 , and cutting elements 26 , such as, for example, polycrystalline diamond compact (PDC) cutting elements, may be secured within the cutting element pockets.
[0025] Also, each of blades 22 may include a gage region 23 that together define the largest diameter of the crown 20 and, thus, the diameter of any wellbore formed using the crown 20 and boring shoe 10 . The gage regions 23 may be longitudinal extensions of the blades 22 . Wear-resistant structures or materials may be provided on the gage regions 23 . For example, tungsten carbide inserts, cutting elements, diamonds (e.g., natural or synthetic diamonds), or hardfacing material may be provided on the gage regions 23 of the crown 20 .
[0026] In additional embodiments, the crown 20 may not include blades 22 and cutting elements 26 , like those shown in FIG. 1 . In such embodiments, the crown 20 may comprise other cutting and/or reaming structures such as, for example, deposits of hardfacing material (not shown) on the exterior surfaces of the crown 20 . Such a hardfacing material may comprise, for example, hard and abrasive particles (e.g., diamond, boron nitride, silicon carbide, carbides or borides of titanium, tungsten, or tantalum, etc.) embedded within a metal or metal alloy matrix material (e.g., an iron-based, cobalt-based, or nickel-based metal alloy). Such deposits of hardfacing material may be shaped into elongated, protruding structures on the exterior surfaces of the crown 20 .
[0027] FIG. 2 is a simplified schematic illustration showing the boring shoe 10 attached to a section of casing 39 and disposed within a wellbore that has been formed in a subterranean formation using the boring shoe 10 . As previously discussed, the casing 39 , with the boring shoe 10 attached thereto, may be rotated and advanced into the subterranean formation as drilling fluid is pumped down through the interior of the casing 39 , out through the apertures 25 in the crown 20 , and up through the fluid courses 24 ( FIG. 1 ) and up through the annular space between the walls of the formation within the wellbore and the exterior surfaces of the casing 39 to the surface of the formation.
[0028] Once the casing 39 has been advanced to a desirable location within the formation, drilling with the boring shoe 10 may be ceased, and the casing 39 may be cemented in place. To cement the casing 39 in place, cement (not shown) or another curable material may be forced through the interior of casing 39 , through the apertures 25 in the crown 20 , up through the fluid courses 24 ( FIG. 1 ), and into the annulus between the wall of wellbore and the outer surface of the casing 39 , where it may be allowed to harden. Of course, conventional float equipment may be used for controlling and delivering the cement through the boring shoe 10 and into the annulus between the wall of the wellbore and the casing 39 . Cementing the casing 39 in place within the wellbore may stabilize the wellbore and seal the subterranean formations penetrated by the boring shoe 10 and the casing 39 .
[0029] In some instances, the size and placement of the apertures 25 that are employed for drilling operations may not be particularly desired for cementing operations. Furthermore, the apertures 25 may become plugged or otherwise obstructed during a drilling operation. As shown in FIGS. 1 and 2 , at least one of the crown 20 and the shank 30 of the boring shoe 10 may include one or more frangible regions 28 that can be breached (e.g. a metal disc that can be fractured, perforated, ruptured, removed, etc.) to form one or more additional apertures that may be used to provide fluid communication between the interior and the exterior of the boring shoe 10 . Drilling fluid and/or cement optionally may be caused to flow through such frangible regions 28 after breaching the same.
[0030] Referring again to FIG. 1 , the boring shoe 10 includes an adaptable shank 30 having a first end 31 A attached to the crown 20 and a second end 31 B that may be adapted and used to couple the boring shoe 10 to a section of casing (not shown in FIG. 1 ). The shank 30 may have a size and shape that allows it to be adapted, after attachment to the crown 20 , for coupling to a wide variety of different casing configurations, as discussed in further detail herein below.
[0031] FIG. 3 is a longitudinal, cross-sectional view of another embodiment of an intermediate boring shoe 50 of the present invention. The intermediate boring shoe 50 is similar to the boring shoe 10 shown in FIG. 1 , and includes a crown 40 having a body 41 that is attached to an adaptable shank 30 , as previously described in relation to FIG. 1 .
[0032] The adaptable shank 30 is a cylindrical structure having a length L. By way of example and not limitation, the length L of the adaptable shank 30 may be between about twenty-five (25) centimeters (about ten (10) inches) and about two hundred (200) centimeters (about seventy-nine (79) inches).
[0033] The adaptable shank 30 has a wall thickness T W that is one-half of the difference between the outer diameter OD of the shank 30 and the inner diameter ID of the shank 30 . The wall thickness T W may vary, depending upon the size (e.g., the diameter) of the crown 40 to which the shank 30 is attached. The wall thickness T W of the shank 30 , however, may be sufficiently large to allow the shank 30 to be adapted for use with a number of different casing sections having a variety of weights and coupling configurations that might be used with the particular size of crown 40 to which the shank 30 is attached. Although the shank 30 of FIG. 3 is shown having an outer diameter that is less than an outer diameter of the crown 40 to which the shank 30 is attached, in additional embodiments, the shank 30 may have an outer diameter that is larger than a diameter of the crown 40 to which the shank 30 is attached.
[0034] Table 1 below lists a variety of different diameters of crowns that are often used in the industry, together with the outer diameter OD, the inner diameter ID, and the wall thickness T W of examples of adaptable shanks 30 of the present invention that may be attached to such crowns. All dimensions in Table 1 are given in inches, and dimensions in centimeters are provided in parenthesis.
[0000]
TABLE 1
Shank T W as
Crown
Casing
Percentage of
Diameter
Diameter
Shank OD
Shank ID
Shank T W
Crown Diameter
6.00
in
4.50
in
5.125
in
3.625
in
0.750
in
12.5%
(15.24
cm)
(11.43
cm)
(13.02
cm)
(9.21
cm)
(1.91
cm)
8.50
in
7.625
in
8.625
in
6.00
in
1.313
in
15.4%
(21.59
cm)
(19.37
cm)
(21.91
cm)
(15.24
cm)
(3.34
cm)
12.25
in
9.625
in
10.750
in
8.310
in
1.220
in
10.0%
(31.12
cm)
(24.45
cm)
(27.31
cm)
(21.11
cm)
(3.10
cm)
17.50
in
13.375
in
14.500
in
12.250
in
1.125
in
6.4%
(44.45
cm)
(33.97
cm)
(36.83
cm)
(31.12
cm)
(2.86
cm)
24.00
in
20.00
in
21.125
in
18.60
in
1.263
in
5.3%
(60.96
cm)
(50.80
cm)
(53.66
cm)
(47.24
cm)
(3.21
cm)
[0035] As shown in Table 1, in some embodiments of the present invention, the crown 40 may have a diameter that is about 12.25 inches or less, and the adaptable shank 30 may have a wall thickness that is about 10% or more of the diameter of the crown 40 , about 12% or more of the diameter of the crown 40 , or even about 15% or more of the diameter of the crown 40 . As one particular non-limiting example, the crown 40 may have a diameter of about 12.25 inches, the shank 30 may have an outer diameter OD of about 10.750 inches, an inner diameter ID of about 8.310 inches or less, and a wall thickness T W of about 1.220 inches or more (i.e., about 10.0% or more of the diameter of the crown 40 ). As another particular non-limiting example, the crown 40 may have a diameter of about 8.50 inches, the shank 30 may have an outer diameter OD of about 8.625 inches, an inner diameter ID of about 6.00 inches or less, and a wall thickness T W of about 1.313 inches or more (i.e., about 15.4% or more of the diameter of the crown 40 ). As yet another particular non-limiting example, the crown 40 may have a diameter of about 6.00 inches, the shank 30 may have an outer diameter OD of about 5.125 inches, an inner diameter ID of about 3.625 inches or less, and a wall thickness T W of about 0.750 inches or more (i.e., about 12.5% or more of the diameter of the crown 40 ). Other non-limiting examples of embodiments of the invention are also set forth in Table 1 above.
[0036] As shown in Table 1, in additional embodiments of the present invention, the crown 40 may have a diameter that is greater than about 12.25 inches, and the adaptable shank 30 may have a wall thickness that is about 5% or more of the diameter of the crown 40 , or even about 6% or more of the diameter of the crown 40 . As one particular non-limiting example, the crown 40 may have a diameter of about 17.50 inches, the shank 30 may have an outer diameter OD of about 14.500 inches, an inner diameter ID of about 12.250 inches or less, and a wall thickness T W of about 1.125 inches or more (i.e., about 6.4% or more of the diameter of the crown 40 ). As another particular non-limiting example, the crown 40 may have a diameter of about 24.00 inches, the shank 30 may have an outer diameter OD of about 21.125 inches, an inner diameter ID of about 18.60 inches or less, and a wall thickness T W of about 1.263 inches or more (i.e., about 5.3% or more of the diameter of the crown 40 ).
[0037] The adaptable shank 30 may be formed from and comprise a metal material such as, for example, an iron-based metal alloy (e.g., a steel alloy). In some embodiments, the adaptable shank 30 may be formed from and comprise a material that exhibits a tensile yield strength of at least about 60,000 pounds per square inch (PSI), at least about 90,000 pounds per square inch (PSI), or even at least about 120,000 PSI pounds per square inch (PSI). As previously mentioned, the adaptable shank 30 may be separately formed from the crown 40 and subsequently attached thereto.
[0038] FIG. 4 is an enlarged cross-sectional view of an interface between the crown 40 and the adaptable shank 30 shown in FIG. 3 . As shown in FIG. 4 , the shank 30 may be attached to the crown 40 by abutting an end surface 34 of the shank 30 against an end surface 48 of the crown 40 and welding an interface between the shank 30 and the crown 40 . In other words, a weld material 60 (e.g., one or more weld beads) may be provided around an exterior surface of the intermediate boring shoe 50 along the interface between the crown 40 and the shank 30 . In some embodiments, the shank 30 may have a beveled, frustoconical surface 36 at the first longitudinal end 31 A thereof, and the crown 40 may have a complementary beveled, frustoconical surface 49 . The frustoconical surface 36 of the shank 30 and the frustoconical surface 49 of the crown 40 may define a weld groove therebetween when the shank 30 is abutted against the crown 40 . A weld material 60 may be deposited in the form of one or more weld beads within the weld groove to weld the shank 30 and the crown 40 together. The shank 30 may be abutted against, and welded to, the crown 40 prior to adapting the shank 30 for attachment to a section of casing.
[0039] In additional embodiments, complementary threads (not shown) may be provided on the crown 40 and the shank 30 to allow the crown 40 and the shank 30 to be threaded together to attach the crown 40 and the shank 30 together. In such embodiments, a weld material 60 also may be provided along the interface between the crown 40 and the shank 30 to further secure the crown 40 and the shank 30 together.
[0040] Referring to FIG. 5 , after attaching the shank 30 and the crown 40 together, the shank 30 may be adapted for attachment to a particular section of casing. The shank 30 may be adapted for attachment to a particular section of casing by, for example, doing one or more of the following: reducing the length L of the shank 30 , reducing the wall thickness T W of the shank 30 , and providing one or more features on the shank 30 , and/or shaping one or more surfaces of the shank 30 , for coupling to an end of a section of casing. The wall thickness T W of the shank 30 may be reduced by reducing the outer diameter of the shank 30 , by increasing the inner diameter of the shank 30 , or by both reducing the outer diameter and increasing the inner diameter of the shank 30 .
[0041] The outer diameter of the shank 30 may be reduced, and the inner diameter of the shank 30 may be increased, as desirable, using, for example, conventional machining processes such as turning processes, milling processes, and combinations of turning and milling processes.
[0042] To configure the shank 30 for coupling to a section of casing, one or more features may be provided on the shank 30 , and/or one or more surfaces of the shank 30 may be provided with a certain shape, as previously mentioned. For example, an inner surface 38 A of the shank 30 may be formed to comprise what is referred to in the art as a “threaded box.”
[0043] To form a threaded box in the inner surface 38 A of the shank 30 , a section of the inner surface 38 A of the shank 30 at the second end 31 B thereof may be formed to comprise a taper, such that the section of the inner surface 38 A has a frustoconical shape have a diameter that is greatest at the opening of the shank 30 at the second end 31 B thereof, the diameter becoming progressively smaller moving in the longitudinal direction toward the first end 31 A of the shank 30 . The angle of the taper of the inner surface 38 A of the shank 30 at the second end 31 B may be selected to correspond to the angle of a taper on the exterior surface of a section of casing to which the shank 30 is to be attached. Such a taper also may be formed in the inner surface 38 A using, for example, conventional machining processes such as turning processes, milling processes, and combinations of turning and milling processes.
[0044] Furthermore, threads 37 may be formed on a section of the inner surface 38 A of the shank 30 at the second end 31 B (e.g., on a tapered section of the inner surface 38 A). The size (e.g., dimensions), shape, and spacing (e.g., pitch) of the threads 37 also may be selected to correspond to the size (e.g., dimensions), shape, and spacing (e.g., pitch) of complementary threads on a section of casing to which the shank 30 is to be attached. The threads 37 also may be formed in the inner surface 38 A using, for example, conventional machining processes such as turning processes, milling processes, and combinations of turning and milling processes. Threads may also be formed by rolling the surface to be threaded against a threading die, as known in the art, and such roll threading processes also may be employed in embodiments of the present invention.
[0045] In some embodiments, threads 37 may be formed on the inner surface 38 A of the shank 30 at the second end 31 B thereof without providing any taper on the inner surface 38 A. In other words, the inner surface 38 A may remain at least substantially cylindrical, and a section of the cylindrical inner surface may be threaded.
[0046] In additional embodiments of the present invention, an outer surface 38 B of the shank 30 may be formed to comprise what is referred to in the art as a “threaded pin,” which is a male pin member having threads on an exterior surface thereof that is configured to mate with, and engage, a female threaded box, as previously described herein.
[0047] Referring to FIG. 6 , after adapting the shank 30 for attachment to a particular section of casing 61 , the shank 30 and the section of casing 61 may be coupled together in preparation for drilling and/or reaming with the boring shoe 50 as the casing 61 and the boring shoe 50 are advanced into a subterranean formation.
[0048] In the embodiment shown in FIG. 6 , a threaded box is provided on the inner surface 38 A of the shank 30 at the second end 31 B thereof, and the section of casing 61 has a threaded pin 62 at an end 64 thereof that is complementary to, and configured to mate with and engage, the threaded box at the second end 31 B of the shank 30 .
[0049] In additional embodiments of the invention, however, the shank 30 may be formed to comprise a threaded pin, and the casing 61 may comprise a complementary threaded box configured to engage the threaded pin of the shank 30 . In yet further embodiments, each of the shank 30 and the casing 61 may comprise a threaded pin, and a collar having a threaded box on both ends thereof may be used to couple the threaded pin of the shank 30 to the threaded pin of the casing 61 . Such collars are commercially available and frequently used in the art.
[0050] Thus, in accordance with some embodiments of methods of the present invention, an adaptable shank may be attached to a crown of a boring shoe prior to identifying the type of casing to which the boring shoe will ultimately be attached. As a result, a manufacturer need not fabricate a variety of different types of shanks for each size of boring shoe, each type corresponding to the different types of casing to which the boring shoe might be attached. In contrast, a single, adaptable shank in accordance with embodiments of the present invention may be fabricated for each size of boring shoe, and the adaptable shank can be adapted, after attachment to a crown, for attachment to a particular type of casing.
[0051] Furthermore, in accordance with some embodiments of methods of the present invention, an adaptable shank may be attached to a crown of a boring shoe prior to identifying the type of casing to which the boring shoe will ultimately be attached. The crown, with the adaptable shank attached thereto, may be transported to another location other than where the crown and shank were attached together (e.g., the location of a distributor, the location of a drilling site, etc.) by way of a vehicle (e.g., a truck, plane, or boat). After transporting the crown, with the adaptable shank attached thereto, to another location, a particular type of casing to which the crown and adaptable shank are to be attached may be identified, and the adaptable shank may be adapted, as previously described herein, for attachment to that particular type of casing.
[0052] While the present invention has been described herein with respect to certain embodiments, those of ordinary skill in the art will recognize and appreciate that it is not so limited. Rather, many additions, deletions and modifications to the embodiments described herein may be made without departing from the scope of the invention as hereinafter claimed. In addition, features from one embodiment may be combined with features of another embodiment while still being encompassed within the scope of the invention as contemplated by the inventors. | Methods of attaching a crown of a boring shoe to a casing section include attaching an adaptable shank to a crown, and machining the adaptable shank to configure an end thereof for attachment to a casing section after attaching the adaptable shank to the crown. Additional methods include welding an end of an adaptable shank to a crown to form a boring shoe, selecting the adaptable shank to have an average wall thickness greater than about five percent (5%) of a maximum diameter of the crown, and configuring an opposite end of the adaptable shank for attachment to a particular type of casing section after welding the shank to the crown. Boring shoes have an adaptable shank attached to a crown, wherein the shank comprises a generally cylindrical wall having an average wall thickness greater than about five percent (5%) of a maximum diameter of the crown. | 4 |
CROSS-REFERENCE TO PRIOR APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 12/993,876, filed Dec. 17, 2010, which is a U.S. National Phase application under 35 U.S.C. §371 of International Application No. PCT/EP2009/003143, filed on Apr. 30, 2009, and claims benefit to German Patent Application No. DE 20 2008 006 986.6, filed on May 23, 2008. The International Application was published in German on Nov. 26, 2009 as WO 2009/141049 under PCT Article 21(2).
FIELD
[0002] The present invention relates to a profile element connecting a motor vehicle pane to a water draining chamber.
BACKGROUND
[0003] A water draining chamber is used in motor vehicles underneath the vehicle pane for instance the windshield, said box collecting water from said pane and draining it sideways. Illustratively an extruded profile element or contoured extrusion molded element is used to affix the water draining chamber to and seal it against the lower edge of the pane and furthermore is fitted with a snap-in groove to detachably receive said box.
[0004] To preclude forming an offset or an edge in the transition zone between the pane surface and the profile element, the published German patent document DE 200 08 555 U1 discloses a design for sealing vehicle panes and including a cross-sectionally hooked profile element which is bonded to the lower edge of the vehicle pane. Said profile element comprises a resilient leg which, together with a ribbed wedge, constitutes an outwardly open snap-in seat. Said snap-in seat receives the water draining chamber which is fitted on its back side with a detent rib. A sealing lip is fitted onto the ribbed wedge and may be fitted between the lower pane edge and the upper edge of the water draining chamber's lid and in its assembled position ends flush with the external surfaces of water draining chamber and vehicle pane. A buffer strip made of a softer material is configured below the snap-in groove and allows resting the seal against the vehicle body.
[0005] The profile element must be supported by the vehicle body because a high resistance must be overcome when the water draining chamber is inserted perpendicularly to the pane surface into the profile element. In turn said resistance is required to always reliably affix the water draining chamber to said element, that is, in order not to accidentally coming loose when in motion on the road or on account of other mechanical or thermal loads. On the other hand maintenance frequently entails detaching the water draining chamber from the vehicle pane and reassembling it for instance when changing a filter.
[0006] However relatively high forces are always encountered when installing the water draining chamber and they directly act on the adhesive bond between the profile element and the vehicle pane. In the absence of the contoured body resting on the vehicle body or absent per se from such a body, there is danger of the installation stresses detaching the profile element from the vehicle pane.
[0007] The profile elements of the state of the art moreover incur the further drawback that resting on the vehicle body may entail annoying noises, especially so when the highly compliant support elements lose their elasticity with time.
SUMMARY
[0008] Accordingly it is the objective of the present invention to overcome the drawbacks of the state of the art and to create a profile element which links a vehicle pane to a water draining chamber and which may be manufactured economically using simple means while also allowing simple, rapid water draining chamber installation without thereby stressing the connection between the profile element and the vehicle pane. Nevertheless the water draining chamber shall be durably affixed to the profile element and withstand even larger loads in problem-free manner.
[0009] As regards a profile element which connects a vehicle pane and a water draining chamber and which comprises a first segment affixable to said pane, further a second segment subtending a snap-in recess designed to detachably affix the water draining chamber, said box being fitted with a rib affixable in frictionally locking and/or geometrically interlocking manner into said snap-in recess, moreover at least one seal which can be inserted between the vehicle pane's lower edge and the water draining chamber's upper edge and which constitutes, in the installed state of the water draining chamber, a substantially smooth transition where the adjoining surfaces are mutually flush, the present invention calls for at least one detent element that is designed to ease inserting the water draining chamber's rib into the snap-in recess in a first direction whereas extracting the rib from the snap-in recess in the opposite direction is made more difficult.
[0010] This design allows installing the water draining chamber easily and quickly because its rib—compared to conventional profile elements—can be inserted at substantially less resistance respectively with much less force into the associated snap-in recess. Accordingly much smaller forces will act on the profile element and on its bond to the vehicle pane, and consequently said profile element cannot unintentionally detach from said pane, not even after installing and dismantling the water draining chamber repeatedly. Furthermore a complex support of the profile element by the vehicle body is not required, this feature advantageously affecting manufacturing and installation costs. Clatter and the like no longer may arise when there is relative displacement between the profile element and the vehicle body.
[0011] On the other hand, extracting the rib requires a much larger force in the design of the present invention of said detent element, and as a result, following its installation, the water draining chamber shall always be firmly affixed to said profile element. The water draining chamber even when subjected to considerable mechanical and thermal stresses is unable to detach off the profile element or even from the vehicle, so that high operational reliability is assured. The system as a whole offers a simple design and is unusually dimensionally stable.
[0012] Advantageously, when controlling the forces of insertion and extraction, the respectively each detent element is configured at an angle to the direction of mating. Illustratively, a slight sideways bending or pressure may be applied when inserting the water draining chamber's rib into the snap-in recess, whereas, when removing said box, the rib first must ram the detent element before latter will release it.
[0013] On account of the angular position of the detent element relative to the direction of installation, the, respectively each, detent element constitutes a barb for the rib inserted into the water draining chamber's snap-in recess, as a result of which said box can be detached off the profile element only after overcoming the barb's resistance by applying a predetermined force, illustratively for the purpose of maintaining or replacing components situated underneath. On the other hand, the resistance presented by the barb encountered when inserting the rib into the snap-in recess is relatively easily overcome and as a result the profile element and its bond to the vehicle pane are hardly stressed.
[0014] Advantageously too the, respectively each, detent element shall be at least partly elastically deformable. Such a detent element will yield relatively easily when inserting the rib into the snap-in recess, whereas making it quite difficult for the detent element to move out of the way when extracting the rib from the profile element in spite of said elasticity, for instance because the detent element perforce being rammed before releasing the rib. The barb operation may be enhanced by fitting the, respectively each, snap-in recess at its free lengthwise edge with a convex or beaked edge which, depending on design, rests on the water draining chamber's rib and/or on the profile element.
[0015] In one embodiment of the present invention, the, respectively each, detent element is configured within the snap-in recess and can be made to engage frictionally and/or in a geometrically interlocking manner with the water draining chamber's rib. This design allows very different embodiment modes. Illustratively the detent element may be mounted, at an angle to the direction of installation, on a bearing rib of the profile element and/or to a resilient leg of the snap-in leg of the snap-in recess.
[0016] Further advantages are attained when the snap-in recess is fitted with or subtends an engagement aperture which is entered at least in part by the, respectively each, detent element. In this manner, when being inserted into the snap-in recess, the water draining chamber's rib at once engages the detent element which initially is thereby forced inward away from the rib, as a result of which the water draining chamber is installed easily, namely not requiring a large force. However, following snapping the rib into the snap-in recess, the detent element will engage the rib. Furthermore said detent element constitutes a barb and, on account of its angular position, may only be forced to the side after overcoming a substantial resistance. In spite of having been easily installed, the water draining chamber no longer may be unintentionally detached from the profile element.
[0017] Additional dimensional stability is assured by a design, whereby the convex, resp. beaked edge, of the, resp. each, detent element rests against the water draining chamber when this chamber is in its installed position. Said rib may be appropriately fitted with an indentation, an offset or the like.
[0018] In addition or alternatively to the above design, the, respectively each, detent element may be mounted at the water draining chamber's rib, the detent element being able to engage the profile element frictionally and/or in geometrically interlocking manner. This approach as well assures both easily and quickly installing the water draining chamber without thereby stressing the connection between the profile element and the vehicle pane during said installation. At the same time the water draining chamber installed on the profile element is affixed so firmly that the entire system easily withstands even larger loads while simultaneously allowing water draining chamber disassembly, without damage to the profile element.
[0019] In this embodiment, the detent element acts as a barb for the profile element, this barb significantly reducing the forces required for connection but nevertheless firmly affixing the installed water draining chamber. In this design the convex or beaked edge of the, respectively each, detent element rests on the bearing rib or the resilient leg that for that purpose may be fitted with an indentation, an offset or the like.
[0020] In another embodiment of the present invention, a bearing rib is subtended between the first and second segments of the profile element and bears the minimum of one seal. Said seal assures sealing the surface transitions between the water draining chamber and the vehicle pane, the bearing rib per se constituting an elastic clamping and/or rest element between the lower windshield edge and the water draining chamber's rib.
[0021] The profile element's snap-in recess is subtended by a resilient leg and the bearing rib, the free end of said leg together with said rib bounding an engagement aperture. The resilient leg in principle may be L, U shaped or hook-like. The free end of the resilient leg moreover may be fitted with an indentation within the snap-in recess to be engaged by the water draining chamber's rib or the detent element.
[0022] Accordingly the water draining chamber's rib when in the locked position always is firmly enclosed by the outwardly projecting resilient leg, the bearing rib for the rib constituting a wedge. Simultaneously the bearing rib supports the seal, as a result of which the profile element not only seals the water draining chamber and the vehicle pane from each other but also connects them frictionally and in geometrically interlocking manner Additional snap-in designs may be provided by an indentation at the bearing rib within the snap-in recess, for instance for the water draining chamber's rib or the detent element.
[0023] The resp. each seal and/or the, resp. each, detent element preferably are firmly bonded to the bearing rib. However all components also may be integral. In this manner many designs are possible, namely by making the particular components in one or more parts.
[0024] Preferably the seal and the detent element are made of a highly resilient material whereas the segments of the profile element and the bearing rib are made of a stiffer but still elastic material. The particular components of the profile element as a whole however may be made of a compound material, for instance in the form of a composite of soft and hard resilient materials. Illustratively the sealing lip may be externally highly compliant outside while of low compliance inside; in particular it may be hollow-hard inside and soft on the outside. Other variations also apply. The detent element may be externally soft and harder but still flexible on the inside. Again its cross-section may vary in shape, for instance being square/rectangular, oval or concave. The detent element's shape also may be individual, namely matching the water draining chamber's rib, or being at least segment-wise tubular. The profile element's bearing rib may be substantially wedge-shaped, stepped, T-like or U-shaped. Other shapes also are conceivable and applicable.
[0025] The first segment, the second segment and/or the bearing rib are fitted at least in part with a resilient stiffening insert. As a result the profile element as a whole can withstand high loads and is permanently dimensionally stable.
[0026] Manufacturing-wise, the first segment, the second segment and/or the bearing rib advantageously shall be extruded as a section. This feature is economical.
[0027] The entire sealing system is intended for vehicle panes, in particular for the lower portion of a motor vehicle windshield. It consists of the vehicle pane, the profile element affixed to it, and the water draining chamber to be affixed therein.
[0028] The profile element enables quickly and simply installing the water draining chamber without requiring applying a large force, as a result of which the connection between the profile element and the vehicle pane shall not be stressed even when repeatedly installing the water draining chamber. At the same time the water draining chamber when in its installed position is kept in frictionally and geometrically interlocking manner in the profile element, resulting in a durable firm connection which also permanently withstands substantial mechanical and thermal loads. Nevertheless the water draining chamber may be repeatedly removed for instance to replace a pollen filter, even though the removal force is larger than that of installation.
[0029] Further features, particulars and advantages are defined in the claims and are discussed in the illustrative embodiment modes below and with respect to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 is a schematic section of an installed sealing system with a profile element of the invention,
[0031] FIG. 2 is a schematic sideview of the sealing system prior to water draining chamber installation, and
[0032] FIG. 3 is a schematic sideview of the sealing system of FIG. 1 during the joining procedure.
DETAILED DESCRIPTION
[0033] The profile element denoted by the overall reference 10 in FIG. 1 connects a vehicle pane 40 and a water draining chamber 50 . Illustratively the vehicle pane 40 is motor vehicle windshield made of a composite glass and integrated in an omitted vehicle body of car (also omitted). The water draining chamber 50 is usually made of plastic and by its upper edge 53 abuts the mostly curved lower edge 42 of the windshield 40 , and guides water running down said windshield to the outside. Preferably the outer surface G of the water draining chamber 50 is situated flush with the outer surface A of the windshield 40 .
[0034] Preferably the profile element 10 is an extruded element of which the length corresponds to the width of the windshield 40 respectively to the width of the water draining chamber. It consists of one or more plastics (thermoplastic or thermosetting) each of a suitable hardness, for instance polypropylene (PP), polyvinylchloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS) or the like and combinations thereof. However elastomers and rubber materials such as EPDM are also applicable. A first segment 20 of the profile element 10 is fitted with a surface 22 for affixation to the vehicle pane 40 . A double-sided adhesive tape 24 is deposited as the adhesive layer 24 on said surface 22 and illustratively is heat activated. The profile element 10 together with the adhesive tape 24 is pressed along the pane edge 42 against the back side 44 of the vehicle pane 40 and bonds to it.
[0035] The profile element 10 further comprises a second segment 30 fitted with a snap-in recess 60 to allow detachably affixing the water draining chamber 50 which is fitted on its back side with a snap-in, respectively protruding rib 51 that can be affixed in frictional and/or geometrically interlocking manner in said snap-in recess 60 . FIG. 1 shows that the water draining chamber's rib 51 runs in a direction R 1 which is approximately perpendicular to the outer surface G of the water draining chamber 50 respectively to the outer surface A of the front pane 40 . The configuration of the vehicle pane 40 , profile element 10 and water draining chamber 50 is moreover selected in a manner that the resilient rib 51 of the water draining chamber 50 can be inserted in the direction R 1 into the snap-in recess 60 of the profile element 10 and also be extracted in the opposite direction R 2 from said profile element 10 .
[0036] The snap-in recess 60 is bounded by a substantially L, U-shaped or hook-like resilient leg 62 and by a bearing rib 80 , the latter being subtended by the first segment 20 and the second segment 30 of the profile element 10 . The free end 64 of the resilient leg 62 and the bearing rib 80 subtend an engagement aperture 61 for the rib 51 of the water draining chamber 50 .
[0037] The cross-section of the bearing rib 80 is approximately wedge-shaped and/or T-shaped. Between the pane's lower edge 42 and the inwardly protruding rib 51 of the water draining chamber 50 , said bearing rib 80 constitutes a clamping, respectively a support element supporting on its face 91 the seal 90 . Said seal 90 preferably is made of a soft-resilient material, for instance a thermoplastic elastomer (TPE), foam rubber or another suitable material such as an elastomer or rubber. It rests in sealing manner by means of a beaked edge 92 against the lower edge 42 of the vehicle pane 40 and—following installation of the water draining chamber 50 —it will be compressed between said pane's lower edge 42 and the top edge 53 of the water draining chamber 50 in a way that the (unreferenced) outer surface of the seal 90 ends flush with the outer surface A of the pane 40 and with the outer surface G of the water draining chamber 50 . As a result a smooth transition flush with the surfaces of the vehicle pane 40 and the water draining chamber 50 is attained.
[0038] Preferably the seal 90 shall be firmly bonded to the bearing rib 80 . However it may also be integral with it.
[0039] Preferably, in region of the lower pane edge 42 , the bearing rib 80 and the first segment 20 of the profile element 10 subtend a space 84 , as a result of which, when in the installed configuration, the bearing rib may yield elastically when resting against the pane 40 . This feature offers more than durably good and reliable sealing. The bearing rib 80 and the sealing lip 90 also may compensate tolerances between the pane 40 and the water draining chamber 50 .
[0040] At its free end 64 within the snap-in recess 60 , the resilient leg 62 is fitted with an indentation 63 . In the installed state of the water draining chamber 50 , said indentation engages from behind a beaked edge 52 at the rib 51 which thereby is always affixed in frictionally and/or geometrically interlocking manner in the snap-in recess 60 of the profile element 10 . To improve the insertion of rib 51 into said snap-in recess a beaked edge 52 and the free end 64 of the resilient leg 62 are fitted within (unreferenced) bevels. The bearing rib 80 also is fitted with the snap-in recess 60 with an indentation 83 which shall be discussed further below.
[0041] To assure installing the water draining chamber 50 both quickly and simply—without thereby stressing the adhesive bond between the profile element 10 and the vehicle pane 40 —a rib-shaped detent element 70 is provided within the snap-in recess 60 and runs in the longitudinal direction of the profile element 10 . Said detent element is at least partly elastically deforming, being made of a highly compliant material such as a thermoplastic elastomer (TPE), a foam rubber, or another appropriate material, and being designed in a manner that only a slight force is required to insert the detent element 51 of the water draining chamber 50 in the direction of assembly R 1 , whereas its extraction from said snap-in recess in the opposite direction R 2 requires a comparatively substantially larger force.
[0042] As shown in FIG. 1 , the detent element 70 is configured within the snap-in recess 60 at an angle α relative to the directions R 1 , R 2 and hence subtends an acute angle with the rib 51 of the water draining chamber 50 . Said detent element furthermore enters at least in part the engagement aperture 61 of said recess and may engage, within this recess, the rib 51 of the water draining chamber 50 in frictionally and/or geometrically interlocking manner, as a result of which, in the installed mode, said rib 51 is locked durably but detachably.
[0043] To reinforce the above feature, the detent element 70 is fitted at its free longitudinal edge 72 with a convex or a beaked edge 71 whereas the rib 51 of the water draining chamber 50 is fitted with an associated beaked edge 52 respectively indentation. In this manner, when the water draining chamber 50 is installed, the free end of the detent element 70 respectively its convex or beaked edge 71 can rest on said chamber's rib 51 which also runs in the longitudinal direction of the profile element 10 , and consequently permanent firm locking has been achieved.
[0044] FIG. 1 further shows that the detent element 70 as well as the seal 90 are affixed to the bearing rib 80 , namely in the region of the indentation 83 . Further said detent element comprises a tapered zone 74 between the connecting zone 73 at the bearing rib 80 on one hand and on the other the terminal convex or beaked edge 71 , resulting in an approximately concave cross-sectional surface. Said surface allows the detent element 70 to get out of the way laterally or transversely to its longitudinal direction as soon as the rib 51 of the water draining chamber 50 has been inserted into the snap-in recess. To enhance this effect, the rib 51 is fitted with a bevel or flank 55 which is able to press the detent element 70 to the side. Depending on the designed magnitude of the applied force used to insert the rib 51 into the snap-in recess 60 , the detent element 70 also may be cross-sectionally a wedge or a rectangle/parallelepiped.
[0045] Both the detent element 70 and the seal 90 are preferably firmly bonded to the bearing rib 80 . However they also may be integral with it.
[0046] FIG. 2 illustrates the sealing system constituted by the vehicle pane 40 , the profile element 10 affixed to said pane and the water draining chamber 50 as yet uninstalled. Accordingly the water draining chamber's rib 50 has not yet entered and engaged said profile element's snap-in recess 60 .
[0047] On the other hand FIG. 3 makes it plain that, when being inserted into the snap-in recess 60 , the rib 51 of the water draining chamber 50 displaces the detent element 70 entering said snap-in recess' engagement aperture 61 at an angle α to the direction of assembly R 1 . In the process the rib 51 by means of its bevel 55 laterally forces the detent element 70 into the indentation 83 of the bearing rib 80 , such displacement being implemented relatively easily on account of the said detent element's selected cross-section as well as its selected material. The water draining chamber's rib 51 therefore is inserted at relatively little effort into the profile element 10 of which the adhesive bond to the vehicle pane 40 is stressed very little. Additional support of the profile element 10 relative to the vehicle body is unnecessary.
[0048] As soon as the water draining chamber 50 has reached its final position, the detent element 70 engages the indentation 54 at the rib 51 , the convex or beaked edge 71 of the detent element 70 resting in frictionally and/or geometrically interlocking manner on the rib 51 . Accordingly the detent element 70 acts as a barb which affixes the water draining chamber 50 respectively its rib 51 against the profile element 10 in frictionally and geometrically interlocking manner in the snap-in recess 60 respectively at the profile element 10 .
[0049] When the water draining chamber 50 must be released from its position locked to the profile element 10 , the rib 51 must overcome the resistance of the barb 70 configured transversely to it within the snap-in recess 60 , however this time against a substantially larger resistance than encountered in the assembly procedure. Accordingly, the water draining chamber 50 is always anchored securely in the profile element 10 , though, when necessary, and as described above, it may also be extracted and, as also described above, it may be reinstalled without resort to a substantial force.
[0050] A reinforcing insert 26 , for instance a strip of aluminum or steel, is preferably fitted into the first segment 20 of the profile element 10 and into the resilient leg 62 of the second segment 30 . This reinforcing insert 26 may run as far as an inflection point 27 between the first segment 20 and the second segment 30 of the profile element, or, as shown, as far as into the resilient leg 62 . Said insert by-and-large follows the shape of the profile element 10 , though it may be shorter or longer than indicated. A reinforcing insert 81 within the bearing rib 80 increases both the dimensional stability of the profile element 10 and the bearing capacity of the rib 80 .
[0051] An omitted row of perforations/holes furthermore may be fitted into the central region of the partial surfaces of the first segment 20 . Two or more rows of holes in the central surface portion of the first segment 20 may also be used. In this manner a cement or the like in addition to an omitted bead of glue deposited on the first segment 20 of the profile element 10 may advance as far as the back side 44 of the pane 40 .
[0052] The present invention is not restricted to the above discussed embodiment modes and may be modified in many ways. Illustratively the detent element may be configured at the bearing rib 80 instead of at the resilient leg 62 . In that design the rib 51 of the water draining chamber 50 would be in mirror-image form. However two detent elements 70 also might be used, that would be mounted on the two sides of the rib 51 . In another variation, at least one detent element 70 is fitted on the rib 51 of the water draining chamber 50 . The convex or beaked edge 71 of the, respectively each, detent element 70 then would rest against the profile element 10 in the case of the installed position of the water draining chamber 50 , as a result of which the detent element engages frictionally and/or in geometrically interlocking manner the profile element. Furthermore, one detent element 70 each may be constituted at the profile element 10 and at the rib 51 of the water draining chamber 50 .
[0053] In an embodiment, the detent element 70 in the form of a barb allows inserting the rib 51 into the snap-in recess 60 without requiring a considerable force. On the other hand extracting the rib 51 out of the snap-in direction 60 is more arduous, so that the water draining chamber 50 is easily installed and firmly affixed and can be detached if needed.
[0054] In summary, the present invention relates to a profile element 10 serving to connect a vehicle pane 40 to a water draining case 50 , said structure 10 comprising a first segment 20 for connection to a vehicle pane 40 and a second segment 30 to detachably affix a water draining chamber 50 . The water draining chamber 50 is fitted with rib 51 which can be affixed in frictionally and/or geometrically interlocking manner in the snap-in recess 60 . At least one seal 90 may be inserted between the lower edge 42 of the vehicle pane 40 and the upper edge 53 of the water draining chamber 50 . Said seal constitutes a substantially smooth and flush transition between the surfaces of the vehicle pane 40 and the water draining chamber 50 .
[0055] A detent element 70 for the rib 51 of the water draining chamber 50 is designed in a manner that it facilitates inserting the rib 51 into the snap-in recess 60 of the profile element 10 while raising the resistance to extracting the rib 51 out of said snap-in recess.
[0056] The detent element 70 is at least partly elastically deforming and subtends an angle α with the direction of assembly, and as a result acts as a barb on the locked rib 51 of the water draining chamber 50 . The detent element 70 enters at least segment-wise the engagement aperture 61 of the snap-in recess 60 and rests by its convex or beaked edge 71 in its engaged state against the rib 51 of the water draining chamber 50 or against the profile element 10 which for that purposes are fitted with indentations 52 , 54 , 63 , 83 .
[0057] A bearing rib 80 is configured between the first and second segments 20 and 30 respectively of the profile element 10 and may be cross-sectionally wedge-shaped, L or U shaped. The minimum of one seal 90 projects outward from said bearing rib 80 .
[0058] The snap-in recess 60 is subtended by the bearing rib 80 and a resilient leg 62 which is cross-sectionally L, U or hook-shaped. The detent element 70 and the seal 90 may be integral with the bearing rib 80 or be firmly bonded to it and in particular may include a high-compliance, deforming convex element.
[0059] The profile element 10 and/or the detent element 70 and/or the resilient leg 90 may be made of a combination of materials, for instance in the form of a composite component which is soft externally and hard internally. The elasticity is enhanced by reinforcing inserts 26 , 81 . Appropriately the said contour structure's rest face 22 comprises contact zones that are mutually offset in height. An adhesive layer may be enclosed in between at the optionally perforated first segment 20 , for instance a double-sided adhesive tape, rests in contact with its opposite walls and also is optionally perforated.
[0060] A profile element 10 to connect a vehicle 40 with a water draining chamber 50 comprises a first segment 20 which can be affixed to said vehicle pane, and a second segment 30 which is fitted with a snap-in recess 60 to allow detachably affixing said box. This water draining chamber 50 is fitted with a rib 51 which is affixable in frictionally and/or geometrically interlocking manner in the snap-in recess 60 , further with at least one seal 60 subtending—in the installed position of the water draining chamber—a substantially smooth and flush transition zone between the vehicle pane 40 and the water draining chamber 50 . To assure both simple and rapid installation of the water draining chamber—without thereby stressing the connection between said profile element and vehicle pane, the invention provides at least one detent element 70 designed in a manner that insertion of the rib 51 of the water draining chamber 50 into the snap-in recess 60 in a first direction R 1 shall be facilitated but extraction of the rib 51 from the snap-in recess 60 in the opposite direction R 2 shall meet a larger resistance.
[0061] All features and advantages, including design details, spatial configurations and procedural steps, implicit in and explicit from the claims, the specification and the appended drawings, may be construed being inventive per se or in arbitrary combinations.
LIST OF REFERENCES
[0000]
A outer surface (of 40 )
G outer surface (of 50 )
R 1 direction
R 2 direction
K vehicle body
α angle
10 profile element
20 first segment
22 surface
24 adhesive layer/tape
26 reinforcing insert
27 inflection point
28 adhesive bead
30 second segment
40 vehicle pane
42 lower pane edge
44 back side
50 water draining chamber
51 rib
52 beaked-edge/indentation
53 upper edge
54 beak-edge/indentation
55 bevel/flank
60 snap-in recess
61 aperture
62 resilient leg
63 indentation
64 free end
70 detent element
71 beaked edge
72 free longitudinal edge
73 connecting zone
74 tapered zone
80 bearing rib
81 reinforcing insert
82 hard/soft boundary
83 indentation
84 space
90 sealing lip
91 bevel
92 beaked edge | A profile element for connecting a vehicle pane to a water draining chamber includes a U-shaped snap-in recess formed by a bearing rib and a resilient leg disposed below the bearing rib. At an entrance into the snap-in recess, the bearing rib protrudes downward towards the resilient leg and the resilient leg protrudes upward towards the bearing rib so as to define an engagement aperture into the snap-in recess between an upper-most part of the protrusion of the resilient leg and a lower-most part of the protrusion of the bearing rib. A detent element is disposed in the snap-in recess behind the engagement aperture in an insertion direction of a rib of the water draining chamber. | 1 |
BACKGROUND OF THE INVENTION
The invention relates to a self-locking safety belt reeling device with a vehicle sensitive and/or belt-sensitive controlled locking device and with a tightening device acting on the belt reeling shaft, comprised of a drive disc driven in rotation by a drive device, wherein the drive disc, upon actuation of the tightening device, is coupled by a tightening coupling to the belt reeling shaft, whereby a force limiting device comprising a torsion bar is provided that, on the one hand, is connected to the rotatable belt reeling shaft and, on the other hand, to a stationary abutment. Further provided is a pawl coupling that is actuated by the tightening device and comprises one or more force limiting pawls for switching on and off the force limiting device as a function of the functional states of the belt reeling device and/or of the tightening device.
A safety belt reeling device combined with a tightening device and a force limiting device, which can be switched on or off according to functional states, is known in different constructive embodiments especially from German Patent Application 43 31 027 and also from European Patent Application 0 627 345. In all of these embodiments the switching on or off of the force limiting device is achieved by a pawl coupling that is controlled by centrifugal force whereby the rotation of the belt reeling shaft caused by the tightening device or by forward movement of the buckled-in person when restrained results in a rotational acceleration and the deflection of the respectively arranged force limiting pawls as a component of the pawl coupling. Since between the functional state of tightening, on the one hand, and the functional state of restraining, on the other hand, a rotational reversal of the belt reeling shaft and thus a forced short term standstill of the belt reeling shaft results, with the known centrifugally controlled pawl couplings the disadvantage is observed that in certain functional positions the force limiting pawls will not remain in the deflected position but upon standstill, due to the loss of centrifugal force, respectively, upon impact, will return into their initial positions so that the directed switching of the force limiting device will not occur. The invention therefor has the object to eliminate this disadvantage for a self-locking safety belt reeling device with the aforementioned features and to provide for a safe control of the force limiting pawls for realizing the desired switched position.
SUMMARY OF THE INVENTION
The solution of this object results, including advantageous embodiments and developments, from the contents of the claims following this description.
The invention is based, in principle, on the idea that the pawl coupling comprises a connecting ring which is rotatable relative to the belt reeling shaft by a certain angular distance in the direction of rotation of the belt reeling shaft determined by the tightening process, whereby the relative rotation of the connecting ring is realized by the mass inertia of the belt reeling shaft relative to the drive disc of the tightening device at the beginning of the tightening step and actuates the force limiting pawl by a forced control into the position corresponding to the functional state. The invention has the advantage that, due to the forced control of the force limiting pawls, a rebound is avoided and the desired switching position is reliably ensured. This also prevents the disadvantage resulting from the reversal of rotational direction (cancellation of the centrifugal force) and the thus occurring short standstill. The forced control of the force limiting pawl is initiated in a simple manner by the relative movement of the coupling ring relative to the belt reeling shaft at the beginning of the tightening movement whereby this relative movement is realized with the already present means in the system, i.e., by employing the mass inertia of the belt reeling shaft relative to the drive of the tightening device. Accordingly, in comparison to known constructions additional components are not required.
A first embodiment of the invention is directed to the constructive embodiment of the aforementioned safety belt reeling shaft in which the torsion bar is arranged in a tubular shaft surrounding it and connected at the end facing the locking device fixedly to the tubular shaft that can be fixed in position by a locking member so as to serve as abutment and with its other end by the tightening coupling to the rotatable belt reeling shaft, whereby the pawl coupling is embodied as a force limiting pawl supported at the belt reeling shaft and engaging a toothing of the tubular shaft. This design is disclosed in detail in German Patent Application 43 31 072 and this disclosure is incorporated by reference. For effecting the forced control in this embodiment, of the invention it is suggested that the coupling ring, provided for the forced control of the force limiting pawl is arranged at the end face of the belt reeling shaft so as to be rotatable relative thereto until reaching a stop provided at the belt reeling shaft and controls in a forced manner by a pin-slot connection the force limiting pawl supported pivotably at the belt reeling shaft.
According to one embodiment of the invention, the coupling ring in its initial position is secured at the belt reeling shaft by a shearing pin. It may also be provided that the coupling ring is rotatable on the belt reeling shaft against the force of a return spring that is supported between the coupling ring and the belt reeling shaft in order to return the safety belt reeling device after the adjusted switched state into its normal function.
For constructive reasons, according to one embodiment of the invention, it may be expedient that the stop for the relative rotation of the coupling ring is provided at a stop ring separate from the belt reeling shaft and arranged adjacent to the coupling ring.
Inasmuch as in the aforementioned belt reeling device the tightening coupling is comprised of a tightening pawl pivotably connected to the drive disc and a toothed ring that is connected to the belt reeling shaft and surrounds with an inner toothing the coupling pawl, according to one embodiment of the invention, it may be provided that the toothed ring of the tightening coupling is embodied as a unitary part of the coupling ring.
A second embodiment of the invention relates to a constructive embodiment of the inventive safety belt reeling device in which the torsion bar is connected with one end directly to the rotatable belt reeling shaft and with the other end to the pawl coupling serving to realize the abutment, whereby the pawl coupling comprises a pawl fixedly stationarily connected to the torsion bar for force limiting pawls connected thereto and a toothed ring with an inner toothing for engagement by the force limiting pawls, whereby the toothed ring is secured at the housing after rotation about a certain angle. The pawl support, upon activation of the tightening device, is coupled by the tightening coupling to the drive disc. This constructive design is disclosed in detail in European patent application 0 627 345 and the disclosure is incorporated by reference. For effecting the forced control in this embodiment of the invention, it is provided that the coupling ring for controlling the force limiting pawl is arranged at the pawl support and is arranged thereat so as to be rotatable relative thereto until contacting a stop provided at the pawl support. The coupling ring comprises cams as well as an inner toothing for coupling the drive disc of the tightening device, whereby the cams, upon rotation of the coupling ring relative to the pawl support, force the force limiting pawls outwardly.
In the same manner as in the first embodiment it may also be provided that the coupling ring is secured at the pawl support by a shearing pin and, with respect to the return of the coupling ring into the initial position, a return spring is positioned between the coupling ring and the pawl support.
According to one embodiment of the invention it is provided that the coupling ring is positioned axially adjacent to the pawl support and engages the circumference of the pawl support with an axial outer projection to thereby secure the force limiting pawls in abutment at the pawl support. The outer projection has windows correlated with the force limiting pawls which, by movement of the coupling ring relative to the pawl support, are moved into a release position to allow penetration thereof by the force limiting pawls until engagement in the toothed ring takes place. This has the advantage that the deflection of the force limiting pawls during tightening takes place in a controlled manner.
With respect to the connection of the pawl support, respectively, of the coupling ring to the tightening coupling, according to one embodiment of the invention, it may be provided that the coupling ring is arranged adjacent to an annularly embodied pawl support and has an axially inner projection relative to the pawl support with an inner toothing for coupling the drive disc of the tightening device whereby the cams for a forced control of the force limiting pawls are radial projections at the inner projection.
BRIEF DESCRIPTION OF THE DRAWING
In the drawing embodiments of the invention are represented which will be explained in the following. It is shown in:
FIG. 1 a first embodiment of the belt reeling shaft of a safety belt reeling device with correlated tightening device as well as force limiting device in a perspective, exploded view;
FIG. 2 another embodiment of the invention of a safety belt reeling device including tightening device and force limiting device in a sectional view;
FIG. 3 a sectional view of the coupling between the tightening device, the force limiting device, and the belt reeling shaft for an object according to FIG. 2 in the initial state;
FIG. 4 the object of FIG. 3 after actuation of the tightening device.
DESCRIPTION OF PREFERRED EMBODIMENTS
In the embodiment of the invention represented in FIG. 1, only the belt reeling shaft as well as the necessary parts for the connection of the tightening device as well as of the force limiting device are represented of the safety belt reeling device. As a component of the force limiting device a tubular shaft 11 is inserted into the belt reeling shaft 10, whereby the tubular shaft 11 has at one end a profiled head 13 which can be locked by a non-represented locking system of the safety belt reeling device in the case of actuation. In the interior of the tubular shaft 11 a torsion bar 12 is arranged which at its two ends has respectively formed pieces 14 for providing a fixed connection. The end of the torsion bar 12 facing the profiled head 13 is fixedly connected to the tubular shaft 11 while the other end of the torsion bar 12 is fixedly connected to a toothed ring 15 which has an inner toothing 16 that is a component of the belt tightening coupling. This belt tightening coupling is comprised of a tightening pawl 17 connected to the drive disc 18 of a non-represented cable tightening device which upon actuation of the tightening device is deflected radially until it engages the inner toothing 16 of the toothed ring 15 and thus transmits the rotational movement of the drive disc 18 onto the toothed ring 15.
The tubular shaft 11 is connected with its end opposite the profiled head 13 to an outer end face toothing 19 which engages the inner toothing 22 of a toothed ring 20 positioned on the tubular shaft so that the tubular shaft 11 and the toothed ring 20 are fixedly coupled to one another.
The toothed ring 20 has an outer toothing 21 which is engaged by a force limiting pawl 27 supported on the belt reeling shaft 10 so that in this initial position secured by a non-represented shearing pin a fixed connection between the belt reeling shaft 10 and the tubular shaft 11 is provided.
Axially adjacent to the belt reeling shaft 10 a connecting ring 23 is supported at the end face of the belt reeling shaft 10. It is supported such that it can rotate relative to the belt reeling shaft by a certain angular distance but is fixedly secured outside of this rotational range by stops fixedly connected to the belt reeling shaft 10, which will be explained in the following. Since the rotation of the coupling ring 23 relative to the belt reeling shaft 10 is to be employed for the forced control of the force limiting pawl 27, the force limiting pawl 27 has a pin 28 which is guided in a slot 29 of the coupling ring 23 such that upon rotation of the coupling ring 23 relative to the belt reeling shaft 10 the force limiting pawl 27 is forced outwardly and thus is disengaged from the outer toothing 21 of the toothed ring 20. For limiting the rotational path of the coupling ring 23, a separate stop ring 24 with a stop 25 is provided whereby a return spring 26 is supported between the stop ring 24 and the coupling ring 23. The coupling ring 23 is then also connected to the toothed ring 15 as a component of the tightening coupling such that the coupling ring 23 and the toothed ring 15 always rotate with one another. For this purpose, the coupling ring 23 and the toothed ring 15 can be embodied as a single component (not represented). During normal operation of the safety belt reeling device, the belt reeling shaft 10 rotates in the removal direction as well as in the winding direction, and since the coupling ring 23 and the stop ring 24 at the end faces are initially connected to the belt reeling shaft 10, the aforementioned components also rotate with the rotational movement of the belt reeling shaft 10. Since furthermore the tubular shaft 11 is coupled by the outer toothing 21 of the toothed ring 20 connected to the tubular shaft 11 and the engaged force limiting pawl 27 with the coupling ring 23, the tubular shaft also rotates together with the belt reeling shaft 10 and, because of the form locking connection of the torsion bar 12 with the end of the tubular shaft 11 facing the profiled head 13 and the form-locking connection at its other end to the toothed ring 15 that is a component of the belt tightening coupling, the torsion bar during normal operation of belt reeling shaft will also rotate. Accordingly, the components of the tightening coupling as well as the components of the force limiting device are switched off during normal operation of the safety belt reeling device.
In the case of activation, when the tightening device is actuated, the drive disc 18 is rotated in the tightening direction (arrow 31) in the clockwise direction. Due to the resulting rotational acceleration, the tightening pawl 17 is deflected and engages the inner toothing 16 of the toothed ring 15. Because of the form-locking connections, the rotation of the toothed ring 15 results in a rotational acceleration of the coupling ring 23. Due to the adjusted relative movement possibility of the coupling ring 23 relative to the belt reeling shaft 10, a rotation of the coupling ring 23 relative to the belt reeling shaft 10 occurs first because the belt reeling shaft 10, due to its own mass inertia, will be slowed with respect to the rotational acceleration acting on the coupling ring 23. Due to this relative movement, after breaking off of the pin, the coupling ring 23 will radially outwardly guide the force limiting pawl 27 by the pin-slot connection 28, 29 in a forced control movement and will disengage it from the outer toothing 21 of the toothed ring 20. Accordingly, the tightening process results in the force limiting device being switched on. The stop ring 24 will then entrain the shaft 10. When now, after completion of the tightening movement, a belt removal is caused by the forward movement of the buckled-in passenger, a rotational reversal will take place with respect to the belt reeling shaft 10 so that the belt reeling shaft 10 will turn in the direction of arrow 30. At this point in time the non-represented locking system will be activated and will lock via the profiled head 13 the tubular shaft 11 and the end of the torsion bar 12 fixedly connected thereto in order to provide a stationary abutment. The rotation of the belt reeling shaft 10 in the direction of arrow 30 is now transmitted by the coupling ring 23 rotating with the belt reeling shaft 10 and the toothed ring 15 connected thereto onto the end of the torsion bar 12 that is form-lockingly secured in the toothed ring 15 so that with the belt removal in the direction of arrow 30 a rotation of the torsion rod with simultaneous work uptake results. During the rotational reversal the drive disc 18 remains in engagement with the toothed ring 15 and thus with the coupling ring 23, whereby due to the mass inertia of the drive disc 18 the coupling ring 23 is further loaded with a force that considerably surpasses the force of the return spring 26 so that the coupling ring 23 remains in its position rotated relative to the belt reeling shaft 10. The force limiting pawl 27 remains disengaged from the outer toothing 21 of the toothed ring 20.
When after completion of such a locking process, belt is wound onto the belt reeling shaft by the return spring, then the belt reeling shaft 10 will "pass" in the direction of arrow 31 the "stationary drive" disc 18 so that the tightening pawl 17 will be disengaged from the inner toothing 16 of the toothed ring 15. Accordingly, the coupling ring 23 will come free from the load of the drive disc 18 and the return spring 26 will return the coupling ring 23 into its initial position relative to the belt reeling shaft 10 whereby the pin-slot connection 28, 29 will again return the force limiting pawl 27 into the outer toothing 21 of the toothed ring 20 connected to the tubular shaft 11. Thus, the force limiting device is deactivated and the safety belt reeling device is again functional.
The second embodiment of the invention represented in FIGS. 2-4 is concerned with a safety belt reeling device with tightening device and force limiting device in which the torsion bar with one end is directly connected to the rotatable belt reeling shaft and with its other end is connected to a counter coupling providing the abutment. In the drawings referring to this embodiment only the components are represented that are required for understanding the invention.
The belt reeling shaft 10 is supported in a U-shaped belt reeling housing 35. At one end it has a locking toothing 36 which is engaged by a non-represented locking pawl pivotably supported in the housing 35 and engaging the locking toothing in a locking situation whereby the movement of the locking pawl is controlled by a vehicle-sensitive and/or belt-sensitive control system that is not represented in detail.
The tightening device connected to one side of the belt reeling shaft is comprised of a drive cable 37 acting when actuated onto the drive disc 38. The pawl wheel 39 is fixedly connected to the drive disc 38. Tightening pawls 40 are connected to the pawl wheel 39 so as to be radially pivotable in order to provide coupling to the belt reeling shaft 10 in a manner to be disclosed in the following.
The force limiting device is comprised of a torsion bar 12 which is connected by a shaped piece 14 directly in a positive-locking manner to the belt reeling shaft 10 and with its other end provided with a shaped piece 14 positive-lockingly in a pawl support 41 supported thereat. The torsion bar 12 extends past the shaped piece 14 having correlated therewith the pawl support 41 as a shaft so that the pawl wheel 39 and its integral drive disc 38 are supported rotatably on this extension of the torsion bar 12. At the pawl support 41 four force-limiting pawls 42 are circumferentially distributed so as to be radially deflectable whereby the force limiting pawls 42 have coordinated therewith a toothed ring 43 with an inner toothing 43a. The toothed ring 43 is arranged at a corresponding leg of the housing 35 such that it is rotatable about an angle toward a stop 44 at the housing 35. The thus possible rotation of the toothed ring 43 relative to the housing 35 allows a controlled disengagement (not represented) of the locking pawl from the locking toothing 36 of the belt reeling shaft. A correspondingly arranged return spring 53 serves as a return force of the toothed ring 43 into its initial position, which will be disclosed in the following.
For a forced actuation of the force limiting pawls 42, being forced outwardly by a spring element 55, a coupling ring 45 is arranged at the coupling support 41 which is rotatable by a certain angular distance relative to the support. The movement of the coupling ring 45 relative to the pawl support 41 is limited by a corresponding stop 46. The coupling ring 45 comprises two concentrically arranged, axially extending projections whereby the outer projection 47 surrounds the circumference of the pawl support 41 and secures the force limiting pawls 42 in the engaged position. The outer projection 47 has windows 48 which, upon rotation of the coupling ring 45 relative to the pawl support 41, will be positioned such that the force limiting pawls 42 can engage through the windows 48 the inner toothing 43a of the toothed ring 43.
The pawl support 41 furthermore has an inner projection 49 which is provided with an inner toothing 50 arranged such that the tightening pawls 40 of the pawl wheel 39 upon actuation of the tightening device will engage the inner toothing 50 of the coupling ring 45. At the outer circumference of the inner projection 49 radially projecting cams 51 are arranged relative to the force limiting pawls 42 such that upon rotation of the coupling ring 45 relative to the pawl support the cams 51 will slide under the force limiting pawls 42 and thus force them into engagement with the inner toothing 43a of the toothed ring 43 and secure the deflected position of the force limiting pawls 42. For a return into the initial position, the coupling ring 45 is supported by a return spring 52 at the pawl support 41.
During the normal function of the safety belt reeling device, the force limiting pawls 42 are disengaged with respect to the toothed ring 43 so that upon rotation of the belt reeling shaft 10 the torsion bar 12 with the pawl support 41 arranged thereat can also rotate. The force limiting device is switched off. The tightening pawls 40 in their non-deflected normal position are also not in engagement with the toothing 50 of the coupling ring 45 so that the belt reeling shaft 10 can rotate freely.
When the tightening device is activated, the pawl wheel 39 is rotated by the drive disc 38 such that the tightening pawls 40 will radially engage the inner projection 49 of the coupling ring 45 and its inner toothing 50. This engagement causes the coupling ring 45 to be rotated whereby the pawl support 41, because of the connection of the torsion bar 12 to the belt reeling shaft 10 and because of its mass inertia, will stay behind the rotational movement of the coupling ring 45. In this manner, after breaking off of the correspondingly arranged shearing pin 45, a relative movement of the coupling ring 45 to the pawl support 41 against a return spring 52 will result which causes, on the one hand, the windows 48 in the outer projection 47 to be positioned above the force limiting pawls 42, and, on the other hand, the cams 51 at the inner projection 49 to move the force limiting pawls radially outwardly and secure them in this position. Upon rotation of the belt reeling shaft in the tightening direction, the force limiting pawls 42 due to the correlation of the inner toothing 43a of the tooth ring 43 will pass across the inner toothing 43a so that in this state no coupling is realized
When after completion of the tightening device with initiated belt removal a reversal of the rotational direction occurs, the force limiting pawls 42 will engage the inner toothing 43a of the toothed ring 43 because of their deflected position caused the cams 51 of the coupling ring 45, whereby the toothed ring 43 is rotated by the predetermined angular distance relative to the housing 45 to the stop 44 and thus retains the locking pawl out of engagement at the locking toothing 36 of the belt reeling shaft 10. In this position, the toothed ring 43 provides the abutment, because of the pawl support 41 is secured by the force limiting pawls 42 and the form-locking connection to the one end of the torsion bar 12, for the force-compensating deformation of the torsion bar 12 upon further rotation of the belt reeling shaft 10 in the removal direction of the safety belt.
When after completion of the load movement a winding of the safety belt is initiated by the non-represented return spring, the return springs 53 for the toothed ring 43 and the return spring 52 for the coupling ring 45 return the parts relative to the housing 35 and the pawl support 41 into the initial position so that the safety belt reeling device is returned into its functional position.
The features of the object of these documents disclosed in the above description, the claims, the abstract, and the drawing maybe important individually as well as in any suitable combination for realizing the invention in its different embodiments.
The specification incorporates by reference the entire disclosure of German priority document 196 09 524.7 of Mar. 11, 1996, as well as of International Application PCT/EP97/01151 of Mar. 7, 1997.
The present invention is, of course, in no way restricted to the specific disclosure of the specification and drawings, but also encompasses any modifications within the scope of the appended claims. | A safety belt reeling device has a belt reeling shaft lockable by a vehicle-sensitive and/or belt-sensitive locking device. A tightening device is provided and a tightening coupling connects the tightening device to the belt reeling shaft when the tightening device is actuated. The tightening device has a drive disc and a drive device for driving the drive disc. A force limiting device having a torsion bar is connected to the belt reeling shaft and to a stationary abutment. A pawl coupling is activated by a tightening movement of the tightening device and the pawl coupling has at least one force limiting pawl for switching on or off the force limiting device as a function of functional states of the safety belt reeling device. The pawl coupling also has a coupling ring performing a rotation by an angular distance relative to the belt reeling shaft in a rotational direction of the belt reeling shaft defined by the tightening movement, wherein the relative rotation of the coupling ring is realized by the mass inertia of the belt reeling shaft, effective at the start of the tightening movement, relative to the drive disc. A forced control controlling the force limiting pawl is provided for switching on or off the force limiting device. | 1 |
SPECIFIC REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional application which claims priority to and incorporates by reference application Ser. No. 09/550,986 filed Apr. 17, 2000.
BACKGROUND OF THE INVENTION
[0002] Obstructive sleep apnea is a common disorder that involves tissue occlusion of the nasopharyngeal airway during sleep which impedes a patient's normal breathing cycle. Multiple sequential apnea episodes may result in severe sleep disruption of which the patient may not even be aware. Moreover, swollen tissue in the airway often results in excessive heavy snoring. Extreme sleep apnea is a serious disease which may affect as much as three percent of the adult population, and heavy snoring is much more common, particularly with overweight individuals.
[0003] Surgical intervention is always an option in alleviating obstructive sleep apnea or heavy snoring, however, most patients prefer to address the problem with non-invasive treatment. One treatment program involves the use of continuous positive airway pressure delivered to the patient's airway to maintain the airway in a continuously open state during sleep. The equipment required to deliver continuous positive airway pressure to the airway of a patient includes a fan or blower for generating a pressurized flow through a hose coupled to a mask or nasal device which the patient places over his or her nose and uses straps about the head to fasten the device in place.
[0004] Many patients cannot tolerate the application of continuous positive airway pressure, particularly because of the discomfort associated with exhalation against a continuous positive pressure. An attempt has been made to alleviate this problem by the provision of a method and apparatus which provides a substantially constant elevated airway pressure to the patient's airway, with periodic short term reductions of the elevated airway pressure to a pressure of lesser magnitude. A further advance in such treatment involves the application of alternative high- and low-level positive airway pressure wherein the low-level pressure coincides with the breath exhalation of the patient's breathing cycle.
[0005] A method and apparatus for the application of continuous positive airway pressure to a patient's airway is disclosed in U.S. Pat. No. 4,655,213, issued to Rapoport et al. The concept of providing a substantially constant elevated airway pressure with periodic short-term pressure reductions is disclosed in U.S. Pat. 4,773,441, issued to John B. Downs. A bi-level system of applying alternating high- and low-level positive airway pressure to a patient's airway is disclosed in U.S. Pat. No. 5,148,802, issued to Sanders et al.
[0006] The methods and apparatus disclosed in the prior art for treating patients afflicted with such maladies as sleep apnea and snoring present a number of problems which need to be addressed. The equipment utilized in such treatment is far too bulky and cumbersome. The air stream delivered to the patient tends to dehydrate the nasopharyngeal tissue. The unnatural sensation and discomfort experienced by the patient in over-coming the positive pressure during breath exhalation results in many patients abandoning the use of a system that is in all other respects quite beneficial.
SUMMARY OF THE INVENTION
[0007] The present invention comprehends the treatment of such disorders as obstructive sleep apnea or heavy snoring by providing an apparatus capable of delivering a pressurized burst or pulse of air to a patient's nasopharyngeal airway at the moment of termination of the patient's breath exhalation during the breathing cycle. The pulse of pressurized airflow is sufficient to prevent the development of airway tissue occlusion and maintain the airway open for normal breathing.
[0008] Hence, it is a primary objective of the present invention to provide a method of alleviating sleep apnea or snoring by delivering ambient air to a patient's airway in the form of an air bolus, wherein the patient's exhaled air is utilized to actuate an energy storing means to cause delivery of the air bolus into the airway.
[0009] Still another objective of the present invention is to provide an apparatus capable of providing a pressurized pulse of air through a nasal device and into the nasopharyngeal airway of a sleeping patient, wherein the pressurized airflow is triggered by the breath exhalation of the patient and will continue sequentially with each exhaled breath.
[0010] It is also an objective of the present invention to provide an apparatus as heretofore described which preferably includes a nasal device for attachment to a patient's nose, and a housing with a chamber capable of storing a fresh air supply for release to the nasal device and into the patient's airway to thus promote a normal breathing cycle.
[0011] It is also an objective of the present invention to provide an apparatus as heretofore described which is self-contained as a unitized structure that obviates the need for auxiliary remote bedside equipment requiring a large fan or compressor.
[0012] Practice of the method of this invention comprises the steps of providing a primary airflow conduit for delivering ambient air into the patient's airway and providing a bolus chamber in airflow connection with the airflow conduit which is capable of delivering a bolus of ambient air. Energy storing means responsive to the patient's breath exhalation is utilized to force the bolus of air from the chamber and through the conduit and into the patient's airway. The patient's exhaled air is used to actuate or trigger the energy storing means and cause, by the release of its energy, the delivery of the bolus of air to the patient's airway.
[0013] The invention also provides an apparatus in the form of a unitary structure, such as a containment housing, with the housing being coupled to a nasal device. The nasal device may be a mask sealed to the patient's face and about the nose or a device comprising a pair of nasal delivery members, such as disclosed in U.S. Pat. No. 5,687,715, issued to Landis et al. The containment housing of the apparatus includes a first chamber for receiving breath exhaled by the patient and a second chamber for storing fresh air for delivery back to the patient at a predetermined time during the patient's breathing cycle. The chambers are expandable and operatively interconnected whereby expansion of the first chamber causes expansion of the second chamber. An energy storing means is provided within the containment housing which is adapted to operate, at the moment of completion of the patient's breath exhalation, to contract both of the expandable chambers and cause a momentary burst of pressurized airflow to be ejected from the second chamber and through the nasal device to the patient's airway. The pressurized airflow is only momentary, whereby completion of air inhalation occurs naturally and voluntarily by the patient.
[0014] Details of the method of the present invention and the elements and structural characteristics of several embodiments of the apparatus will become apparent from the ensuing detailed description when considered in reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] [0015]FIG. 1 is a schematic representation which illustrates both the method and basic apparatus for practicing the present invention.
[0016] [0016]FIGS. 2 and 3 are schematic representations which illustrate the physical principles underlying the method and basic operation of the apparatus of the present invention.
[0017] [0017]FIGS. 4 and 5 are elevational views in vertical section of a bench-test embodiment of the apparatus of the present invention.
[0018] [0018]FIG. 6 is an elevational view in vertical section of the apparatus which incorporates the structural and operative characteristics first disclosed in FIGS. 1 - 5 .
[0019] [0019]FIG. 7 is an elevational view in partial vertical section illustrating an alternative embodiment of the apparatus of the present invention.
[0020] [0020]FIG. 8 is an elevational view in vertical section illustrating still another alternative form for the apparatus of the present invention.
[0021] [0021]FIG. 9 is a perspective view of certain components intended for use in still another embodiment of the present invention.
[0022] [0022]FIG. 10 illustrates a novel or ancillary use contemplated for the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] [0023]FIG. 1 schematically illustrates an assembly 10 including an airflow generator 12 , an electromagnetic solenoid 14 , a dual valve assembly 16 , a normally-open electrical switch 18 , and a mask 20 . The airflow generator 12 may be a blower or fan of the type used to produce a pressurized airflow. The solid line arrows mark the air stream flow path, beginning with ambient air drawn into the airflow generator as indicated by arrow 22 . The electric current to operate the flow generator is supplied through conductors 24 and 26 , which also supply current to solenoid 14 through switch 18 . The airflow generator 12 is intended to operate continuously whereby a constant head of pressurized air is maintained to the solenoid 14 . However, the solenoid 14 is normally closed and will permit air passage there through to the dual valve assembly 16 only when the solenoid 14 is caused to open by switch 18 .
[0024] The dual valve assembly 16 of FIG. 1 includes a flexible circular diaphragm 28 and a disc valve 30 mounted on the diaphragm 28 . In its relaxed position (not shown), the diaphragm 28 will cover and seal apertures, such as aperture 32 and aperture 34 . The disc valve 30 is a circular flexible thin rubber membrane which normally seals against the inside surface of the diaphragm 28 but will flex open in response to pressurized airflow from the solenoid 14 and allow the airflow to pass through the valve arrangement and thence into mask 20 .
[0025] It should be noted that the mask 20 is provided with a normally-closed disc valve 36 which will respond to inhalation by the patient and open to permit entry of ambient air. The mask 20 is meant to be worn in sealed relation to the nose of a patient whereby ambient air during inhalation will pass into the mask past valve 36 . Exhaled breath will cause valve 36 to close whereby the breath flow will be in the direction of the dotted line arrow 38 and into the dual valve assembly 16 . Breath pressure entering the dual valve assembly 16 causes the disc 30 to seal against the diaphragm 28 and stretches the diaphragm 28 from a sealing linear disposition (not shown) to the position shown in FIG. 1. A spring-biased switch trigger or toggle 40 extending from switch 18 is contacted by the outwardly-flexed diaphragm 28 whereby the toggle 40 is pivoted from left to right as shown in FIG. 1. This pivoting action of the toggle 40 sets the switch internally whereby, as the diaphragm 28 relaxes, the toggle 40 will pivot back to its original position and, at the same, close internal contacts of the toggle 40 to complete the electrical circuit to the solenoid 14 . The solenoid 14 is thereby caused to cycle open and then immediately re-close after having permitted a burst of pressurized air to move into the dual valve assembly 16 and past the disc valve 30 and into the mask 20 . The pressurized airflow burst is directed into the nasopharyngeal airway of the patient as the patient's inhalation action occurs, and ambient air moves through valve 36 to allow the patient to complete the breath intake voluntarily. The subsequent exhalation by the patient repeats the described process whereby a pulse or burst of pressurized air is delivered to the mask 20 and thence to the patient's airway as a function of each breathing cycle.
[0026] Although FIG. 1 broadly illustrates the underlying method of the present invention, it is preferred that the apparatus for practicing the method be contained in a compact housing positioned adjacent the head of the patient and that it is not dependent upon a continuously operating bedside blower or household electrical connection for its energy source. Presently preferred embodiments of the invention involve utilization of dual chambers contained in a compact housing, as illustrated and explained hereinafter with references to FIGS. 2 - 8 .
[0027] [0027]FIGS. 2 and 3 demonstrate the physical principles underlying the mechanical operation of the several embodiments set forth and hereafter discussed in reference to FIGS. 4 - 8 . FIG. 2 shows a pneumatically expandable-contractible exhalation chamber 50 that becomes inflated by the exhaled air from a patient at a certain pressure above atmospheric pressure so that a top plate 52 of the chamber 50 , having an area A 1 , is raised against a compressible elastic element 54 . The elastic element 54 may be a compression spring having a constant K. The total vertical force exerted against the elastic element 54 is the product exhaled air pressure multiplied by the top plate area Al. The elastic element 54 is compressed until its downward force equals the upward force of the top plate 52 . An equilibrium position is obtained when the total upward force equals the spring constant multiplied by a distance d, where d is the distance of movement measuring the shortening of the elastic element 54 .
[0028] [0028]FIG. 3 shows a pneumatically expandable-contractible bolus chamber 60 that works against an elastic element 54 1 . The force in the compressed elastic element 54 1 is then applied to the bolus chamber 60 that is already filled with fresh air at atmospheric pressure when the exhaled breath is released from chamber 50 . The elastic element 54 1 exerts a downward force on a top plate 62 of the chamber 60 . The top plate 62 has an area A 2 , where A 1 (FIG. 2) is greater than A 2 . The air contained in the chamber 60 is under a positive initial pressure which is available to create a momentary airflow or bolus capable of relieving an apneic obstruction in a patient's airway. Valve and linkage means (not shown) operatively-connected between chamber 50 and chamber 60 would be utilized to mechanically translate the expanding action of chamber 50 to cause chamber 60 to simultaneously expand and draw in ambient air, and to allow both chambers to simultaneously expand and draw in ambient air, and to allow both chambers to simultaneously contract when the momentary positive airflow (bolus) has been ejected from chamber 60 .
[0029] [0029]FIGS. 4 and 5 illustrate bench model apparatus for practicing and demonstrating the method of the present invention. FIG. 4 shows a structure or apparatus 70 defining an exhalation chamber 72 and a bolus chamber 74 . In the use of the apparatus exhaled breath from the patient enters the exhalation chamber 72 through an entry port 76 . Inboard from the entry port 76 is a circular semi-flexible silicon disc 78 a which co acts with spaced-apart valve seats 78 b and 78 c . The disc 78 a is movable between a first position, as shown in FIG. 4, to a second position, as shown in FIG. 5, and is responsive to low pressure airflow to change its position. Air enters chamber 72 through entry port 76 , causing the disc 78 a to close off an outlet passage 84 whereby all entering air will flow to the chamber 72 . Sidewall structure serves as linkage 86 between the chambers. The expansion of chamber 72 in response to airflow directed thereto through the entry port 76 causes the linkage 86 to shift to the left as shown in FIG. 4 also undergoes expansion. Both of the chambers 72 and 74 have pleated accordion-like exterior sidewalls 88 and 90 which facilitate expansion of the chambers. As chamber 74 expands from the disposition shown in FIG. 4 to that which is shown in FIG. 5, and in response to the expansion of chamber 72 , motion of linkage 86 causes chamber 74 to expand and draw air in through a central passage 92 . The airflow through passage 92 moves past open flapper valve 80 and into the chamber 74 . The initial negative pressure in chamber 74 as it begins to expand causes a valve 82 to close and valve 80 to open whereby the chamber 74 takes in ambient air through the passage 92 . The expansion of the chambers 72 and 74 and the movement of linkage 86 causes a compression spring 94 to compress from its expanded disposition shown in FIG. 4 to a contracted position as shown in FIG. 5. When both chambers 72 and 74 have fully expanded and the exhalation has ended, the force of energy in the spring 94 causes the linkage 86 to shift back from the disposition shown in FIG. 5 to that which is shown in FIG. 4 whereby the volume of air in each chamber is pressurized to create simultaneous discharge airflows. Specifically, the lack of pressure from exhalation and contraction of chamber 72 causes the valve disc 78 a to close off the port 76 whereby air from the chamber 72 will be discharged through the outlet 84 . Simultaneously, contraction of the chamber 74 causes valve 80 to close and valve 82 to open and eject pressurized air though passage or discharge port 96 . The bolus of air forced out of chamber 74 past valve 82 constitutes air available for delivery to a patient's airway.
[0030] [0030]FIG. 6 illustrates apparatus in accordance with the present invention which operates pursuant to the principles explained in reference to FIGS. 2 - 5 . The apparatus 104 shown in FIG. 6 comprises a mask 106 and a housing 108 . The housing 108 is rigidly attached to the mask assembly whereby the mask 106 , once strapped in operative position against the face of a patient, serves as a housing support. In the embodiment of the invention illustrated in FIG. 6, it is not particularly important that the mask seals against the patient's face because a nasal device 110 is utilized for airflow communication attachment to the patient's nares as hereafter explained in greater detail. Within the housing 108 is a bolus chamber 112 and an exhalation chamber comprised of four compartments 114 , 116 , 118 , and 120 . The housing 108 has a central air passage 122 adapted to take in ambient air through a filter 124 . The air passage 122 constitutes a conduit extending from the filter 124 and centrally through the housing 108 and into the bolus chamber 112 . The apparatus 104 as heretofore described presents a means of practicing the method of the invention in a unitary compact form that is relatively simple in its operational concept. With the mask 106 disposed against the face and about the nose of the patient, air is inhaled centrally through the housing passage 122 . Valve structure 132 opens during inhalation whereby the air moves from the passage 122 and across the bolus chamber 112 and thence past the valve structure 132 and through a conduit 126 to the patient's airway. The valve structure 132 constitutes a stretchable diaphragm 132 a , a flexible valve disc 132 b carried on the diaphragm, and opposed valve seats 132 c and 132 d . The valve 132 is a dual valve structure which normally seals against the valve seat 132 c to prevent passage of air from passage 122 to and into conduit 126 . The valve structure is a diaphragm 132 a that supports a flexible disc 132 b that normally seals against an opening in the center of the diaphragm 132 a . The valve 132 allows airflow in one direction only by the peripheral flexure of the disc 132 b away from the diaphragm 132 a , and the diaphragm 132 a is capable of stretching or rolling, in response to airflow from passage 122 , to passage 146 . Inhalation by the patient though the nose connection 110 establishes an ambient airflow into the filter 124 , across the passage 122 , and through the valve 164 and 132 to the conduit 126 . Upon exhalation, airflow from the airway of the patient is delivered through conduit 126 and downwardly into passage 146 , with the valve 132 preventing any airflow into bolus chamber 112 . The exhaled air stream from the patient moves through the passage 146 and into valve structure 148 and thence into a manifold or distribution chamber 150 . The pressurized airflow from the manifold 150 is distributed through openings 152 into compartments 114 - 120 , which constitute the exhalation chamber.
[0031] The resultant build-up of air pressure within the compartments 114 - 120 of the exhalation chamber causes a shift in the internally-disposed rigid linkage 162 . The linkage 162 is adapted to shift from a chamber-empty position (not shown) and to the right, as viewed in FIG. 6, to a chamber-filled position. As the exhalation chamber takes in air and expands, ambient airflow causes valve 164 to open to allow the ambient air to fill bolus chamber 112 . Termination of the patient's exhaled breath results in a slight back pressure in the manifold 150 , causing the disc 148 a to shift from its sealed position against valve seat 148 b to a second sealed position against valve seat 148 c . An energy storing means, in the form of compression spring 166 , acts to push the rigid linkage 162 from right to left as viewed in FIG. 6, thereby causing contraction of the exhalation chamber and the bolus chamber 112 .
[0032] This results in the air within the exhalation chamber compartments 114 - 120 to be expelled through outlet port 154 . Air pressure within the bolus chamber 112 causes valve 164 to close whereby the bolus of air is forced against the diaphragm 132 such that disc 132 b will peripherally flex to allow the bolus to proceed into conduit 126 and thence through the nasal connection 110 and into the patient's airway. The ambient air previously captured in the bolus chamber 112 is forced as a pulse or thrust into the patient's airway just as the patient is starting to inhale. The bolus of air delivered to the patient's airway is sufficient to cause the inhalation to begin. The apneic obstruction in the airway is caused to relax whereby the patient finishes the breath inhalation as part of the natural breathing cycle.
[0033] Also illustrated in FIG. 6 is a reservoir 170 into which medication in liquid form may be stored and allowed to disperse into the bolus chamber 112 , the rate of dispersal being controlled by a metering device 172 . Many patients who are afflicted with sleep apnea also suffer asthmatic symptoms, including swelling of mucous membranes and bronchial tube spasms manifested by shortness of breath, whereby gasping causes the individual to awaken. The administration of medication into the air stream and thence into the bronchial tubes during inhalation is now common and can be quite effective in promoting natural sleep. The provision of the reservoir 170 for this purpose, whereby droplets of medication can be metered into the bolus of air in the chamber 112 , is an elective option that can be made available to the user of the device illustrated in FIG. 6.
[0034] [0034]FIG. 7 illustrates an alternate embodiment of the apparatus of the present invention comprising a unified structure 180 . The structure 180 includes a housing 182 coupled to a mask 184 . Within the housing 182 is a bolus chamber 186 partially defined by a flexible diaphragm 188 . A nasal device 214 constitutes a means for attaching the apparatus in flow communication with a patient's airway. The function of apparatus 180 begins immediately upon it being placed in its operative position, with the nasal device 214 inserted into the patient's nares. As the patient inhales, ambient air enters through inlet 190 and moves through passage 194 and thence into the chamber 186 . Flapper valve 198 pivots to an open position during inhalation. Inhalation continues by passage of air through the conduit 200 and into the patient's airway. Exhaled breath passes out through the conduit 200 and into the chamber 186 . A slight pressure is sufficient to close valve 198 whereby the exhaled breath progresses past open valve 202 and outwardly through passage 204 . A pressure-sensitive electrical switch 206 is caused to close its contacts by the exhaled breath moving thereagainst, completing a circuit to an energy storing means in the form of batteries 208 that actuate a solenoid 210 . Closure of the switch 206 is only momentary and sufficient to energize the solenoid 210 whereby its plunger 212 acts against the diaphragm 188 , causing the diaphragm to flex from right to left as shown in FIG. 7, and then return to its start position. The resulting increased air pressure within the chamber 186 is forced through the conduit 200 and into the patient's airway. Means, in the form of a thumb screw 216 threaded into an accommodating aperture in the housing 182 , may be utilized to regulate the intensity of the air pressure bolus within the chamber 186 by allowing minimal controlled leakage.
[0035] [0035]FIG. 8 illustrates apparatus 220 which utilizes the interaction of permanent magnets to cause delivery of a bolus of air to the patient's airway. The apparatus 220 comprises a housing 222 and a mask 224 . The mask 224 must, in this embodiment, be of the type that seals tightly about the nose of the patient whereby breathing occurs entirely through the apparatus. Within the housing 222 is a bolus chamber 225 partially defined by a flexible rolling diaphragm 230 . Centrally located on the diaphragm 230 is a flexible disc valve 230 A which normally blocks apertures 234 and 236 provided in the face of a piston 238 . The only outlet from the chamber 225 is a passage 240 normally closed by a valve structure 244 . The valve structure 244 comprises a flexible diaphragm 244 a with openings 244 b therethrough and a centrally-attached flexible disc 244 c . The piston 238 is mounted to be reciprocal within the housing 222 from a retracted position, as shown in FIG. 8, to a fully extended position which would be to the left.
[0036] To facilitate its operation, the apparatus 220 is positioned: usually strapped in place, against a patient's face whereby the nose is within the mask 224 . Ambient air is inhaled by the patient through an opening 246 . The inhaled airflow is drawn through the hollow body of the piston 238 and through the openings 234 and 236 . Disc valve 230 a is caused to flex open by the pressure of the inhaled air stream whereby air passes through chamber 225 and thence through openings 244 b in the valve structure 244 . Disc valve 244 c is flexed open by the positive pressure of the inhaled air stream. Upon completion of inhalation, the patient exhales, causing the valve structure 244 to close whereby the exhaled breath is channeled through a conduit 250 and thence into a rearward chamber 252 in the housing 222 . Within the chamber 252 , the exhaled air stream strikes against a rotatable impeller 254 having an axle 256 and radially outwardly-extending blades 258 . The hub 260 of the impeller 254 has a recessed area containing a coil spring 262 . Attached to the impeller 254 is a split disc-shaped permanent magnet 264 . Spaced from the magnet 264 and attached to the piston 238 is another permanent magnet 266 . The magnets 264 and 266 are preferably rare earth Neodymium discs, one of which is firmly attached to the hub 260 of the impeller 254 , and the other being firmly affixed to the back side of the piston 238 . Such magnets, made from a Neodymium iron-boron material, have seven to ten times more holding or repulsion force than other magnetic materials. The magnets are magnetically charged to repulse each other whereby, when magnet 264 is rotated on its axis 180° the repulsive force causes the magnet 266 to move from right to left as viewed in FIG. 8, thereby causing the piston 238 to move from its first or starting position to its second or extended position such that diaphragm 230 is deformably distended in the direction of the mask 224 .
[0037] As shown in FIG. 8, the magnets 264 and 266 are in an equilibrium position, however, when exhaled air from the patient moves through conduit 250 and thence through the rearward chamber 252 , the air pressure against the impeller blades 258 cause the impeller 254 to rotate 180° until the air stream escapes through housing opening 246 . The rotation of the impeller 254 rotates the split magnet 264 relative to the split magnet 266 whereby a magnetic repulsive force acting between the magnets causes the piston to move away from the magnet 264 . A light-duty return spring 262 disposed about the shaft and bearings of the impeller 254 returns the impeller 254 to its starting position whereby the repulsive force between the magnets is neutralized. When the piston 238 is driven from its first position to its second position within the housing 222 , the bolus of air contained within the chamber 224 is driven against and past the valve structure 244 and thence to the airway of the patient. The apparatus 220 serves to provide a bolus of air into the patient's airway at the termination of each exhalation by the patient during the patient's breathing cycle and, in each sequential cycle, the patient completes inhalation naturally and without assistance before the next exhalation occurs.
[0038] In view of the description of the operation of the various embodiments of the present invention heretofore presented, it should be apparent to those skilled in the art that the method of the invention may be practiced by the provision of a mechanical variation such as shown in FIG. 9. FIG. 9 illustrates a pair of vanes 270 rotatably mounted on an axis 272 . The vanes 270 can be driven to rotate by exhaled breath coming from a mask 274 to thereby rotate the shaft or axis 272 and correspondingly wind an energy-storing device 278 . At the completion of each exhalation by the patient, a wound spring within the energy-storing device 278 will then cause the shaft 272 to counter-rotate whereby an impeller 280 and planetary gears 282 will force a pressurized airflow back into the mask and thence into the airway of the patient. The aforedescribed function occurs as an incident of each breathing cycle of the patient.
[0039] A further use of the invention is contemplated as shown in FIG. 10 which would include first and second masks 284 and 286 by which a first person 288 could provide hands-free ventilation to a second distressed person 290 . For this embodiment, momentary positive air pressure would be provided to the first mask 284 , an exhalation chamber, and a collection or bolus chamber (not shown) as illustrated in accordance with the invention embodiments herein previously described. The exhalation chamber would receive the exhaled breath of the first assisting person 288 , and the bolus chamber would be adapted to deliver fresh ambient air to the second distressed person 290 . With the device 292 coupled intermediate to the first and second persons, by means of hoses 294 and 296 , a pressurized flow of ambient air could be delivered from the assisting person 288 to the distressed person 290 as a resuscitation measure.
[0040] While various embodiments of the present invention have been disclosed and described herein, it should be understood that the preferred version of the apparatus is compact, portable, and comparatively inexpensive as compared to prior art devices that utilize large blowers or compressors to achieve a similar function by continuous or bi-level airflow provision. It should be further understood that while the invention has been disclosed and described with reference to specific alternative embodiments, there are variations and modifications which may be introduced that will nevertheless come within the scope and spirit of the invention as defined by the appended claims. | A method is provided for effecting improved airway ventilation of a patient which involves delivering a momentary pulse, thrust or bolus of pressurized air into the patient's airway at commencement of inhalation. This process is repeated at the termination of breath exhalation by the patient. | 0 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This Application claims the benefit of priority and is a Continuation application of the prior International Patent Application No. PCT/KR2015/010086, with an international filing date of Sep. 24, 2015, which designated the United States, and is related to the Korean Patent Application No. 10-2014-0129581, filed Sep. 26, 2014, the entire disclosures of all applications are expressly incorporated by reference in their entirety herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine, and more particularly, to a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine from a conventional liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine through phase change using an organic solvent.
[0004] 2. Description of Related Art
[0005] Racemic or optically active D or L-α-glycerophosphorylcholine is a compound represented by Formula 1 below, and is known to have excellent effects in treatment of senile cognitive impairment (decreased memory, confusion, loss of sense of direction, decreased motivation and spontaneity, decreased concentration) such as secondary symptoms due to cerebrovascular deficiency and degenerative organic brain syndromes and senile pseudo-depression such as emotional and behavioral changes (anxiety disorder, irritability, lack of interest), and specifically, is known to be an excellent drug that normalizes functions of damaged neurons and abnormalities of the cholinergic system due to acetylcholine deficiency by promoting production of acetylcholine, a neurotransmitter in the brain.
[0000]
wherein * indicates a chiral center and Formula 1 represents a racemic and optically active D or L-α-optical isomer.
[0007] Known methods of crystallizing liquid-phase a-glycerophosphorylcholine are as follows. First of all, in J. Am. Chem. Soc. 70, 1394-1399 (1948), it was reported that a water-containing glycerophosphorylcholine prepared by a pure synthetic method can be solidified in an alcohol solution, but no specific crystallization method or crystal structure was mentioned.
[0008] According to a method disclosed in Korean Patent No. 262,281, glycerophosphorylcholine is prepared by performing deacylation reaction by alcoholysis in a reactor containing basic ion exchange resins, lipophilic impurities are removed using non-polar adsorptive resins, the glycerophosphorylcholine is dissolved in methanol, to which an about 20-fold amount of n-butanol is further added, and then the mixture is subjected to vacuum concentration, followed by cooling and filtering to recover anhydrous crystals. However, in this method, it was reported that microcrystals having high hygroscopicity were formed, and there was no mention of specific crystal structure.
[0009] According to methods disclosed in Korean Patent Application Publications No. 10-2013-0063520 and No. 10-2013-0063521, conventional liquid-phase L-α-glycerophosphorylcholine is concentrated, dissolved in an alcohol solution, and seed crystals are added to trigger crystallization, followed by aging and filtering to obtain crystals of L-α-glycerophosphorylcholine in anhydrous form and L-α-glycerophosphorylcholine-type in the form of a monohydrate. However, the above methods have problems in that the methods use seed crystals and that yield is low due to crystal formation by difference in solubility.
[0010] According to a method disclosed in Korean Patent Application Publication No. 10-2001-7005577, L-carnitine, which is a hygroscopic solid, is polished with acetone and filtered to obtain solid L-carnitine. Until now, there has been no method of preparing solid glycerophosphorylcholine by such a method.
[0011] Accordingly, the present inventors have made intensive efforts to solve the problems of the conventional technologies, and as a result, have developed a method to solidify racemic or optically active D or L-α-glycerophosphorylcholine in a simpler and easier way and confirmed that the solidified D or L-α-glycerophosphorylcholine may be mass-produced at high purity and low cost, and thus the present invention was completed.
BRIEF SUMMARY OF THE INVENTION
[0012] The object of the present invention is to provide a method of mass-producing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine in a simple manufacturing process and at low cost.
[0013] One aspect of the present invention provides a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine, wherein a liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine represented by Formula 1 below undergoes phase change by adding one or more organic solvents selected from the group consisting of alcohols, hydrocarbons, ketones, ethers and cyanides and stirring the mixture.
[0000]
wherein * indicates a chiral center, and Formula 1 represents an isomer of racemic and optically active D or L-α-glycerophosphorylcholine.
[0015] Another aspect of the present invention provides solid powders of glycerophosphorylcholine, which are prepared according to the above method, wherein the solid powders exhibit peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, and exhibit endothermic peaks in a range of 71±2° C. to 129±2° C. for endothermic onset temperature and endothermic peaks in a range of 100±2° C. to 137±2° C. for endothermic temperature in differential scanning calorimetry (DSC).
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a result of powder X-ray diffraction (XRD) analysis of solid glycerophosphorylcholine prepared using hexane according to an embodiment of the present invention.
[0017] FIG. 2 is a result of powder X-ray diffraction (XRD) analysis of solid glycerophosphorylcholine prepared using hexane according to an embodiment of the present invention.
[0018] FIG. 3 is a result of powder X-ray diffraction (XRD) analysis of solid glycerophosphorylcholine prepared using methanol and acetone according to an embodiment of the present invention.
[0019] FIG. 4 is a result of powder X-ray diffraction (XRD) analysis of solid glycerophosphorylcholine prepared using isopropanol and acetonitrile according to an embodiment of the present invention.
[0020] FIG. 5 is a result of differential scanning calorimetry (DSC) analysis of solid glycerophosphorylcholine prepared using hexane according to an embodiment of the present invention.
[0021] FIG. 6 is a result of differential scanning calorimetry (DSC) analysis of solid glycerophosphorylcholine prepared using methanol and acetone according to an embodiment of the present invention.
[0022] FIG. 7 is a result of differential scanning calorimetry (DSC) analysis of solid glycerophosphorylcholine prepared using isopropanol and acetonitrile according to an embodiment of the present invention.
[0023] FIG. 8 shows images of the morphologies of a solid form of racemic or optically active D or L-α-glycerophosphorylcholine prepared according to an embodiment of the present invention.
[0024] FIG. 9 is a microscopic analysis result of solid glycerophosphorylcholine prepared using isopropanol according to an embodiment of the present invention.
[0025] FIG. 10 is a microscopic analysis result of solid glycerophosphorylcholine prepared using hexane according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0026] 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. In general, nomenclature used herein and experimental methods described below are well known and commonly used in the art.
[0027] Unlike conventional methods using difference in solubility in a solvent, the present invention aimed to develop a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine from a liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine through phase change using an organic solvent. In addition, the present invention was intended to demonstrate that this method was capable of preparing the solid form in an easier way and at a high yield.
[0028] Therefore, according to one aspect of the present invention, the present invention relates to a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine, wherein a liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine represented by Formula 1 below undergoes phase change by adding one or more organic solvents selected from the group consisting of alcohols, hydrocarbons, ketones, ethers and cyanides and stirring the mixture. Further, another feature of the present invention is that powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and solid form may be different depending on solvents, stirring time or temperature. This can be confirmed from FIGS. 1 to 8 .
[0000]
wherein * indicates a chiral center.
[0030] The present invention relates to a method of preparing a solid form of racemic or optically active D or L-α-glycerophosphorylcholine represented by Formula 1 below. According to the method, the solid form of racemic or optically active D or L-α-glycerophosphorylcholine is prepared by drying a liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine to a moisture content of 0 to 10% by weight, and then adding the organic solvents in an amount of 1 to 20 times the volume of the liquid phase of racemic or optically active D or L-α-glycerophosphorylcholine and stirring at a temperature of 0 to 70° C. for 1 to 24 hours.
[0000]
wherein * indicates a chiral center, and Formula 1 represents an isomer of optically active D or L-α-glycerophosphorylcholine.
[0032] In the present invention, the temperature is 0 to 70° C., preferably 30 to 60° C., and the stirring time is 0 to 24 hours, preferably 0.1 to 12 hours. When the stirring temperature is less than 0° C. or greater than 70° C., the production rate of solid decreases and overall yield may decrease.
[0033] In the present invention, the moisture content is 0 to 10% by weight, preferably 0 to 7% by weight. When the moisture content exceeds 10% by weight, the production rate of solid decreases and overall yield may decrease.
[0034] In the present invention, solvents selected from the group consisting of alcohols, hydrocarbons, ketones, ethers and cyanides may be used alone or in combination of two or more as the organic solvents. More preferably, solvents selected from the group consisting of alcohols having 1 to 8 carbon atoms, alkane having 1 to 8 carbon atoms, ketones having 1 to 8 carbon atoms, and ethers and cyanides having 1 to 8 carbon atoms may be used alone or in combination of two or more as the organic solvents.
[0035] For specific example, solvents selected from the group consisting of alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-phentanol, 2-phentanol, 3-phentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, ethylene glycol, and propylene glycol; hydrocarbon-based solvents such as dichloromethane, dichloroethane, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, toluene, xylene, naphtha, and petroleum benzin; halogenated hydrocarbon-based solvents such as chloroform, carbon tetrachloride, trichloroethylene, and perfluoropropane; ketone-based solvents such as acetone, methylethylketone, methylisobutylketone, and acetophenone; ether-based solvents such as propyl ether, n-butyl ether, tetrahydrofuran, diethyl ether, and t-butyl methyl ether; and cyanide solvents such as acetonitrile and the like may be used alone or in combination of two or more as the organic solvents, without being limited thereto.
[0036] In the present invention, the amount of the organic solvent to be used is 1 to 20 times, preferably 2 to 7 times. When the amount of the organic solvent is less than 1 time, the production rate of solid may decrease. On the other hand, when the amount is more than 20 times, cost may greatly increase.
[0037] In another aspect, the present invention relates to solid powders of glycerophosphorylcholine, which are prepared according to the above method, wherein the solid powders exhibit peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, and exhibit endothermic peaks in a range of 71±2° C. to 129±2° C. for endothermic onset temperature and endothermic peaks in a range of 100±2° C. to 137±2° C. for endothermic temperature in differential scanning calorimetry (DSC).
[0038] The solid powders of glycerophosphorylcholine may exhibit peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, and may exhibit an endothermic peak at 71±2° C. for endothermic onset temperature and at 100±2° C. for endothermic temperature, respectively, in differential scanning calorimetry (DSC);
the solid powders may exhibit peaks at 2θ diffraction angles of 9.7±0.2°, 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, and may exhibit an endothermic peak at 129±2° C. for endothermic onset temperature and at 137±2° C. for endothermic temperature, respectively, in differential scanning calorimetry (DSC); the solid powders may exhibit peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2°, 29.9±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, and may exhibit an endothermic peak at 118±2° C. for endothermic onset temperature and at 132±2° C. for endothermic temperature, respectively, in differential scanning calorimetry (DSC); or the solid powders may exhibit peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 15.7±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° in powder X-ray diffraction (XRD) analysis, may exhibit an endothermic peak at 105±2° C. for endothermic onset temperature and at 130±2° C. for endothermic temperature, respectively, in differential scanning calorimetry (DSC).
[0042] Hereinafter, the present invention is described in more detail with reference to examples. It will be apparent to those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
EXAMPLES
Example 1
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Isopropanol
[0043] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 10% was dried at a temperature of 105° C. for 3 hours to reduce the moisture content to about 6%. 100 ml of isopropanol was added thereto, and the mixture was stirred at a temperature of 50° C. for 5 hours.
[0044] Precipitated solid was filtered and dried to obtain 7.8 g (yield: 92%) of L-α-glycerophosphorylcholine as a white solid.
Example 2
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Heptane
[0045] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 16% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 5%. 50 ml of heptane was added thereto, and the mixture was stirred at a temperature of 60° C. for 6 hours.
[0046] Precipitated solid was filtered and dried to obtain 7.65 g (yield: 90%) of L-α-glycerophosphorylcholine as a white solid.
Example 3
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Hexane
[0047] 20 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 14.5% was dried at a temperature of 105° C. for 5 hours to reduce the moisture content to about 3.5%. 60 ml of hexane was added thereto, and the mixture was stirred at a temperature of 50° C. for 30 minutes.
[0048] Precipitated solid was filtered and dried to obtain 15.73 g (yield: 92%) of L-α-glycerophosphorylcholine as a white solid.
[0049] Powder X-ray Diffraction (XRD) Analysis
[0050] Powder X-ray diffraction (XRD) analysis of the solid prepared in Example 3 showed that the solid exhibited specific peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° ( FIG. 1 ).
[0051] Differential Scanning Calorimetry (DSC) Analysis
[0052] Differential scanning calorimetry (DSC) analysis of the solid prepared in Example 3 showed that the solid exhibited an endothermic peak at 71±2° C. for endothermic onset temperature and at 100±2° C. for endothermic temperature, respectively (Top curve in FIG. 5 ).
Example 4
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Hexane
[0053] 20 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 14.5% was dried at a temperature of 105° C. for 5 hours to reduce the moisture content to about 3.5%. 60 ml of hexane was added thereto, and the mixture was stirred at a temperature of 40° C. for 6 hours.
[0054] Precipitated solid was filtered and dried to obtain 16.07 g (yield: 94%) of L-α-glycerophosphorylcholine as a white solid.
[0055] Powder X-ray Diffraction (XRD) Analysis
[0056] Powder X-ray diffraction (XRD) analysis of the solid prepared in Example 4 showed that the solid exhibited specific peaks at 2θ diffraction angles of 9.7±0.2°, 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° ( FIG. 2 ).
[0057] Differential Scanning Calorimetry (DSC) Analysis
[0058] Differential scanning calorimetry (DSC) analysis of the solid prepared in Example 4 showed that the solid exhibited an endothermic peak at 129±2° C. for endothermic onset temperature and at 137±2° C. for endothermic temperature, respectively (Lower curve in FIG. 5 ).
Example 5
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Octanol
[0059] The moisture content of 4.5 g of a liquid phase of L-a-glycerophosphorylcholine was reduced to about 2% using MgSO 4 . 45 ml of octanol was added thereto, and the mixture was stirred at a temperature of 50° C. for 4 hours.
[0060] Precipitated solid was filtered and dried to obtain 3.47 g (yield: 91%) of L-α-glycerophosphorylcholine as a white solid.
Example 6
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Isopropanol and Ethanol
[0061] 20 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 5%. 5 ml of ethanol and 50 ml of isopropanol were added thereto, and the mixture was stirred at a temperature of 50° C. for 5 hours.
[0062] Precipitated solid was filtered and dried to obtain 15.81 g (yield: 93%) of L-α-glycerophosphorylcholine as a white solid.
Example 7
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Isopropanol and Methanol
[0063] 10 g of a liquid phase of L-α-glycerophosphorylcholine was dried at a temperature of 105° C. for 4 hours to reduce a moisture content to about 6%. 5 ml of methanol and 50 ml of isopropanol were added thereto, and the mixture was stirred at a temperature of 50° C. for 4 hours.
[0064] Precipitated solid was filtered and dried to obtain 7.65 g (yield: 90%) of L-α-glycerophosphorylcholine as a white solid.
Example 8
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Acetone
[0065] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 5 hours to reduce the moisture content to about 3%. 100 ml of acetone was added thereto, and the mixture was stirred at a temperature of 50° C. for 4 hours.
[0066] Precipitated solid was filtered and dried to obtain 7.65 g (yield: 90%) of L-α-glycerophosphorylcholine as a white solid.
Example 9
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Acetone
[0067] The moisture content of 15.6 g of a liquid phase of L-α-glycerophosphorylcholine was reduced to about 2% using MgSO 4 . 156 ml of acetone was added thereto, and the mixture was stirred at a temperature of 0° C. for 20 hours.
[0068] Precipitated solid was filtered and dried to obtain 12.07 g (yield: 91%) of L-α-glycerophosphorylcholine as a white solid.
Example 10
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Methanol and Acetone
[0069] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 4%. 33 ml of methanol and 16 ml of acetone were added thereto, and the mixture was stirred at a temperature of 50° C. for 2 hours.
[0070] Precipitated solid was filtered and dried to obtain 7.99 g (yield: 94%) of L-α-glycerophosphorylcholine as a white solid
[0071] Powder X-ray Diffraction (XRD) Analysis
[0072] Powder X-ray diffraction (XRD) analysis of the solid prepared in Example 10 showed that the solid exhibited specific peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 19.8±0.2°, 25.3±0.2°, 29.9±0.2° and 40.4±0.2° ( FIG. 3 ).
[0073] Differential Scanning Calorimetry (DSC) Analysis
[0074] Differential scanning calorimetry (DSC) analysis of the solid prepared in Example 10 showed that the solid exhibited an endothermic peak at 118±2° C. for endothermic onset temperature and at 132±2° C. for endothermic temperature, respectively ( FIG. 6 ).
[0075] Microscope Analysis
[0076] The solid prepared in Example 10 was analyzed by a microscope and the analysis result is shown in FIG. 9 .
Example 11
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Isopropanol and Acetonitrile
[0077] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 4%. 10 ml of isopropanol and 50 ml of acetonitrile were added thereto, and the mixture was stirred at a temperature of 50° C. for 5 hours.
[0078] Precipitated solid was filtered and dried to obtain 8.08 g (yield: 95%) of L-α-glycerophosphorylcholine as a white solid.
[0079] Powder X-ray Diffraction (XRD) Analysis
[0080] Powder X-ray diffraction (XRD) analysis of the solid prepared in Example 11 showed that the solid exhibited specific peaks at 2θ diffraction angles of 11.9±0.2°, 14.2±0.2°, 5.7±0.2°, 19.8±0.2°, 25.3±0.2° and 40.4±0.2° ( FIG. 4 ).
[0081] Differential Scanning Calorimetry (DSC) Analysis
[0082] Differential scanning calorimetry (DSC) analysis of the solid prepared in Example 11 showed that the solid exhibited an endothermic peak at 105±2° C. for endothermic onset temperature and at 130±2° C. for endothermic temperature, respectively ( FIG. 7 ).
[0083] Microscope Analysis
[0084] The solid prepared in Example 11 was analyzed by a microscope and the analysis result is shown in FIG. 10 .
Example 12
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using Isopropanol and Acetonitrile
[0085] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 4%. 10 ml of isopropanol and 30 ml of acetonitrile were added thereto, and the mixture was stirred at a temperature of 30° C. for 5 hours.
[0086] Precipitated solid was filtered and dried to obtain 7.82 g (yield: 92%) of L-α-glycerophosphorylcholine as a white solid.
Example 13
Preparation of Solid Form of Optically Active L-α-glycerophosphorylcholine Using t-butyl Methyl Ether
[0087] 10 g of a liquid phase of L-α-glycerophosphorylcholine having a moisture content of 15% was dried at a temperature of 105° C. for 4 hours to reduce the moisture content to about 4%. 50 ml of t-butyl methyl ether was added thereto, and the mixture was stirred at a temperature of 50° C. for 40 minutes.
[0088] Precipitated solid was filtered and dried to obtain 8.08 g (yield: 95%) of L-α-glycerophosphorylcholine as a white solid.
Comparative Example 1
Preparation of Crystals of Optically Active L-α-glycerophosphorylcholine Using Ethanol
[0089] Reference was made to the method disclosed in Korean Patent Application Publication No. 10-2013-0063520.
[0090] 23 ml of ethanol was added to 11.5 g of powders of L-α-glycerophosphorylcholine and the powders were sufficiently dissolved at 50° C. The solution containing L-α-glycerophosphorylcholine was cooled to 9° C. and stirred for 5 hours. However, crystals were not formed. That is, no solid was produced when seed crystals were not administered as in Korean Patent Application Publication No. 10-2013-0063520.
[0091] In the case of the method of Comparative Example 1 (Korean Patent Application Publication No. 10-2013-0063520), L-α-glycerophosphorylcholine is sufficiently dissolved in alcohol at a high temperature, and then the temperature is lowered, and difference in solubility by temperature is used to generate crystals, which are specific forms of solids. Therefore, seed crystals of L-α-glycerophosphorylcholine were required for crystal formation.
[0092] On the other hand, in the case of an embodiment according to the present invention, when an organic solvent was added to a liquid phase of L-α-glycerophosphorylcholine while maintaining temperature and stirring was performed, water was moved to the organic solvent and moisture in the L-α-glycerophosphorylcholine was reduced, and the property was transformed into a solid.
[0093] It was also confirmed that powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and solid form were different depending on solvents, stirring time, temperature, and the like. FIGS. 1 to 4 showed differences in powder X-ray diffraction (XRD), FIGS. 5 to 7 showed differences in differential scanning calorimetry (DSC), and FIGS. 8 to 10 showed differences in properties of solid.
INDUSTRIAL APPLICABILITY
[0094] Compared to a conventional liquid form of racemic or optically active D or L-α-glycerophosphorylcholine, a solid form of racemic or optically active D or L-α-glycerophosphorylcholine prepared according to the present invention is easier to store and pack, is more stable, and has a higher purity. In addition, patient's medication compliance is high due to easy formulation modification and capacity change. Therefore, there is an advantage that various preparations can be mass-produced in a simple process.
[0095] Thus, specific portions of the present invention have been described in detail. It will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. Accordingly, the actual scope of the present invention will be defined by the appended claims and equivalents thereof. | The present invention is characterized in that racemic or optically active D- or L-α-glycerophosphoryl choline solids are prepared from liquid type racemic or optically active D- or L-α-glycerophosphoryl choline using an organic solvent. The present invention can produce solids at a high yield more easily through phase transformation rather than a method using a difference in solubility in a solvent, which is an existing method. | 2 |
BACKGROUND
[0001] Semiconductor die, wafers, and/or substrates may be joined to other semiconductor die, wafers, and/or substrates with an adhesive. Application of adhesive to the semiconductor die, wafers, and/or substrates to be joined, however, may be complicated by topography of the semiconductor die, wafers, and/or substrates. In addition, establishing a uniform layer of adhesive on the areas of the semiconductor die, wafers, and/or substrates to be joined may be challenging.
BRIEF DESCRIPTION OF THE DRAWINGS
[0002] FIG. 1 schematically illustrates one example of an adhesive transfer and bonding process.
[0003] FIG. 2 schematically illustrates another example of an adhesive transfer and bonding process.
[0004] FIG. 3 illustrates one example of application of an adhesive transfer and bonding process.
[0005] FIG. 4 illustrates one example of application of an adhesive transfer and bonding process.
DETAILED DESCRIPTION
[0006] In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration specific examples in which the disclosure may be practiced. In this regard, directional terminology, such as “top,” “bottom,” “front,” “back,” “leading,” “trailing,” etc., is used with reference to the orientation of the Figure(s) being described. Because components of examples of the present disclosure can be positioned in a number of different orientations, the directional terminology is used for purposes of illustration and is in no way limiting. It is to be understood that other examples may be utilized and structural or logical changes may be made without departing from the scope of the present disclosure. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present disclosure is defined by the appended claims.
[0007] FIG. 1 schematically illustrates one example of an adhesive transfer and bonding process 100 . At 102 , process 100 includes reducing viscosity (i.e., increasing flowability) of an adhesive used in process 100 . An example of an adhesive used in process 100 includes a dual-cure adhesive such as EMS 405 - 57 from Engineered Materials Systems Inc.
[0008] Reducing viscosity of the adhesive helps facilitate dispensing and depositing of the adhesive during subsequent processing. In one example, viscosity of the adhesive is reduced by diluting or thinning the adhesive with a solvent. An example of a solvent used for diluting or thinning the adhesive in process 100 includes cyclopentanone.
[0009] At 104 , process 100 includes depositing the diluted adhesive on a dummy wafer or donor substrate 10 . More specifically, a layer of diluted adhesive 12 is deposited on a surface 11 of donor substrate 10 . In one example, adhesive 12 is deposited on surface 11 of donor substrate 10 by spin coating.
[0010] Next, at 106 , process 100 includes transferring adhesive 12 from donor substrate 10 to an intermediate or carrier substrate 13 . An example of a material used for intermediate or carrier substrate 13 includes a flexible film including a polyester film such as Mylar.
[0011] In one example, transferring adhesive 12 from donor substrate 10 to intermediate or carrier substrate 13 includes contacting or pressing a surface 14 of intermediate or carrier substrate 13 against adhesive 12 deposited on donor substrate 10 . As such, adhesive 12 is transferred to surface 14 of intermediate or carrier substrate 13 such that a layer 15 of adhesive 12 is formed on intermediate or carrier substrate 13 and remains on intermediate or carrier substrate 13 when intermediate or carrier substrate 13 is separated, peeled, or removed from donor substrate 10 .
[0012] In one example, layer 15 of adhesive 12 is a substantially uniform layer, and has a thickness less than a total thickness of adhesive 12 deposited on donor substrate 10 such that a layer of adhesive 12 remains on donor substrate 10 after transferring adhesive 12 to intermediate or carrier substrate 13 .
[0013] After transferring adhesive 12 to carrier substrate 1 . 3 , at 108 , process 100 includes removing the solvent from adhesive 12 of layer 15 . In one example, removing the solvent from adhesive 12 includes heating layer 15 of adhesive 12 and carrier substrate 13 at a predetermined temperature for a predetermined time so as to evaporate the solvent from adhesive 12 .
[0014] In one example, at 110 , process 100 includes partially cross-linking or “B-staging” adhesive 12 as provided on carrier substrate 13 . In one example, partially cross-linking or “B-staging” adhesive 12 includes semi-curing adhesive 12 by exposing layer 15 of adhesive 12 to ultra-violet (UV) light. Partially cross-linking or “B-staging” adhesive 12 essentially “freezes” adhesive 12 in position to reduce wicking of adhesive 12 , and reduces a tack of adhesive 12 such that carrier substrate 13 with layer 15 of adhesive 12 may be “staged” or held for a period of time, and/or may be more easily handled during subsequent processing.
[0015] At 112 , process 100 includes transferring adhesive 12 of layer 15 from carrier substrate 13 to a device wafer or substrate 16 . In one example, device wafer or substrate 16 includes a patterned substrate having a topography of raised portions or areas 17 . As such, transferring adhesive 12 of layer 15 from carrier substrate 13 to substrate 16 includes transferring adhesive 12 to raised portions or areas 17 of substrate 16 .
[0016] In one example, transferring adhesive 12 from carrier substrate 13 to substrate 16 includes pressing layer 15 of adhesive 12 against substrate 16 and contacting raised portions or areas 17 of substrate 16 with layer 15 of adhesive 12 . As such, adhesive 12 from layer 15 is transferred to raised portions or areas 17 of substrate 16 and remains on raised portions or areas 17 of substrate 16 when carrier substrate 13 is separated, peeled, or removed from substrate 16 . Thus, a pattern of adhesive 12 transferred to substrate 16 follows and is aligned with a pattern of substrate 16 such that adhesive 12 transferred to substrate 16 is self-patterned and self-aligned.
[0017] Partially cross-linking or “B-staging” adhesive 12 (as described, for example, at 110 ) reduces wicking of adhesive 12 so that adhesive 12 , after transfer at 112 , remains on raised portions or areas 17 of substrate 16 instead of wicking into recessed areas or regions among raised portions or areas 17 of substrate 16 .
[0018] At 114 of process 100 , substrate 16 with self-patterned and self-aligned adhesive 12 is aligned with another substrate 18 for bonding with substrate 18 such that at 116 of process 100 , substrate 16 and substrate 18 are bonded together by adhesive 12 . In one example, substrate 16 and substrate 18 are bonded together by placing substrate 16 and substrate 18 in a thermal bonding machine at a predetermined temperature for a predetermined time. Thereafter, at 118 of process 100 , adhesive 12 is cured by heating substrates 16 and 18 at a predetermined temperature for a predetermined time.
[0019] FIG. 2 schematically illustrates another example of an adhesive transfer and bonding process 200 . At 202 , process 200 , similar to process 100 , includes reducing viscosity of an adhesive used in process 200 . Similar to 102 of process 100 , viscosity of the adhesive is reduced by diluting or thinning the adhesive with a solvent.
[0020] At 204 , process 200 includes depositing the diluted adhesive on a dummy wafer or donor substrate 20 . More specifically, a layer of diluted adhesive 22 is deposited on a surface 21 of donor substrate 20 . In one example, similar to 104 of process 100 , adhesive 22 is deposited on surface 21 of donor substrate 20 by spin coating.
[0021] Next, at 206 , process 200 includes transferring adhesive 22 from donor substrate 20 to an intermediate or carrier substrate 23 . An example of a material used for intermediate or carrier substrate 23 includes a flexible film including a polyester film such a Mylar.
[0022] In one example, similar to 106 of process 100 , transferring adhesive 22 from donor substrate 20 to intermediate or carrier substrate 23 includes contacting or pressing a surface 24 of intermediate or carrier substrate 23 against adhesive 22 deposited on donor substrate 20 . As such, adhesive 22 is transferred to surface 24 of intermediate or carrier substrate 23 such that a layer 25 of adhesive 22 is formed on intermediate or carrier substrate 23 and remains on intermediate or carrier substrate 23 when intermediate or carrier substrate 23 is separated, peeled, or removed from donor substrate 20 .
[0023] In one example, similar to layer 15 of adhesive 12 , layer 25 of adhesive 22 is a substantially uniform layer, and has a thickness less than a total thickness of adhesive 22 deposited on donor substrate 20 such that a layer of adhesive 22 remains on donor substrate 20 after transferring adhesive 22 to intermediate or carrier substrate 23 .
[0024] After transferring adhesive 22 to carrier substrate 23 , at 208 , process 200 includes removing the solvent from adhesive 22 of layer 25 . In one example, similar to 108 of process 100 , removing the solvent from adhesive 22 includes heating layer 25 of adhesive 22 and carrier substrate 23 at a predetermined temperature for a predetermined time so as to evaporate the solvent from adhesive 22 .
[0025] At 210 , process 200 includes transferring adhesive 22 of layer 25 from carrier substrate 23 to a semiconductor die or substrate 26 . In one example, semiconductor die or substrate 26 includes a patterned substrate formed by a singulated wafer resulting in a topography of raised portions or areas 27 on a backing member (e.g., saw tape) 28 . As such, transferring adhesive 22 from carrier substrate 23 to substrate 26 includes transferring adhesive 22 to raised portions or areas 27 of substrate 26 .
[0026] In one example, similar to 112 of process 100 , transferring adhesive 22 from carrier substrate 23 to substrate 26 includes pressing layer 25 of adhesive 22 against substrate 26 and contacting raised portions or areas 27 of substrate 26 with layer 25 of adhesive 22 . As such, adhesive 22 from layer 25 is transferred to raised portions or areas 27 of substrate 26 and remains on raised portions or areas 27 of substrate 26 when carrier substrate 24 is separated, peeled, or removed from substrate 26 . Thus, a pattern of adhesive 22 transferred to substrate 26 follows and is aligned with a pattern of substrate 26 such that adhesive 22 transferred to substrate 26 is self-patterned and self-aligned.
[0027] In one example, at 212 , process 200 includes partially cross-linking or “B-staging” adhesive 22 as provided on substrate 26 . In one example, partially cross-linking or “B-staging” adhesive 22 includes semi-curing adhesive 22 by exposing adhesive 22 to ultra-violet (UV) light. Partially cross-linking or “B-staging” adhesive 22 essentially “freezes” adhesive 22 in position to reduce wicking of adhesive 22 , and reduces a tack of adhesive 22 such that substrate 26 with self-patterned and self-aligned adhesive 22 may be “staged” or held for a period of time, and/or may be more easily handled during subsequent processing. Partially cross-linking or “B-staging” adhesive 22 also reduces wicking of adhesive 12 into areas or regions between raised portions or areas 27 of substrate 26 or along edges of substrate 26 after transfer at 210 .
[0028] At 214 of process 200 , substrate 26 with self-patterned and self-aligned adhesive 22 is stacked with another silicon or semiconductor die or substrate 29 for bonding to silicon or semiconductor die or substrate 29 with adhesive 22 .
[0029] FIG. 3 illustrates one example of application of an adhesive transfer and bonding process as described herein. In one example, adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 is used in fabrication of a fluid ejection device 300 .
[0030] Schematically illustrated in cross-section in FIG. 3 , one example of fluid ejection device 300 includes an electronics wafer or substrate 310 , a piezeoelectric wafer or substrate 320 attached to electronics wafer 310 , a piezoelectric element 330 supported by piezoelectric wafer 320 , a cap wafer or substrate 340 attached to piezoelectric wafer 320 , and a nozzle plate 350 attached to cap wafer 340 .
[0031] In one example, piezoelectric wafer 320 is attached to electronics wafer 310 with an adhesive layer 360 formed using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 . In addition, in one example, cap wafer 340 is attached to piezoelectric wafer 320 with an adhesive layer 370 formed using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 , and nozzle plate 350 is attached to cap wafer 340 with an adhesive layer 380 also formed using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 .
[0032] In one example, electronics wafer 310 includes a fluid (or ink) feed hole 312 communicated with a supply of fluid (or ink), and piezoelectric wafer 320 includes fluidic routing communicated with fluid feed hole 312 of electronics wafer 310 such that application of an electrical signal to piezoelectric element 330 deflects piezoelectric element 330 and ejects fluid (or ink) through cap wafer 340 and out a nozzle 352 of nozzle plate 350 .
[0033] In one example, as illustrated in FIG. 4 , fluidic routing of piezoelectric wafer 320 includes fluid channels 322 separated and formed by spaced ribs 324 , and includes pinch points 326 communicated with fluid channels 322 and formed by spaced posts 328 . Using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 , adhesive is applied to ribs 324 and posts 328 for bonding of piezoelectric wafer 320 to electronics wafer 310 . By using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 , a layer of self-patterned and self-aligned adhesive is applied to ribs 324 and posts 328 without blocking fluid channels 322 or spilling over the edges of ribs 324 to adjacent fluid channels 322 , and without blocking pinch points 326 or spilling over the edges of posts 328 .
[0034] By using adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 , as described herein, a self-aligned and self-patterned adhesive layer may be formed on a semiconductor die, wafer, and/or substrate while minimizing wicking or flow of adhesive beyond edges of an intended application area for the adhesive. In addition, with adhesive transfer and bonding process 100 and/or adhesive transfer and bonding process 200 , a thin layer of adhesive of substantially uniform thickness providing for a thin bond line may be selectively applied to a semiconductor die, wafer, and/or substrate having a topography of small or narrow features.
[0035] Although specific examples have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a variety of alternate and/or equivalent implementations may be substituted for the specific examples shown and described without departing from the scope of the present disclosure. This application is intended to cover any adaptations or variations of the specific examples discussed herein. Therefore, it is intended that this disclosure be limited only by the claims and the equivalents thereof. | An adhesive transfer method includes depositing an adhesive on a first substrate, transferring a layer of the adhesive from the first substrate to an intermediate substrate, and transferring adhesive from the layer of the adhesive to at least one area of a second substrate. | 8 |
FIELD OF THE INVENTION
The present invention relates to a configuration of roughening ribs for a heat transfer surface.
BACKGROUND
Heat transfer between a surface and an adjacent gas stream flowing substantially parallel thereto is affected by a variety of factors, including gas velocity, surface roughness, gas density, etc. It is known in the art to use roughening ribs or ridges disposed generally transversely with respect to the flow direction of the adjacent gas stream for the purpose of augmenting overall heat transfer coefficients and rates. Such roughening ribs may be disposed perpendicularly, skewed, or in chevrons as disclosed in U.S. Pat. No. 4,416,585 issued to Abdel-Messeh. Such configurations, while generally increasing overall heat transfer coefficient and hence rates, do not provide consistent or determinable augmentation of local heat transfer coefficient between the surface and the adjacent gas stream.
For certain applications, and in particular for internally cooled gas turbine airfoils exposed to an external stream of high temperature turbine working fluid, it is particularly desirable to minimize the flow of internal cooling gas through the turbine blade while still maintaining thermal protection at the external blade surface. As will be appreciated by those skilled in the art of turbine blade cooling, the heat loading at the exterior of the blade is not uniform with chordal displacement, having a peak at the leading edge of the blade and subsequent intermediate peaks at various locations disposed along the pressure and suction sides of each individual blade. Prior art heat transfer augmenting ribs are typically sized to achieve sufficient overall internal heat transfer rates so as to protect the high heat load zones of the blade, thereby overcooling other, lesser loaded zones.
A heat transfer augmenting configuration which permits the designer to allocate and vary heat transfer augmentation transversely with respect to the cooling gas flow would achieve protection of the blade exterior at reduced overall internal cooling mass flow.
SUMMARY OF THE INVENTION
According to the present invention, a plurality of roughening ribs are provided on a heat transfer surface for disrupting the boundary layer of a stream of gas flowing generally parallel to the surface. The roughening ribs increase local turbulence in the gas flow, thereby increasing both local and overall surface heat transfer coefficient.
The present invention also provides for transversely varying local heat transfer coefficient with respect to the gas flow direction by providing each rib with two parallel, but offset end portions, connected at the proximate ends of each, to a third intermediate portion which is oriented approximately perpendicular to the end portions. Test results have shown that this "zig-zag" or "N-shaped" ridge of the present invention provides increased local heat transfer not only at the upstream end of each ridge, but also at each end of the intermediate portion, without increasing the overall gas side frictional pressure loss or diverting the bulk of the gas flow laterally as compared to prior art roughening ribs configurations.
The rib configuration of the present invention is particularly well suited for the internal surface of a cooling conduit in a gas cooled airfoil. Opposite internal conduit surfaces provided with roughening ribs according to the present invention may be "tailored" to match the local internal heat transfer coefficient with the expected external thermal loading on the airfoil suction and pressure sides. A turbine airfoil provided with a tailored internal heat transfer surface would thus achieve maximum cooling protection with the least flow of internal cooling fluid. Increased operating efficiency with minimal costs is the result.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a plan view of a prior art skew heat transfer surface with skewed ridges.
FIG. 2 shows a plan view of a prior art heat transfer surface with chevron ridges.
FIG. 3 shows a plan view of a heat transfer surface according to the present invention.
FIG. 4 shows a sectional view of the surface of FIG. 3.
FIG. 5 shows a spanwise sectional view of the internal cooling arrangement of the turbine airfoil.
FIG. 6 shows a sectional view of the airfoil of FIG. 5 as indicated therein.
DETAILED DESCRIPTION
FIG. 1 shows a heat transfer surface 10 which includes a plurality of trip strips or ridges 12 extending generally laterally with respect to a flow of gas 14 moving parallel to the surface 10. The strips 12 interrupt the boundary layer of the gas moving adjacent the flat portion 16 of the surface 10, thereby increasing turbulence as well as the local convective heat transfer coefficient between the surface 10 and the gas stream 14.
As is well known in the art, the local heat transfer coefficient for the arrangement of FIG. 1 is highest at the upstream ends 18 of the individual ridges 12. The remainder of the surface 10 not in the vicinity of the upstream ends 18 achieves a substantially uniform heat transfer coefficient.
FIG. 2 shows a prior art chevron arrangement of ridges 20, 22 disposed in a surface 24. Again the ridges 20, 22 disrupt the boundary layer of the flowing gas 14 moving generally parallel to the flat portion 26 of the surface 24, augmenting both local and overall heat transfer coefficient. The chevron style, as with the skewed arrangement shown in FIG. 1, also provides for a locally elevated heat transfer coefficient in the vicinity of the upstream ends 28, 30 of the individual ridges 20, 22. One drawback which occurs, however, with the use of chevron style arrangement of FIG. 2 is the diversion of the gas stream 14 away from the lateral edges 32, 34 of the surface 24 toward the center as a result of the chevron arrangement 20, 22. The diverted gas stream is thus reduced in velocity adjacent the edges 32, 34 resulting in a concurrent decrease in local heat transfer rate.
It is known, in a channel arrangement wherein the gas flow 14 is confined between two opposite facing surfaces, to provide oppositely skewed chevrons on each of the facing surfaces thereby preventing the channeling of the gas stream 14. Such arrangement, while effective in reducing the channeling for diversion of the gas stream 14 toward the center of the surface 14 is also effective in increasing the uniformity of heat transfer coefficient over the entire heat transfer surface 24, thereby reducing the ability of the designer to tailor the local heat transfer coefficient of the surface 24 to achieve a locally varying heat flux distribution.
FIG. 3 shows a plan view of a heat transfer surface 36 according to the present invention. A plurality of ridges 38 extend generally laterally across the gas stream 14. The ridges 38 are spaced streamwisely with respect to the gas flow 14, with each ridge 38 including three distinct portions. Each ridge 38 includes a first end portion 40, a second end portion 42, aligned generally parallel with the first portion 40 but offset with respect thereto as shown in FIG. 3. Connecting the proximate ends 44, 46 of the respective first and second end portions 40, 42 is an intermediate portion or segment 48 which is preferably oriented perpendicular to the end portions and in the range of 1/3 to 1/4 of the width of the heat transfer surface 36 measured perpendicular to the gas flow.
The resulting form, termed herein "zig-zag" or "N-shaped" ridge 38 provides heretofore unrealized opportunities for tailoring the local heat transfer coefficient in a heat transfer 36. For ridges having end portions skewed by an angle φ with respect to the general direction of the gas flow 14, it has been determined experimentally that locally elevated heat transfer coefficient in the vicinity of the upstream ends 50 of the first segments 40, as well as in the vicinity of the proximate ends 44, 46 of the first and second end portions 40, 42. Thus, a designer may locate the intermediate segments 44 of a plurality of heat augmenting ridges 38 according to the present invention so as to achieve a region of elevated heat transfer characteristics intermediate the lateral sides 52, 54 of the heat transfer surface 36.
The angle φ between the flowing gas 14 and the end portions 40, 42 is preferably 45° as shown in FIG. 3, but may vary between 30° and 60° and still achieve the desired local augmentation. In terms of the height and spacing of the ridges 38 relative to the intermediate surface 56 and gas stream 14, FIG. 4 shows the indicated cross-sectional view taken in FIG. 3. The height E and spacing P of the individual ridges 38 can vary depending on the degree of augmentation of the surface heat transfer coefficient desired. It has been found that a ratio of P/E of approximately 4 is the most effective in increasing the surface heat transfer coefficient with the least increase of gas side pressure loss, however, ratios of P to E as great as 15 have been found likewise effective. In general, the linear spacing of the ridges 38 is a function of the desired degree of augmentation of heat transfer with decreasing spacing resulting in increased overall and local heat transfer coefficients. In some circumstances, manufacturing capability may dictate the minimum height and hence, minimum spacing of the ridges 38.
FIG. 5 shows a turbine blade 56 having a plurality of serpentine interior passages 58, 60, 62 for conducting a flow of cooling air 66 through the interior of the blade 56 for the purpose of protecting the blade surface and material from externally flowing high temperature fluid. Such internally cooling blades are common in gas turbine technology with the internal passages and cooling gas flow rate sized to maintain the blade airfoil surface below temperatures at which substantial oxidation or other deterioration is known to occur.
As will be appreciated by those skilled in the art of blade cooling, the external heat loading of a blade airfoil is non-uniform, particularly with respect to chordal displacement. Thus, high heat loading represented by elevated heat flux at the blade surface occurs at the blade leading edge 64 as well as additional locations spaced chordally from the leading edge 64.
Prior art practice using augmented heat transfer surfaces such as those shown in FIGS. 1 and 2 provide increased overall interior heat transfer coefficient within the internal passages 58, 60. Such increased overall heat transfer can result in overcooling of certain regions of the turbine blade, thus, resulting in a decrease in overall engine fuel and operating efficiency.
By using a heat transfer surface 36 having zig-zag ridges 38 according to the present invention, a designer may tailor the local heat transfer coefficient of the interior surface of the blade cooling channels 58, 60 so as to provide increased internal heat transfer coefficients conchordally with those regions on the exterior blade surface which are likely to be subject to increased heat loading. Thus, the arrangement of trip strips 38, 38' in passages 58, 60 of the blade 56 results in a region 68 of locally increased heat transfer coefficient adjacent the leading edge 64 of the airfoil 56 and a secondary region 70 of locally increased heat transfer coefficient spaced chordally with respect to the first region 68.
By tailoring the local heat transfer coefficient so as to match the blade airfoil exterior heat loading, the heat transfer surface 36 according to the present invention provides increased local heat transfer rates and hence, cooling, at exactly the locations necessary to protect the blade material. By thus avoiding overcooling of the areas of the blade not subject to elevated heat loading, the surface 36 according to the present invention permits a reduction in blade internal gas coolant flow 60, thereby increasing overall engine efficiency without sacrificing blade servico life.
As will be appreciated by thos skilled in the art, opposing interior surfaces 36, 36' which define the internal cooling channels 58, 60 of an airfoil 56 as shown in cross section in FIG. 6 may be provided with individually configured ridges 38 so as to particularly address the individual heat loading of the pressure 72 and suction 74 sides of the blade 56. | Augmenting ribs (40) of zig-zag configuration are provided on a heat transfer surface (38) for increasing local heat transfer in a selected zone (68,70) of the surface (38). | 5 |
RELATED APPLICATIONS
[0001] This application is a continuation application of U.S. application Ser. No. 14/062,271, filed on Oct. 24, 2013, which is a continuation application of U.S. application Ser. No. 13/713,756, filed Dec. 13, 2012, now U.S. Pat. No. 8,591,619, which is a continuation application of U.S. application Ser. No. 13/403,362, filed on Feb. 23, 2012, now U.S. Pat. No. 8,349,047, which is a continuation application of U.S. application Ser. No. 13/022,921, filed Feb. 8, 2011, now U.S. Pat. No. 8,137,426, which is a continuation of U.S. application Ser. No. 12/691,219, filed on Jan. 21, 2010, now U.S. Pat. No. 7,905,938, which is a continuation application of U.S. application Ser. No. 11/344,749, filed Feb. 1, 2006, now U.S. Pat. No. 7,670,401, which claims the benefit of U.S. Provisional Application Serial No. 60/648,892, filed Feb. 1, 2005, U.S. Provisional Application Ser. No. 60/661,529 filed Mar. 14, 2005, and U.S. Provisional Application Ser. No. 60/737,190, filed Nov. 16, 2005, the contents of each of which are incorporated herein by reference, in their entirety.
BACKGROUND OF THE INVENTION
[0002] Portable fans, such as box fans, are popular as a cost-efficient means for cooling or ventilating interior areas of commercial and residential buildings. Box fans are inexpensive, light, and portable, and can be easily repositioned to provide a desired interior air flow.
[0003] Filters have been applied to box fans as a means for removing air-borne contaminants from the air flow. A number of mounting configurations have been devised that secure a filter to a box fan. U.S. Design Pa. No. DES 377,390 discloses a filter mount that is incorporated within the body of a box fan. This configuration requires a specialized fan chassis, and therefore is not applicable to general-purpose box fans. U.S. Pat. No. 4,781,526 discloses a filter mount that is affixed to an exterior portion of a fan body. In this configuration, the filter bracket is permanently affixed to holes formed in the fan body using specialized mounting hardware, such as machine screws. U.S. Pat. No. 6,527,838 discloses a filter mount including a plurality of brackets that adhere to a side surface of the fan. The brackets are permanently affixed to the fan, and take the form of specialized hardware, which, when mounted to a particular fan body, cannot be re-used on another fan. In alternative embodiments disclosed in the U.S. Pat. No. 6,527,838, a filter bracket is applied to a fan body using hook and loop fasteners or screws about a periphery of the body of the fan. Again, such specialized attachment hardware is semi-permanent, can disfigure the fan body, and cannot be re-used on another fan.
SUMMARY OF THE INVENTION
[0004] The present invention is directed to a filter mount for a box fan. A filter mount in the form of a frame is removably mountable to a fan chassis and does not cause any permanent disfigurement to the fan body. The filter frame is adapted and shaped to receive a standard air filter, such as the type of filter commonly used in residential heating systems. The filter and frame are preferably sized to closely match, and cover, a standard-sized fan grill at the input or output face of the fan, so that a substantial amount of air flow passes through the filter.
[0005] The filter frame is preferably sized to have a narrow profile so as not to inhibit the air flow induced by the fan. In one embodiment, straps are provided to secure the frame to the fan body, such that the frame is readily removable. In one embodiment, the straps comprise elastic bands. Tension in the elastic bands, when mounted, secures the filter frame to the fan chassis. The elastic bands are optionally adjustable in length so that the filter frame is compatible with a variety of fan chassis types and a variety of fan chassis thicknesses.
[0006] In another embodiment, the frame includes features that attach to a grill of a fan, for example, features that mate with one or more grill apertures. The frame can include, for example rigid pegs or hooks that are inserted in one or more grill apertures at one of a top and bottom of the fan grill, and spring-loaded hooks that are inserted in one or more grill apertures at the other of the top and bottom of the fan grill to secure the frame in place against the fan grill.
[0007] In another embodiment, a filter frame can be integrated directly into the grill of the fan. In this embodiment, the fan grill can be formed in a molding process to include integral filter guides at left side, right side, and bottom side portions of the fan grill. In this manner, the fan grill includes an integral filter frame that can accept standard-sized filters.
[0008] In this manner, a cost-effective means for filtering a flow of air is provided for residential and commercial settings. The filter frame is adaptable to a variety of standard box fan types of different styles and dimensions. The frame is configured to accommodate standard filters, such as those readily available from retail hardware stores and home centers.
[0009] In one embodiment, the filter frame includes one or more elastic bands, or bungy cords. Each elastic band is attached at a first end to one of the side members of the filter frame. A second end of each elastic band includes a hook that is adapted to attach to one of the front and rear grills of the fan, or other feature of the fan. The frame is mounted to one face of the fan body, and the elastic band or bands stretch about the sides of the fan to the other face of the fan body. The hooks operate in conjunction with the tension in the stretched band or bands to secure the filter frame to the fan body.
[0010] In one embodiment, a single pair of bands is employed, one band interfacing with each respective left and right side member of the frame at or near a central position of the side members. In some configurations, a single pair of bands is sufficient for securing the frame to the fan body. In another embodiment, where additional securing force is required, multiple pairs of bands are employed, each band of each pair interfacing with a left or right side member at top and bottom regions of the side members.
[0011] The elastic bands may be permanently attached to the frame, for example, by rivets or screws, or by tying the bands to the frame. Alternatively, the elastic bands are removable from the frame, for example, by hooks, buttons, loops, or other attachment mechanisms. One end, or both ends, of each elastic band can be removably or permanently attached to the frame.
[0012] In an embodiment where both ends of each elastic band attach to the frame, one or more of the bands loop around the fan body, for example over the top, bottom, left and/or right sides of the fan body, to secure the frame to the fan body. As mentioned above, the ends of each elastic band may be permanently or removably attached to the frame.
[0013] In an embodiment where a first end of each elastic band is attached to the frame, the second end includes a hook for attaching the elastic band to a feature of the fan chassis, for example, a fan grill, handle, or other feature. In another embodiment, elastic bands from left and right sides of the frame each include hooks, or other clasping features, such that the second ends of paired elastic bands can be coupled to each other to form one large band that extends about the fan chassis. In another embodiment, the frame includes pegs that extend from the frame and extend between adjacent cross members of the rear or front grill of the fan, such that the pegs prevent the frame from shifting or sliding relative to the cross members.
[0014] In another embodiment, the filter frame includes mounting knobs at spaced-apart coupling locations, and the elastic bands each include an array of holes at first ends of the bands. The holes of the elastic bands mate with the coupling knobs as a convenient mechanism for removably attaching the elastic bands to the filter frame. The second ends of the elastic bands may include hooks, as described above, for attaching to a fan chassis feature. Alternatively, the elastic bands include an array of holes at both ends, and the bands stretch about the body of the chassis, and couple to both sides of the frame. The mounting knobs secure the bands, and retain the elastic bands in a tensioned state, securing the filter frame to the fan. The array of holes are distributed along the length of the end of each band to allow for adjustment in the length of the elastic band. In this manner, the filter frame is adapted to accommodate fan bodies of different thicknesses.
[0015] In another embodiment, the filter frame is secured to the fan chassis by elongated bolts that extend through the body of the fan. Holes are included in the frame to receive the bolts. The holes are preferably elongated to allow for play in positioning the frame relative to the fan body, so that the frame is compatible with different fan grill configurations. The elongated bolts are secured to the filter frame and fan with washers and wing nuts, which, when tensioned, retain the filter frame against the body of the fan. The bolts are configured so as to avoid interference with fan operation.
[0016] In another embodiment, the filter frame is secured to the fan chassis using fasteners that are bolted to the frame. In one embodiment, the fastener is inserted into the fan grill in a horizontal position between cross members of the rear or front grill of the fan, and is then rotated to a vertical position and tightened in place to affix the filter frame to the fan. The fastener is sized to accommodate a range of fan grill configurations.
[0017] In an alternative embodiment, the frame is attached to the rear or front grill of a fan with standard cable ties.
[0018] In another embodiment, the filter frame is unitary and formed in a molding process, for example in a straight-pull injection molding process.
[0019] In another embodiment, the filter frame is adapted to receive multiple filters.
[0020] In another embodiment, the filter frame is unitary and formed in a molding process and includes spring-loaded hooks for securing the filter frame to the grill of the fan.
[0021] In another embodiment, the filter frame is integral with the front or rear grill of the fan body. The filter frame is molded on an outer portion of the front or rear grill, the filter frame and the front or rear grill being unitary.
[0022] In one aspect, the present invention is directed to a removable filter frame for a fan. A frame body includes opposed first and second side channels. Each of the first and second side channels has a longitudinal axis and the first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter. The removable filter frame further comprises a coupler that extends from the frame body in a direction transverse to the longitudinal axes of the first and second side channels. The coupler is constructed and arranged to couple the frame body to a grill of a fan.
[0023] In one embodiment, the frame body is unitary. Further, in another embodiment, the frame body is formed in a straight-pull injection molding process.
[0024] In another embodiment, the first and second side channels of the frame body are formed as separate units that are mounted together.
[0025] In another embodiment, the frame body further includes at least one cross member between the first and second side channels that provides for lateral rigidity to the frame body.
[0026] In another embodiment the first and second side channels each comprise a side surface of the frame body and tabs that extend from the frame body in a horizontal direction to define the first and second side channels.
[0027] In another embodiment, the stop is positioned at a bottom of at least one of the first and second side channels. In another embodiment, the stop comprises a portion of the frame body that extends in a horizontal direction between the longitudinal axes of the first and second side channels. Further, in another embodiment, the stop comprises a horizontal channel extending in the horizontal direction between bottom portions of the first and second side channels.
[0028] In another embodiment, the coupler comprises at least one tab that extends from the frame body and is constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0029] In another embodiment, the coupler comprises at least one hook that extends from the frame body and is constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0030] In another embodiment, the at least one hook is spring-loaded.
[0031] In another embodiment, the coupler comprises one of multiple fasteners, multiple elongated bolts, and multiple cable ties that extend from the frame body and are constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0032] In another embodiment, the removable filter frame further comprises elastic bands that are coupled to the frame body and are constructed and arranged to couple about a chassis of a fan.
[0033] In another embodiment, the removable filter frame further comprises a foam pad coupled between the frame body and a grill of a fan.
[0034] In another embodiment, the first side channel and the second side channel are constructed to have a depth such that multiple filters can be inserted in the frame body.
[0035] In another aspect, the present invention is directed to a removable filter frame for a fan. A frame body includes opposed first and second side channels. The first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter. At least one elastic band is coupled to the frame body, the at least one elastic band is constructed and arranged to extend about a portion of a fan chassis so that when installed, tension in the at least one elastic band operates to secure the frame body to a fan.
[0036] In one embodiment, the frame body is unitary.
[0037] In another embodiment, the frame body is formed in a straight-pull injection molding process.
[0038] In another embodiment the first and second side channels of the frame body are formed as separate units that are mounted together.
[0039] In another embodiment, the frame body further includes at least one cross member between the first and second side channels that provides lateral rigidity to the frame body.
[0040] In another embodiment, the first and second side channels each comprise a side surface of the frame body and tabs that extend from the frame body in a horizontal direction to define the first and second side channels.
[0041] In another embodiment, the stop is positioned at a bottom of at least one of the first and second side channels. In another embodiment, the stop further comprises a portion of the frame body that extends in a horizontal direction between the first and second side channels. In another embodiment, the stop comprises a horizontal channel extending in the horizontal direction between bottom portions of the first and second side channels.
[0042] In another embodiment, the at least one elastic band comprises a plurality of elastic bands, each coupled at both ends to the frame body.
[0043] In another embodiment, the at least one elastic band comprises a plurality of elastic bands, each coupled at one end to the frame body.
[0044] In another embodiment, each of the elastic bands of the plurality of elastic bands further comprises a hook at at least one end. The hook is constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0045] In another embodiment, each of the elastic bands of the plurality of elastic bands comprises a hook at a first end and a plurality of holes at a second end and the frame body further comprises knobs. The plurality of holes at the second end of each of the plurality of elastic bands is adapted to mate with one of the knobs to define a length of each of the elastic bands between the knob of the frame body and the hook.
[0046] In another embodiment, the at least one elastic band is removably coupled at at least one end to the frame body.
[0047] In another embodiment, the at least one elastic band is fixed at at least one end to the frame body.
[0048] In another embodiment, the first and second side channels are constructed to have a depth such that multiple filters inserted in the frame body.
[0049] In another embodiment, the removable filter frame further comprises a coupler extending from the frame body in a direction transverse to longitudinal axes of the first and second side channels. The coupler is constructed and arranged to couple the frame body to a grill of a fan.
[0050] In another embodiment, the coupler comprises at least one tab that extends from the frame body and is constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0051] In another embodiment, the coupler comprises at least one hook that extends from the frame body and is constructed and arranged to couple the frame body to a grate of a grill of a fan. In another embodiment, the at least one hook is spring-loaded.
[0052] In another embodiment, the coupler comprises one of multiple fasteners, multiple elongated bolts, and multiple cable ties that extend from the frame body and are constructed and arranged to couple the frame body to a grate of a grill of a fan.
[0053] In another aspect, the present invention is directed to grill for a fan. A latticed grate includes cross members and openings and has an inner surface and an outer surface. Retaining members extend from the outer surface of the grate in a direction transverse to the outer surface at first and second outer regions of the grill to define opposed first and second side channels. The first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter.
[0054] In one embodiment, the grate and the retaining members are formed in a molding process so that they are unitary. In another embodiment, the grate and the retaining members are formed in a straight-pull injection molding process.
[0055] In another embodiment, the retaining members are L-shaped. A first portion of each retaining member extends from the outer surface in a direction transverse to the outer surface and a second portion of each retaining member extends from the first portion of the retaining member in a direction substantially parallel to the outer surface and toward a middle region of the grate.
[0056] In another embodiment, the stop is L-shaped. A first portion of the stop extends from the outer surface in a direction transverse to the outer surface and a second portion of the stop extends from the first portion of the stop in a direction substantially parallel to the outer surface and toward a middle region of the grate.
[0057] In another embodiment, the stop is integrated into the retaining members at a low end of the slot.
[0058] In another embodiment, each of the first and second side channels includes multiple retaining members.
[0059] In another embodiment, each of the first and second side channels includes a single retaining member.
[0060] In another embodiment, the stop comprises multiple stops.
[0061] In another aspect, the present invention is directed to a fan. The fan includes fan blades and a motor that operates the fan blades. A fan chassis surrounds the motor and fan blades. Front and rear grills shield the fan blades and allow for air movement through the fan. Each of the front and rear grills includes a latticed grate having cross members and openings and has an inner surface and an outer surface. Retaining members extend from the outer surface of the grate of at least one of the front and rear grills in a direction transverse to the outer surface at first and second outer regions to define opposed first and second side channels. The first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter.
[0062] In one embodiment the grate and the retaining members are formed in a molding process so that they are unitary.
[0063] In another aspect, the present invention is directed to a method of mounting a filter to a fan. The method includes coupling a frame body having opposed first and second side channels, each of the first and second side channels having a longitudinal axis, to a grill of a fan by couplers extending from the frame body in a direction transverse to the longitudinal axes of the first and second side channels. The couplers engage a grate of the grill through an opening in the grate. The first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter. An air filter is inserted into an upper end of the slot.
[0064] In one embodiment, coupling the frame body to the grill of the fan further comprises coupling the frame body to a grate of the grill of the fan using at least one tab extending from the frame body.
[0065] In another embodiment, coupling the frame body to the grill of the fan further comprises coupling the frame body to a grate of the grill of the fan using at least one hook extending from the frame body. In another embodiment, the at least one hook is spring-loaded.
[0066] In another aspect, the present invention is directed to a method of mounting a filter to a fan. The method comprises coupling a frame body having opposed first and second side channels to a grill of a fan by at least one elastic band extending about a portion of a fan chassis so that when installed, tension in the at least one elastic band operates to secure the frame body to a fan. The first and second channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter. An air filter is inserted into an upper end of the slot.
[0067] In another aspect, the present invention is directed to a method that comprises forming a grill for a fan including a latticed grate including cross members and openings and having an inner surface and an outer surface. The method further comprises forming retaining members that extend from the outer surface of the grate in a direction transverse to the outer surface at first and second outer regions of the grill to define opposed first and second side channels. The first and second side channels define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop for restricting further movement of an inserted air filter. The method further comprises mounting the grill to a fan chassis.
BRIEF DESCRIPTION OF THE DRAWINGS
[0068] The foregoing and other objects, features and advantages of the invention will be apparent from the more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
[0069] FIGS. 1A and 1B are perspective views of an embodiment of the present invention. FIG. 1A is a perspective view of a filter frame including elastic bands and FIG. 1B is a perspective view of the filter frame of FIG. 1A attached to a box fan, in accordance with the present invention.
[0070] FIGS. 2A-2D are perspective views of another embodiment of the present invention. FIG. 2A is a perspective view of an elastic band including an array of holes. FIG. 2B is a perspective view of the elastic bands of FIG. 2A attached to a box fan. FIG. 2C is a perspective view of a filter frame including mounting knobs. FIG. 2D is a perspective view of the filter frame of FIG. 2C attached to the box fan of FIG. 2B by the elastic bands of FIG. 2A , in accordance with the present invention.
[0071] FIGS. 3A and 3B are perspective views of another embodiment of the present invention. FIG. 3A is a perspective view of a filter frame attachable to a box fan using elastic bands that are attached to the frame at both ends of the bands. FIG. 3B is a perspective view of the filter frame of FIG. 3A attached to a grill of a box fan, in accordance with the present invention.
[0072] FIG. 4 is a perspective view of another embodiment of the present invention including a filter frame attachable to a grill of a box fan using elongated bolts, washers and wing nuts.
[0073] FIG. 5 is a perspective view of another embodiment of the present invention including a filter frame attachable to a grill of a box fan using a threaded fastener and bolt.
[0074] FIGS. 6A and 6B are perspective views of another embodiment of the present invention. FIG. 6A is a perspective view of a standard cable tie and FIG. 6B is a perspective view of a filter frame attachable to a grill of a box fan using the standard cable tie of FIG. 6A , in accordance with the present invention.
[0075] FIG. 7 is a perspective view of another embodiment of the present invention, in which the filter frame includes first and second side members and no base member, and in which a foam pad is applied between the frame and the fan body, in accordance with the present invention.
[0076] FIG. 8 is a perspective view of another embodiment of the present invention, in which the filter frame includes a widened channel that is adapted to receive both a universal filter and a HEPA-standard filter, in accordance with the present invention.
[0077] FIG. 9 is a close-up perspective view of a side member of the filter frame of FIGS. 7 and 8 , including a channel stop at an end of the channel, in accordance with the present invention.
[0078] FIGS. 10A and 10B are illustrations of another embodiment of the present invention. FIG. 10A is a front view of another embodiment of a filter frame formed in a mold process. FIG. 10B is a close-up perspective view of a side edge of the filter frame of FIG. 10A .
[0079] FIGS. 11A , 11 B, 11 C and 11 D are perspective views of another embodiment of the present invention. FIG. 11A is a perspective view of another embodiment of the molded filter frame of FIGS. 10A and 10B including spring-loaded hooks for latching the filter frame to the grill of the fan. FIG. 11B is a close-up perspective view of a top corner of a rear face of the filter frame of FIG. 11A including the spring-loaded hooks. FIG. 11C is a close-up perspective view of a corner of a front face of the filter frame of FIG. 11A . FIG. 11D is a perspective view of the filter frame of FIG. 11A mounted to a fan body.
[0080] FIGS. 12A-12C are perspective views of another embodiment of the present invention. FIG. 12A is a perspective view of another embodiment of the molded filter frame of FIGS. 10A and 10B including spring-loaded hooks for latching the filter frame to the grill of the fan. FIG. 12B is a close-up perspective view of a bottom corner of a rear face of the filter frame of FIG. 12A including spring-loaded hooks. FIG. 12C is a close-up perspective view of a top corner of a rear face of the filter frame of FIG. 12A .
[0081] FIGS. 13A-13E are perspective views of another embodiment of the present invention. FIG. 13A is an embodiment of the filter frame integral with a fan grill attached to the fan body. FIG. 13B is a close-up perspective view of a side edge of the filter frame and the fan grill of FIG. 13A . FIG. 13C is an exploded perspective view of an embodiment of a box fan and fan grill with an integral filter frame. FIGS. 13D and 13E are assembled views of alternative embodiments of the fan grill with an integrated filter frame.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0082] FIG. 1A is a perspective view of a filter frame 32 adapted to be secured to a body of a portable fan, such as a standard box fan, using elastic bands 33 . A filter frame 32 is configured to include frame channels in a U-shaped arrangement having first and second side members 42 and a base member 44 . Cross-members 37 are coupled between opposite corners of the frame to provide lateral rigidity. The first and second side members 42 include longitudinal channels 46 that are spaced apart and opposed, and that provide a slot or seat for receiving side edges of an inserted filter. The base member 44 extends between the first and second side members 42 and includes a similar longitudinal channel 47 that is aligned with the longitudinal channels 46 of the side members 42 for receiving a bottom edge of an inserted filter. Top portions of the side member frame channels 46 are open to provide an insertion and removal location for the filter. The side members 42 , base member 44 , and cross members 37 of the filter frame 32 comprise extruded aluminum, plastic, graphite, or other suitable light-weight and durable material that is molded or otherwise machined or formed. The members may be riveted, bolted, welded, or otherwise coupled together, or may be molded and formed as a complete unit.
[0083] Elastic bands 33 are permanently attached, at first ends, to a top right corner, bottom right corner, top left corner and bottom left corner of the filter frame 32 . The elastic bands 33 are, for example, riveted, bolted, tied, or otherwise attached to the frame 32 . The elastic bands 33 further include hooks 34 , or other clasping mechanisms, at a second end. The elastic bands 33 comprise, for example, bungy cords, elastic ribbons, or straps. In alternative embodiments, the hooks 34 on the elastic bands 33 are tied, coupled to, or integral with, the elastic bands 33 at their second ends. The hooks 34 are preferably coated with a soft plastic or rubber material to avoid scratching the fan chassis.
[0084] The frame 32 is preferably sized to closely match, and cover, a standard-sized fan grill at an input or output face of the fan, so that a substantial amount of air flow induced by the fan passes through the inserted filter. The side members 42 , base member 44 and cross members 37 of the filter frame are preferably sized to have a narrow profile so as to reduce the restriction of air flow. In one embodiment, the frame channels 46 are spaced apart a suitable distance, and formed of a depth, so as to accommodate a general purpose forced-air filter, for example ¾″ by 20″ by 20″ in size. The 20″ by 20″ filter profile matches well with a variety of box fan sizes. Therefore, the depth of the channel 46 in this example is made to be slightly larger than ¾″ and the side members 42 are spaced apart slightly more than 20″ in order to accommodate an inserted filter. Other filter sizes and other channel depths can also be applied to accommodate fans and filters of varying dimensions, and are equally applicable to the present invention.
[0085] FIG. 1B is a perspective view of the filter frame 32 of FIG. 1A attached to a box fan 31 . The frame 32 is positioned at a first face 52 of the box fan 31 and the elastic bands 33 are pulled about the sides of the fan chassis to a second face 54 of the fan 31 . The hooks 34 are clasped to an existing feature of the box fan 31 , for example a grate of a grill 71 on the second face 54 of the fan. Tension in the stretched elastic bands 33 retains the filter frame 32 against the fan body 31 . Although the above described embodiment illustrates multiple bands 33 with hooks 34 at each of the first and second side members 42 , each side member 42 can optionally include a single elastic band/hook, depending on the application. The elastic band configuration is equally applicable to any of the filter frame embodiments described herein.
[0086] FIGS. 2A-D are perspective views of another embodiment of the present invention. FIG. 2A is a perspective view of an elastic band 38 having a hook 34 at a proximal end and an array of holes 50 at a distal end. In one embodiment, the holes 50 are spaced ¾″ apart and are distributed longitudinally along the end of the elastic band 38 .
[0087] FIG. 2B is a perspective view of the elastic bands 38 of FIG. 2A hooked onto a grate of a grill 71 at a second face 54 of the box fan 31 at top right, bottom right, top left, and bottom left positions by the hooks 34 .
[0088] FIG. 2C is a perspective view of a filter frame 32 of a construction generally similar to that described above in FIG. 1A . In this embodiment, however, the elastic bands are not permanently attached. Instead, the filter frame 32 includes mounting knobs 41 that extend from the body of the frame 32 at top right, bottom right, top left and bottom left corners of the frame. The mounting knobs 41 have relatively narrow necks with relatively wide heads, such that when the holes 50 at the distal ends of the elastic bands 38 , held in place at their proximal ends by the hooks 34 , are pulled over the knobs 41 , the elastic bands 38 are seated in position by the heads of the knobs 41 .
[0089] FIG. 2D is a perspective view of the filter frame of FIG. 2C attached to the box fan 31 of FIG. 2B by the elastic bands 38 of FIG. 2A . The holes 50 of the elastic bands 38 are pulled over the mounting knobs 41 of filter frame 32 to secure the four corners of the filter frame 32 to the box fan 31 . Tension in the stretched elastic bands 38 retains the filter frame 32 against the body of the fan 31 . Different holes 50 of the elastic bands 38 can be used to accommodate fan bodies 31 of different thicknesses, and to accommodate a range of different positions for hooking the hooks 34 on the grill, or other feature, of the fan. The mounting knob/elastic band configuration can be applied to any of the frame embodiments described herein.
[0090] In another embodiment, each of the upper and lower pairs of elastic bands 33 , 38 of the FIG. 1 and FIG. 2 embodiments described above can be dimensioned in length so that their hooks 34 , or other clasping features, can be coupled to each other to form one large band that extends about the fan chassis to secure the filter frame 32 in place.
[0091] FIGS. 3A and 3B are perspective views of another embodiment of the present invention. FIG. 3A is a perspective view of a filter frame 32 attachable to a box fan using elastic bands. In this embodiment, the elastic bands 25 a, 25 b are permanently coupled to the opposed first and second side members 42 of the filter frame 32 . A first elastic band 25 a extends across the filter frame 32 from the top right corner to the top left corner, and a second elastic band 25 b extends from the bottom right corner to the bottom left corner of the filter frame 32 . When mounting the frame 32 to a box fan 31 , as shown in FIG. 3B , the first elastic band 25 a is pulled over the top of the box fan 31 , and the second elastic band 25 b is pulled over the bottom of the box fan 31 . Alternatively, the first and second elastic bands 25 a, 25 b can both be pulled over the top or the bottom of the box fan 31 and positioned into place. The tension in the elastic bands 25 a, 25 b retains the filter frame 32 against the box fan 31 . In alternative embodiments, one end, or both ends, of the elastic bands 25 a, 25 b are removable from the filter frame 32 , for example using the holes and knobs combination described above with reference to FIGS. 2A-2D . This elastic band configuration is equally applicable to any of the filter frame embodiments described herein.
[0092] FIG. 4 is a perspective view of another embodiment of the present invention including a filter frame attachable to a grill of a box fan 31 using elongated bolts 53 , washers 65 and wing nuts 64 . In this embodiment, the filter frame 32 is secured to the fan chassis 31 by elongated bolts 53 that extend through the fan 31 . For example, the bolts 53 can be configured to be of a length so as to extend through grate openings that exist in both the front and rear grills 71 of the fan 31 . Holes 62 are included in the frame 32 at the cross members 37 or side members 42 to receive the bolts 53 . The holes 62 are preferably elongated to allow for play in positioning the frame 32 relative to the fan body 31 , so that the frame 32 is compatible with different fan grill configurations. The elongated bolts 53 are secured to the filter frame 32 and fan 31 with washers 65 and wing nuts 64 , which, when tensioned, retain the filter frame 32 against the body of the fan 31 . The holes 62 and bolts 53 are configured to align with the four corners of the fan grill, so as to avoid interference with fan operation. The bolts 53 are preferably of a length so as to accommodate fan bodies of different depths. Tightening the wing nuts 64 creates a tension in the bolts that retains the filter frame 32 against the fan body 31 . The wing nuts 64 and bolts 53 are readily mountable by an individual without the need for tools. The elongated bolt and wing nut mounting configuration can be applied to any of the filter frame embodiments described herein.
[0093] FIG. 5 is a perspective view of another embodiment of the present invention including a filter frame 32 attachable to a grill of a box fan 31 using fasteners 18 . The fasteners 18 are bolted to the frame 32 , for example at cross-members 37 or side members 42 . Holes 67 are included in the frame 32 to receive the bolts 66 . The holes 67 are preferably elongated to allow for play in positioning the frame 32 relative to the fan body 31 , so that the frame 32 is compatible with different fan grill configurations. A fastener 18 is inserted into a fan grill 71 in a horizontal position between cross members of the rear or front fan grill 71 of the fan, and is then rotated to a vertical position and tightened in place with bolt 66 to affix the filter frame 32 to the fan 31 . The fastener 18 is sized to accommodate a range of fan grill configurations. The fastener 18 may include a threaded hole 68 to receive the bolt 66 , or, optionally washers and nuts may be employed. Tightening the bolt 66 relative to the fastener 68 provides tension which holds the frame 32 against the box fan 31 . The fastener configuration described in FIG. 5 is equally applicable to any of the filter frame embodiments described herein.
[0094] FIGS. 6A and 6B are perspective views of another embodiment of the present invention. In this embodiment, a plurality of standard cable ties 69 as shown in FIG. 6A are used to mount the filter frame 32 to the grill of the box fan 31 as shown in FIG. 6B . Holes 67 , for example elongated holes, are formed in the cross members 37 or side members 42 of the frame 32 , and standard cable ties 69 are wrapped around the holes 67 and a grate of the fan grill 71 , and tightened, to secure the filter frame 32 against the fan grill 71 . The excess portion of the cable tie 20 is preferably cut off to avoid vibration during fan operation, and to avoid interference with an inserted filter. The cable ties 69 are tightened so as to create sufficient tension to secure the filter frame 32 to the box fan 31 . The cable tie configuration described in FIG. 6 is equally applicable to any of the filter frame embodiments described herein.
[0095] FIG. 7 is a perspective view of another embodiment of the present invention. In this embodiment, the filter frame 32 includes first and second side members 42 A, 42 B and no base member. In this embodiment, rather than including a base member 44 as shown in the above embodiments of FIGS. 1-6 , the side members 42 A, 42 B of the present embodiment each include a channel stop 106 at or near a distal end of the channel 46 , in order to limit or stop the insertion of a filter 100 , as shown in FIG. 9 . The channel stop 106 can take the form of a solid face, a mesh surface, a peg, a dimple, or any suitable means for restricting downward movement of the filter 100 in the channel 46 . The channel stop structure can be applied to any of the filter frame embodiments described herein.
[0096] Further, in the embodiment of FIG. 7 , a single pair of elastic bands 33 and hooks 34 is included for mounting the filter frame 32 to the fan body. A single pair of elastic bands 33 can be equally as effective as a double pair as shown above in FIGS. 1 , 2 and 3 for securing the frame 32 to the fan body 31 , depending on the application.
[0097] In addition, the embodiment of FIG. 7 includes an optional foam pad 108 or gasket that is applied between the filter frame 32 and the fan body 31 . The foam pad 108 includes an opening 109 that allows free passage of air, the opening 109 being about as large as the cross-section of the volume of air that the fan is designed to push, so as not to restrict air flow. The foam pad 108 prevents air from entering the fan at a gap that may be present between the filter frame 32 and the surface of the fan body 31 . In this manner, the foam pad 108 causes more of the air that is pushed by the fan to pass through the filter 100 , thereby improving the air cleaning efficiency of the system. Further, if the foam pad 108 is cut to closely match the diameter of the fan blades, back draft in the corners of the box fan can be prevented. By preventing the back draft in the box fan, an air flow can be created that flows in a single direction, thus making the fan more efficient in configurations in which negative air pressure is created. The foam pad configuration can be applied to any of the filter frame embodiments described herein.
[0098] FIG. 8 is a perspective view of another embodiment of the present invention. In this embodiment, the filter frame 32 includes a widened channel 46 . The channel 46 is widened so as to accommodate both a universal pre-filter 100 and a High Efficiency Particulate Air (HEPA) type filter 102 , in accordance with the present invention. The widened channel 46 , in one embodiment, is a single channel that is of a width so as to accommodate both the universal pre-filter 100 and the HEPA filter adjacent each other. In another embodiment, the channel 46 may comprise a double channel that includes a central rail for partitioning first and second slots of the channel. In this manner, either, or both, filters 100 , 102 can be properly seated in designated slots of the channel 46 . This widened channel configuration can be applied to any of the filter frame embodiments described herein.
[0099] Further, the embodiment of FIG. 8 includes pegs or bumps 104 that extend in a direction transverse to the longitudinal direction of the filter channels from a face of each side member 42 A, 42 B or optionally from the cross members 37 or other portion of the frame 32 . The pegs 104 are adapted to rest in an opening between adjacent grates of the fan grill 71 . The pegs 104 prevent the frame 32 from shifting or sliding in a downward direction when the frame 32 is mounted to the fan and prevent movement of the frame 32 relative to the fan as a result of vibration. In one embodiment, the pegs 104 are approximately ¼″ in length. The peg configuration is equally applicable to any of the filter frame embodiments described herein.
[0100] FIGS. 10A and 10B are illustrations of another embodiment of the present invention. FIG. 10A is a front view of another embodiment of a filter frame 74 that is suitable for formation in a mold process. This embodiment of the filter frame 74 includes first and second spaced-apart and opposing side channels 46 that are defined by a plurality of side channel tabs 76 . The channels 46 provide a guide for receiving opposite edges of an inserted filter. The frame 74 further includes cross-members 37 that are coupled between opposite corners of the frame to provide lateral rigidity. The lowest side tabs 76 of the channels 46 are provided with bottom surfaces 78 that operate as a stop to limit the vertical position of the inserted filter. A top portion 89 of the frame 74 is open to provide an insertion and removal location for the filter. The left and right edges of the frame include mounts 80 , each comprising an opening for attaching elastic bands, bolts and nuts, hooks, or other fastening means to secure the filter frame 74 to the fan body, for example in the manner of the other embodiments described herein.
[0101] FIG. 10B is a close-up perspective view of a side edge of the filter frame 74 of FIG. 10A . In this view it can be seen that a void 82 is provided in the channel 46 under each respective side tab 76 . In this manner, the filter frame of the present embodiment can be formed in a straight-pull injection molding process, such that there are no secondary movements required inside the mold during the molding process. An extension formed in the lower mold passes through a region where the voids 82 are to be formed. When the upper and lower molds are in position, material is injected, and the extension formed in the lower mold defines a lower part of the side tabs 76 . When the mold is retracted, the extensions pass through the voids that are formed below the tabs, so as to form the frame in a straight-pull injection molding process. In this embodiment, the side edges, side tabs 76 , bottom surfaces 78 , notches 80 , and cross members 37 of the filter frame 74 comprise aluminum, plastic, composite, graphite, or other suitable light-weight and durable material that can be formed in a molding process. The molded filter frame of FIG. 10A formed in the straight-pull injection molding process is equally applicable to any of the filter frame embodiments described herein.
[0102] FIGS. 11A , 11 B, 11 C and 11 D are perspective views of another embodiment of the present invention. FIG. 11A is a perspective view of another embodiment of the molded filter frame of FIGS. 10A and 10B including spring-loaded or spring-biased hooks for attaching the frame directly to a grill of the fan. FIG. 11B is a close-up perspective view of a top corner of a rear face of the filter frame 74 of FIG. 11A . FIG. 11C is a close-up view of a corner of a front face of the filter frame 74 of FIG. 11A . In this embodiment, springs 92 are attached to the top corners of the filter frame 74 . A first end of each spring 92 is attached to the filter frame 74 at a spring seat 90 , for example in a press-fit relationship, or alternatively by a fastener or adhesive. A second end of each spring 92 extends through a corresponding hole 96 at each top corner of the filter frame. In this embodiment, the second ends of the springs 92 include integral hooks 94 . The hooks 94 are adapted to secure the filter frame 74 to the grate of the fan grill, and are shaped to interlock with features of common fan grills, for example rectangular openings and grates of the fan grill. The hooks 94 extend in a direction transverse to the longitudinal axes 101 of the channels 46 , and fingers 94 A at the ends of the hooks are configured to be inserted through an aperture in the fan grill and to latch a surface of the fan grill, for example an inner surface of a grate of the fan grill. In this manner, a top portion 89 of the filter frame 74 is removably secured to the fan body at the fan grill by a downward force of the springs 92 . The filter frame 74 further includes lower tabs 93 at a bottom region of the filter frame 74 . The lower tabs 93 can be integral with the filter frame 74 and can be molded on or otherwise attached to the filter frame 74 . The lower tabs 93 are adapted to secure the filter frame 74 to the fan grill and are shaped to extend from the filter frame 74 in a direction transverse to the longitudinal axes 101 of the channels 46 of the filter frame 74 so as to interlock with a feature of a common fan grill, for example the openings and grates of the fan grill. Lips, or other interlocking features, that extend from the lower tabs 93 are adapted to latch with the inner surfaces of the grates of the fan grill, through openings in the grate. The lower tabs 93 operate to counteract the downward force of the springs 92 . The tension between the springs 92 and the lower tabs 93 operates to retain the filter frame against the fan body 31 . The present spring-loaded hook and tab configuration is applicable to any of the filter frame embodiments described herein. FIG. 11D is a perspective view of the filter frame 74 of FIG. 11A mounted to a fan body 31 . Hooks 94 are inserted through apertures 75 of the fan grill and interlocked with the cross-members of the grate 73 of the fan grill 71 . Lower tabs 93 extend through apertures 75 of the fan grill and are latched with the inner surfaces of the grates 73 of the fan grill 71 .
[0103] FIGS. 12A , 12 B and 12 C are perspective views of another embodiment of the present invention. FIG. 12A is a perspective view of another embodiment of the molded filter frame 74 of FIGS. 10A and 10B including spring-loaded or spring-biased hooks. FIG. 12B is a close-up perspective view of a bottom corner of a rear face of the filter frame 74 of FIG. 12A . FIG. 12C is a close-up of a top corner of a rear face of the filter frame 74 of FIG. 12A . This embodiment is similar in structure and form to the embodiment of FIG. 11 above, except that in this embodiment, the tabs 93 are at an upper portion of the filter frame 74 and the springs 92 are at lower portion of the filter frame 74 . In the present embodiment, the tabs 93 include fingers 99 that are oriented in a downward direction, and therefore, when inserted in a grate of a fan grill, through an opening in the grate, the tabs 93 bear the weight of the filter frame 74 and mounted filter. The springs 92 include upward-oriented hooks which, when engaged with the grate of the fan grill, operate to hold the filter frame 74 in place against the grill. Mounts 80 are also included at far left and right edges of the filter frame 74 for further mounting the frame to the fan body using optional elastic bands, as described above. The present embodiment can be applied to any of the filter frame embodiments described herein.
[0104] FIGS. 13A-13E are perspective views of another embodiment of the present invention in which a filter frame is integral with a fan grill of the fan body. Referring to FIG. 13A , the grill 111 includes a latticed grate that includes cross members and openings. The grill 111 of the box fan 31 includes multiple side tabs 110 that form first and second side channels 118 and multiple bottom tabs 112 that form a base channel 119 . The side tabs 110 operate as retaining members for an inserted filter, and extend outwardly from the grill 111 surface in a direction transverse to a longitudinal axis of the first and second side channels 118 , and then in an inward direction toward a center of the grill. The bottom tabs 112 operate as stops for an inserted filter and, in the embodiment shown in FIG. 13A , extend from the surface of the fan grill 111 in a manner similar to the side tabs 110 . The side and bottom tabs 110 , 112 are molded with the grill 111 of the box fan 31 , such that the filter frame and the grill 111 of the box fan are unitary. The side tabs 110 and bottom tabs 112 in combination provide a slot or seat for securing an inserted filter to the grill 111 of the box fan 31 . The side channels 118 are spaced apart, as described above, and are dimensioned to provide a seat for receiving opposite edges of an inserted filter. The bottom tabs 112 operate as a stop at a bottom portion of the slot to provide a location for vertical positioning of the inserted filter. A top portion 89 of the slot provided by the filter frame is open to provide an insertion and removal location for the filter. With reference to FIG. 13B , in an alternative embodiment, the side tabs 110 can be molded directly to the grill 111 . The side tabs 110 each include a first portion 110 a that extends in an outward direction from the surface of the fan grill and a second portion 110 b that extends from the first portion 110 a in a direction toward a central region of the fan, for example L-shaped, so as to form a channel 118 . The tabs 110 , 112 and underlying voids 111 a are preferably shaped so as to accommodate a straight-pull injection molding process for forming the grill 111 , as described above. FIG. 13C is an exploded perspective view of an embodiment of a box fan and fan grill including an integral filter frame. The box fan has fan blades 117 and a motor for operating the fan blades 117 . A fan chassis surrounds the fan blades and motor. The fan grill shields the fan blades 117 and allows for air movement through the fan. The filter frame may be integral with the front grill, the rear grill, or both the front and rear grills of the box fan 31 .
[0105] With reference to FIG. 13D , the side tabs 110 are integral with the grill 111 . In this embodiment, the lowest side tabs 110 of the channels 118 are provided with bottom surfaces 114 that operate as a stop to prevent further insertion of the filter. Therefore, in this embodiment, additional bottom tabs are not necessary.
[0106] FIG. 13E is an assembled view of another embodiment of the grill 111 with an integrated filter frame including single, elongated, left and right side tabs 116 and a single bottom tab 120 , rather than multiple tabs as shown above.
[0107] In one embodiment of a method of mounting a filter to a fan 31 , the method includes coupling the filter frame 32 , 74 that has opposed first and second side channels 46 , each of the first and second side channels 46 having a longitudinal axis, to a grill 71 of a fan by couplers, for example elongated bolts 53 and wing nuts 64 , fasteners 18 , cable ties 69 , hooks 94 or tabs 93 , extending from the frame body in a direction transverse to the longitudinal axes of the first and second side channels 46 . The couplers engage a grate 73 of the grill 71 through an opening 75 in the grate. The first and second side channels 46 define a slot for insertion of an air filter. The slot has an upper portion 89 that allows for insertion and removal of an air filter, and a lower end that includes a stop 44 , 106 , 78 , for restricting further movement of an inserted air filter. An air filter 100 , 102 is inserted into an upper end of the slot. Coupling the frame body to the grill of the fan optionally further includes coupling the frame body to the grate 73 of the grill of the fan using at least one tab 93 extending from the frame body 32 , 74 . Further, coupling the frame body 32 , 74 to the grill of the fan optionally further includes coupling the frame body to the grate 73 of the grill of the fan using at least one hook 94 extending from the frame body 32 , 74 .
[0108] In another embodiment of a method of mounting a filter to a fan 31 , the method includes coupling a frame body 32 , 74 having opposed first and second side channels 46 to a grill of a fan by at least one elastic band 33 , 38 , 25 a, 25 b extending about a portion of a fan chassis so that when installed, tension in the at least one elastic band 33 , 38 , 25 a, 25 b operates to secure the frame body to the fan 31 . The first and second channels 46 define a slot for insertion of an air filter. The slot has an upper portion 89 that allows for insertion and removal of an air filter, and a lower end that includes a stop 44 , 106 , 78 for restricting further movement of an inserted air filter. An air filter 100 , 102 is inserted into an upper end of the slot.
[0109] In another embodiment, a method for forming a grill 111 for a fan 31 comprises forming a latticed grate including cross members and openings and having an inner surface and an outer surface. The method further includes forming retaining members 110 , 116 extending from the outer surface of the grate in a direction transverse to the outer surface at first and second outer regions of the grill 111 to define opposed first and second side channels 118 . The first and second side channels 118 define a slot for insertion of an air filter. The slot has an upper end that allows for insertion and removal of an air filter, and a lower end that includes a stop 112 , 114 , 120 for restricting further movement of an inserted air filter. The grill 111 is mounted to a fan chassis.
[0110] In this manner, the present invention provides a filter frame that can be readily mounted to and removed from a chassis of a fan, without causing permanent disfigurement of the fan body. In addition, the present invention provides a filter frame that is integrated into the grill of the frame, to further ease the application of a filter to a fan.
[0111] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made herein without departing from the spirit and scope of the invention as defined by the appended claims. | A filter frame is removably attachable to a box fan. The filter frame is adapted for receiving a standard HVAC-style filter for removing contaminants from air flow induced by the fan. In this manner, a cost-effective means for filtering a flow of air is provided for residential and commercial settings. The filter frame is adaptable to a variety of standard box fan types of different styles and dimensions. The frame is configured to accommodate standard filters, such as those readily available from retail hardware stores and home centers. | 5 |
BACKGROUND OF THE INVENTION
Carpeting is manufactured from yarns or tows produced from natural or synthetic staple fibers or continuous synthetic filaments, respectively. The fibers are delivered to a yarn spinning plant in bales while the filament is shipped on cones. The yarn maker generally blends all of the staple fiber of a particular lot (generally 10 to 50 bales), through an opening process which consist of mixing portions of each bale in the lot in one or more opening operations (a process by which the compressed bale fibers are separated and by taking fibers from several bales at a time the fibers of the entire lot are blended, thus insuring a greater uniformity among the fibers, by carding as a first operation which tends to draw the fibers parallel and form long ropes of the fiber called card-slivers which are several inches in diameter). The output of these operations, the redistribution of the many fibers in the lot into a card-sliver, insures more uniform yarn properties, such as dye acceptance. In some instances the fibers are blended twice, or cross blended as this practice is referred to in the trade. Depending upon the ultimate use of the yarn, various treatments may be undertaken during blending, such as tinting for lot identification and/or application of lubricants and the like. The blended fibers in this rope-like card sliver are fed to pin drafters, an operation tending to further parallel the individual fibers and draw down the diameter of the resulting sliver. It is customary for the sliver to be pin-drafted several times so that the yarn (referred to as a singles) subsequently produced will be of the desired weight and, of course, obtain uniformity through further combining and paralleling of the fibers.
A yarn, or more properly a tow, may also consist of an assembly of any number of continuous mono-filaments drawn from several cones which are combined and twisted to give a continuous multi-filament tow singles.
Normally these singles yarns, from both staple and continuous filaments, are plied, two ply being the most common, by twisting the singles in a reverse direction to the singles twist, a process referred to as cabling.
In most modern day carpet mills the yarns or tows are "tufted" or punched through a scrim or primary backing made from jute, polypropylene or other woven or non-woven mmaterial on machines which may be and usually are computerized to enable numerous designs both as to length of the loop, type of loop, number of loops per inch, etc. to be made. This assembly can be, and usually is, dyed in one of the numerous batch or continuous dye machines commonly in use today. The so tufted carpet may have the loops cut, if a cut loop pile is desired, and an adhesive, such as latex, urethane or the like, applied and cured onto the back of the carpet to anchor the tufts to the primary backing. The carpet is usually trimmed to the desired width either at this point or before the latex is applied. To provide stability and weight to the carpet, a secondary backing of jute, polypropylene, or the like, may be attached to the back side of the carpet.
At the present time in order to produce reliable anti-static carpets for the most demanding uses, the electronics industry, it has become common practice for the carpet manufacturer to incorporate a metallic grid into the primary backing system. Such a technique is expensive and creates several problems for the manufacturer. The manufacturer must handle a heavy scrim which is less flexible than the ordinary scrim, and, because of the metallic grid, creates problems with the standard machinery used for tufting and handling carpet for dyeing, etc.
When the end use of the carpet is not to be placed under the severe criteria of the electronics industry, the mills have begun to blend or have blended into the staple fibers from which the yarn is spun a small amount of a conductive fiber to act as a static dissipation element. Such fibers are composites made conductive by incorporating into a hollow fiber a core of carbon (graphite) or by coating a fiber with a sheath made of a composite containing carbon (graphite), among the more common methods. These electroconductive fibers may be blended with the polymer fibers at the staple cutting stage. However, in many instances these composite fibers after, being made into staples, are added to the synthetic staple fibers at the opening stage. In most instances while electrostatic charges are dissipated to some degree when either of the afore described electroconductive fiber (sheath coated or hollow fiber filled with carbon (graphite) composites are employed only modest results are achieved.
It would therefore be advantageous for the consumer to have a more effective antistatic carpet. It would also be advantageous from the carpet manufacturers position to have a better conductor and a more readily incorporatable technique for placing the conductive fiber (carbon or graphite) into the existing carpet process to obtain a more uniform distribution and greater assurance that the contact with a substantial number of tufts, loop or pile of the carpet assembly are made to carry the static charge away from the source, i.e., distribute the charge over a large area of the carpet. In addition it would be advantageous for the manufacturer to eliminate the wire in the primary backing and thus eliminate the problems inherent therewith.
BRIEF DESCRIPTION OF THE INVENTION
In accordance with the present invention a primary carpet backing having antistatic discharge properties is prepared by incorporating into the backing or applying to the backing an electroconductive tow or yarn , made from continuous filaments or staple fibers yarns, or thin fluff-like web the individual fibers of the yarn or the filaments of the tow and web having spring-like structure or coil-like configurations capable of reversible deflection of greater than 1.2 times the length of the spring-like structure when in a relaxed condition, prepared from stabilized petroleum pitch, coal tar pitch or a synthetic fiber forming material, such as polyacrylonitrile, which on at least partial carbonization is electroconductive, for example, polyacrylonitrile, and are formed into the coil-like fibers or filaments by winding the stabilized but uncarbonized tow or staple yarn on a mandrel, but preferably by knitting the tow or yarn into a cloth, and heat treating the so formed tow or yarn to a carbonizing temperature (450° C. to about 1000° C.) to set a coilure (a non-textile crimp) therein as well as electroconductance thereto. The carbonaceous material included in the primary backing or scrim weaving process by incorporation into the fibers, yarn or tows or as a separate warp or fill yarn, filament assembly or tape at any one of several steps in the scrim yarn making process or applied to the scrim in one of several convenient manners produce the electrostatic charge dissipating scrim material.
When non-woven scrim material is employed, the carbonaceous material, prepared in the same manner and preferably chopped into approximately seven inch lengths is distributed throughout the non-woven conventional material during some stage in its processing to the ultimate non-woven product.
The preferred point at which the carbonaceous material of the present invention is introduced into backing material is when the backing material is being manufactured using any number of the present commercially employed methods. It is of course to be understood that the carbonaceous material can be added to the backing material at any stage prior to tufting or applied to the backing after tufting as more fully described hereinafter.
It is also to be understood that, a tow or yarn of or containing the carbonaceous filaments may be heat-set in conventional textile crimp stabilizing apparatus, carbonized in accordance with the present invention and either cut into staple or fed as a continuous filament to the continuous filament twisting or cabling stage, combining with the conventional filaments to produce a yarn or tow having static dissipation properties and used in the scrim manufacturing processes as described above or be applied to the backing surfaces. This carbonaceous material, however, has less desirable properties than the non-textile crimp material of the present invention, since it does not have the deflection or spring-like nature imparted to the non-textile crimp coil-like structure of the present invention and thus is more susceptible to being reduced to shorter elements during handling and such degradation of continuity affects the ultimate electrostatic dissipation properties.
In the case of non-woven scrim the carbonaceous material of the present invention may be added during the preparation of the mats as a staple or laid into the mat as long filaments, readily adapting its inclusion to the existing machinery for making such non-woven materials.
In addition the carbonaceous material can be spread onto the scrim or primary backing as neat fiber or blended with other fiber (nylon, polyethylene, etc.) and adhered thereto by taking advantage of the softening characteristics of the conventional synthetic fiber material or backing.
The knit fabric is preferably deknitted the resulting yarn or tow having a coilure configuration, chopped into appropriate length for blending with the standard scrim staple, made into yarns and woven into scrim. Similarly, continuous filaments, treated in the same manner to form the coilure structure, as by knitting into a cloth, are retrieved from the cloth by deknitting and introduced into the tows of continuous filaments of polypropylene, for example , used to make scrim from such tows.
The tows or yarns retrieved from the deknitting of the cloth or removal from the mandrel may be carded to produce fluff-like materials which can be applied to the scrim during the tufting process or secured to the scrim after tufting. The fluff may also be chopped and added to chopped staple used in preparing non-woven materials used to form the primary backings. In accordance with the present invention and as a means to further improve the static dissipation properties of the finished carpet, the anti-static carbonaceous material may also be added, and preferably is added to the yarns used in manufacturing the carpet, as fully described in our co-pending application, Ser. No. 773,961, filed Sep. 11, 1985, entitled Method and Materials for Manufacture of Antistatic Carpet, now U.S. Pat. No. 4,463,931, issued Feb. 17, 1987, incorporated in toto herein. This is accomplished by incorporating an electro- conductive tow or yarn, made from continuous filaments or staple fibers, respectively, prepared from stabilized petroleum pitch, coal tar pitch or polyacrylonitrile, preferably as a knit, heat-treated to a carbonizing temperature and thereafter deknitted, chopped into appropriate length and blended with the standard carpet fibers or yarn at any one of several steps in the yarn making process to produce a yarn having static dissipation properties.
The preferred point at which the carbonaceous material is introduced into textile carpet staple yarn making processes is at the blenders because there will be obtained a more uniform blending and distribution throughout the ultimate yarn. It is of course to be understood that the carbonaceous material can be added in sliver form at the pin drafters or as a staple fiber at the opening cards, or as a continuous yarn tow during twisting or cabling.
It is to be understood that a tow or yarn of the carbonaceous filaments can be heat-set in conventional textile crimp stabilizing apparatus, carbonized and either cut into staple and mixed with the conventional staple fiber during spinning or fed as a continuous filament to the continuous filament twisting or cabling stages, combining with the conventional filaments to produce a textile yarn or tow having static dissipation properties, but of poorer performance characteristics than the carbonaceous material prepared in accordance with the preferred concepts of the present invention.
The carbonaceous material useful in accordance with the present invention is more fully described in U.S. patent application Ser. No. 558,239, entitled Energy Storage Device, filed Dec. 5, 1983, and Ser. No. 678,186, entitled Secondary Electrical Energy Storage Device and Electrode Therefore, filed Dec. 4, 1984, each by Francis P. McCullough and Alvin F. Beale, which is incorporated in toto herein, which when modified in accordance with U.S. patent application Ser. No. 722,440 and its continuation-in-part Ser. No. 827,567, each entitled Novel Fabric and Fiber, filed April 18, 1985 and Feb. 10, 1986, respectively, the latter being a continuation-in-part of the earlier filed application by Francis P. McCullough and David M. Hall and U.S patent application Ser. No. 856,305, filed April 16, 1986, by said McCullough and Hall entitled Carbonaceous Fibers with Spring-like Reversible Deflection and Method of Manufacture which is a continuation-in-part of Ser. No. 827,567 serves as a preferred embodiment of the carbonaceous material suitable for use in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with one embodiment of the present invention the fibers from bales of an undyed lot of polypropylene, although other fiber material such as nylon or other synthetic fiber or natural fibrous material commonly used as backing materials, the fibers of which are approximately seven inches long, are introduced into the opening (blending) process by alternately feeding to several blenders a small portion of the fibers from each bale along with a small amount of the fibers of the carbonaceous material (preferably derived from knitting, carbonizing, deknitting and cutting to similar staple length (about 7") a stabilized filament prepared from a petroleum pitch, coal-tar pitch or polyacrylonitrile spun filament). The ratio of synthetic fibers to carbonaceous material is generally greater than about 100 to 200 times the amount of undyed fibers from the lot to the carbonaceous staple coilure non-textile crimped material, on a weight basis. The resulting fibrous card slivers are generally rebaled and thereafter blended again feeding a small amount from each bale almost simultaneously to the blenders. At this point the slivers can be introduced into the yarn spinning process or into the non-woven scrim process. In the yarn spinning processes following opening or blending, the fibers are carded. The output of several cards are fed to conventional pin drafting and spinning operations and usually two of these yarns are ply twisted together in a reverse direction to the single's yarn twist to form a two ply yarn. Such yarns are subsequently woven into a scrim material by conventional weaving machines.
A scrim or backing can also be produced from continuous filament yarns or tapes, split film, fibrilated films or the like. When such materials are used the carbonaceous fibers of the present invention may be present as an element of the tow or as a separate tow or yarn introduced into the weaving process as one does a pattern in any woven goods. Thus, the carbonaceous material, as a tow of a few filaments or single filaments can be introduced into the twisting and cabling step for continuous filament yarns or merely fed with the tape to the weaving process or introduced as a separate yarn once every 4 to 20 rows.
It is to be understood that not every yarn has to have associated with it a carbonaceous fiber or filament, but it is advantageous to have such distribution.
The present invention is especially useful when the carpet yarns also contain the carbonaceous material and they are used in combination with a primary backing or scrim which also contain the carbonaceous material.
In addition to the other techniques employed as above described, the carbonaceous material, either crimped or not, can be incorporated into the scrim, woven or non-woven, by spreading the fibers or filament either neat or as a blend with other fibers, onto the scrim surface and subjecting the scrim to a heating process, whereby the scrim material is softened and the carbonaceous material is thus adhered loosely onto the scrim backing surface.
In accordance with the preferred embodiment of the present invention a carpet is prepared from yarns, the fibers of which are derived in part from bales of undyed nylon or other suitable synthetic fiber combined with the carbonaceous fibers above described. Thus, staple fibers, which are approximately seven inches long, are introduced into the opening (blending) process by alternately feeding to several blenders a small portion of the fibers from each bale along with a small amount of the fibers of the carbonaceous material (the latter preferably derived from knitting, carbonizing, deknitting and cutting to staple length (about 7") a stabilized filament prepared from a petroleum pitch, coal-tar pitch or polyacrylonitrile or similar spun filament). The ratio of synthetic fibers to carbonaceous material is generally greater than about 100 to 200 times the amount of undyed fibers from the lot to the carbonaceous staple crimped material, on a weight basis. The resulting fibrous mats or card slivers are rebaled and thereafter blended again feeding a small amount from each bale almost simultaneously to the blenders. Following opening or blending, the fibers are carded then pin drafted. The output of several pin drafters are fed to a conventional spinning operations and usually two of these yarns are ply twisted together in a reverse direction to the single's yarn twist to form a two ply yarn. Such two ply yarns are subsequently tufted into a primary backing or scrim in the carpet manufacturing process, again preferably, having the carbonaceous material incorporated into it in any of the preceding manners. This product is dyed, trimmed and backed.
In a representative operation the carbonized, deknitted, staple length cut carbonaceous fiber was blended with several bales from a lot of staple fiber and the resulting blanket carded and pin drafted. This sliver was combined, at the appropriate pin drafters (first, second or third) depending on the ratio of carbonaceous fiber to synthetic fiber desired, e.g. with 100 to 200 times its weight of additional slivers containing no carbonaceous material prepared as afore described, at the pin drafters. There is thus obtained a sliver which has the carbonaceous fibers distributed throughout but introduced at a different point in the staple yarn making (spinning) process.
Conventional Carpet Backing
Carpet backings are most preferably manufactured from polypropylene yarns, tapes films, split films etc such as those produced by Amoco fabrics Co. and Wayntex or spun bonded products such as those produced by Typar. The accepted standard for the industry for woven backing is a 24×11 construction using warp yarn in the 450-500 denier range and fill yarns 1100-1200 denier; however, other combinations are possible. Generally the woven polypropylene substrates are needle punched with a light weight fiber web (usually Nylon as practiced by the Ozite Corp. see Ozite Corp patent) so as to provide a dyeable surface to match the coloration of the face yarn. This is typically known in the trade under such trade names as "Angle Hair", "FLW", or "FUZZ-BAC" and referred to generically as capcoating. This capcoated product is presently available from most backing producers in a variety of fiber weight and fabric combinations and comprised 30-35% of all polypropylene capcoated primary backing in 1979. As stated the primary purpose of the capcoat is to prevent "grin-through" when low density face pile (less than 28 oz/yd 2 ) is used.
Examples of Invention
EXAMPLE 1
About 1 oz of the conductive fiber is blended with an equal amount of the Nylon fiber web. About 3-4 oz of this web is needle punched per yard onto the polypropylene primary backing to give a conductive carpet. Static discharge tests conducted on this material showed the material to be conductive, the 5000 volt static charge being dissipated in less than 1/10th second.
EXAMPLE 2
A web of conductive fibers with no filler fiber is needle punched at a rate of 1-2 oz. per yard onto the face of the polypropylene primary backing to give a conductive backing. In like manner the conductive fibers were needle punched into the following backings: Fiberglass backing, a spun bonded backing product (Typar), and a woven jute backing. Each backing was subjected to the static dissipation test and each performed in a similar manner, discharged to zero in less than 1/10th second.
EXAMPLE 3
A web containing 1-2 oz of conductive fiber is glued per yard to the face of several polypropylene primary backing using
1. A latex adhesive followed by curing to harden the latex.
2. A hot melt adhesive.
3. A rubber based adhesive
4. A latex containing conductive carbon as in number 1.
Static discharge tests on each backing gave similar results as the foregoing Examples, zero discharge in less than 1/10th second.
EXAMPLE 4
Continuous filament webs instead of staple fiber webs are anchored to the primary backing face using
1. Needle punch
2. Adhesive (followed by curing when appropriate)
a. Latex
b. Hot melt adhesive
c. Rubber cement.
Each of the above backings was tested for its ability to discharge a static charge and found to dissipate the charge in less than 1/10th second.
EXAMPLE 5
Monsanto 1879 nylon (trilobal) fiber was blended with 0.5% by weight of a conductive fiber which had been prepared by heating an oxidatively stabilized polyacrylonitrile multi-filament tow which had been knitted into a fabric, heat-set at about 750° C., de-knitted and cut into staple approximately 7 inches in length. The blended fibers were carded and the resulting sliver was pin drafted three times-recombination ratios were 10:1, 3:1, and 5:1, respectively. The resulting drafted sliver was spun into a single ply yarn with an average twist of about 4.75 and the single yarn was plied with a nylon yarn made in the same fashion but containing no carbonaceous fiber. The 3.00/2 ply yarn which was heat set on a Suessen heat setting apparatus was thereafter tufted into a 1/8 gauge, 47 oz.,5/8 in. pile height carpet (a cut loop form) with approximately 8 stitches per inch. The resulting carpet was tested for static discharge properties by charging the carpet to 5000 volts while in an atmosphere having a relative humidity of less than 20%. The static charge was dissipated to 0% of original charge in less than one second, and some of the samples discharged in less than 1/10 second. The standard for the industry is a discharge to 0% in 2 seconds or less.
Thus it has been found that sufficient static dissipation properties are obtained if the material of the present invention is incorporated into yarns or tows used in the scrim manufacturing process or in the carpet yarn manufacturing process, particularly when the two aspects are combined and such yarns used as the 3rd, 4th, 5th or even every 6th warp or fill yarn. | There is described an electroconductive tow or yarn, made from continuous filaments or staple fibers yarns, prepared from stabilized petroleum pitch, coal tar pitch or a synthetic fiber forming material which on at least partial carbonization is electroconductive, for example, polyacrylonitrile, are formed into coil-like fibers or filaments by winding the tow or yarn on a mandrel, but preferably by knitting the tow or yarn into a cloth, and heat treating the so formed tow or yarn to a carbonizing temperature (450° C. to about 1500° C.) to set a coilure (a non-textile crimp) therein as well as electroconductance thereto, and incorporating the coilure structure into scrim yarns, scrim capcoats, composites with tuft-lock components as well as incorporation into the carpet yarns, to provide an anti-static property to the finished carpet. | 3 |
This application claims the benefit of U.S. Provisional Application No. 60/774,400, filed Feb. 17, 2006, and incorporates same by reference.
BACKGROUND OF THE INVENTION
The invention relates to a clamping mechanism and is particularly concerned with the clamping of a vibrator to a reinforcing bar.
In the construction industry, it is frequently necessary to lay a large area of concrete. Such areas can include, for example, foundations for buildings, floors, driveways, columns, walls, ramps, etc.
Concrete is a mixture of cement, sand, and stones, Lime is an ingredient in cement, and water is mixed with the components of the mixture to activate the lime and form a mix or slurry. Concrete exhibits characteristics of strength in compression but is relatively weak in tension.
To increase strength in tension, it is common practice to prepare a grid of reinforcing bars (“rebars”) and then to pour concrete over and around the grid, so that the reinforcing bars improve the tension strength of the poured concrete. After the wet concrete has been poured over and around the grid of reinforcing bars, it is common practice in the art to vibrate the concrete to remove air and voids from the poured mix. In this manner, when the concrete hardens, the slab will be more compact and undesirable pockets within the hardened concrete are avoided, without compromising the integrity of the concrete.
The most common form of concrete vibrator comprises a metal cylinder within which a shaft carrying an eccentric weight is rotatable to cause the metal cylinder to vibrate. The cylinder is mounted on one end of a flexible drive which serves to rotate the shaft and hence vibrate the cylinder. When the vibrating cylinder is introduced into, and immersed in, the wet concrete mix or slurry, vibrations—which may be in the region of 10,000 per minute—agitate the slurry to an extent sufficient to remove air and voids from the slurry.
Another method involves imparting vibrations to the slurry through vibrating the reinforcing bar themselves. Top-mounted vibrators are described in U.S. Pat. No. 6,950,011 and JP 07048927. But these vibrators have certain problems. If a reinforcing bar is too tall—for example, it projects a distance above scaffolding—it is too high for the vibrator operator to reach the top of the bar and the vibrator cannot be mounted for use. A top-mounted vibrator also cannot be used if the end of the reinforcing bar is bent or hooked. Also, if a plurality of reinforcing bars are incorporated in a grid, there may be no individual bars with upwardly projecting ends for mounting in a vibrator.
SUMMARY OF THE INVENTION
It has therefore been found desirable to mount a vibrator laterally on the side of a reinforcing bar or on such a bar incorporated in a grid. A quick engagement/release mechanism enables an operator to switch the vibrator from bar to bar in an assembly of bars or grid and thereby impart vibrations through an area of slurry.
According to the present invention, there is provided a clamping mechanism including a frame, a channel within said frame, and a slot extending across said frame and intersecting said channel, said channel being longitudinally open in one direction at one side of said intersecting slot and longitudinally open in the opposite direction at the other side of said intersecting slot whereby an elongated member can be positioned in said slot and said clamping mechanism then turned in a direction in which portions of said elongated member on opposite sides of said slot respectively pass through the longitudinal open portions of the channel to a position in which the elongated member lies in and longitudinally along said channel.
According to a further aspect of the invention, there is provided a vibrator attachable to a bar, said vibrator including a casing, means within said casing for vibrating said casing, and a clamp associated with said casing for engaging a bar, said clamp including a frame, a channel extending longitudinally through said frame, a slot extending across said frame and intersecting said channel at a location intermediate the ends thereof, said channel being longitudinally open in one direction at one side of said intersecting slot and longitudinally open in the opposite direction at the other side of said intersecting slot, said channel, said channel openings, and said intersecting slot all being dimensioned to accommodate said bar whereby said slot can be seated over said bar to adopt a position in which said bar lies across said channel whereupon the frame encompassing the elongated channel can be rotated in a direction in which a portion of the bar to one side of the slot passes through the longitudinal channel opening on said one side of the slot and a portion of the bar to the opposite side of the slot passes through the oppositely directed longitudinal channel opening on the opposite side of the slot to a position in which said bar lies in and along said channel within the frame.
According to a still further aspect of the invention, there is provided a method of preparing a concrete structure including the steps of forming an area to confine the structure, positioning at least one reinforcing bar in the confined area, pouring a concrete slurry into said confined area to surround and partially envelope said at least one reinforcing bar, engaging said at last one reinforcing bar by a vibrator according to claim 3 such that said bar lies in the slot and across the channel, rotating said vibrator to move said engaged bar from said slot into said channel, orienting said vibrator to create an interference hold between the channel walls and the bar, and activating said vibrator to vibrate said at least one reinforcing bar and impart vibrations into the surrounding slurry.
DESCRIPTION OF THE DRAWINGS
The invention will now be described with reference to the accompanying drawings in which:
FIG. 1 shown an exploded view of a vibrator;
FIG. 2A shows a perspective view of a housing of the vibrator;
FIG. 2B shows a perspective view of an insert accommodated in the vibrator housing;
FIG. 2C shows an exploded view of the vibrator housing shown in FIG. 2A with the insert shown in FIG. 2B in position;
FIG. 3 shows a first step in the mounting of the vibrator on a reinforcing bar;
FIG. 4 shows a subsequent step of the mounting of the vibrator on the reinforcing bar;
FIG. 5 shows a front elevation of the vibrator mounted on the reinforcing bar.
FIG. 6 shows a side elevation of the vibrator mounted on the reinforcing bar; and
FIG. 7 shows a rear elevation of the vibrator mounted on the reinforcing bar.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings, and specifically to FIG. 1 , a vibrator 10 includes a housing 30 including a cylindrical vibration portion 32 and a clamping portion 31 . In the preferred embodiment, most clearly shown in FIGS. 2A and 2C of the drawings, the cylindrical vibration portion 32 and the clamping portion 31 are two parts of an integral casing. However, the cylindrical portion 32 and the clamping portion 31 could be separate components secured to each other. Such separate components could be secured to each other by, for example, mating keyways, bolts, rivets, or like fasteners. However, in operation, the vibrator vibrates on the order of 10,000 vibrations per minute and separate components could, in some circumstances, create problems. Thus, in the preferred embodiment the cylindrical portion and the clamping portion are an integral unit, and the unit could be an integral casting of, for example, aluminum or the two component portions could be permanently welded together. The actual vibrating mechanism is, essentially, of conventional construction and vibrations are caused by rotating an eccentric weight at high speeds.
To this end, the vibrating mechanism includes a rotatable shaft 26 disposed coaxially within the cylindrical vibration portion 32 . Bearings 22 and 24 accommodated within the cylindrical portion permit free rotation of the shaft therewithin, and an eccentric weight carried by the shaft will impart vibrations to the housing 30 when the shaft 26 is rotated at high speed. The eccentric weight 28 can be keyed or otherwise secured on the shaft or, preferably, the shaft can comprise two or more axially aligned coupled segments and the eccentric weight can be a unitary casting with one such segment.
The shaft and eccentric weight are rotatable at speeds of the order of 10,000 revs per minute by an external power source (not shown) which is connected to the rotatable shaft by a flexible drive 14 coupled to the drive shaft 26 via a coupling 36 . The coupling 36 seals one end of the cylindrical portion 32 and protects the bearing 22 . The opposite end of the cylindrical portion 32 is closed by a cap 38 which similarly seals the remote end of the vibrator housing and protects the bearing 24 . In the embodiment shown in the drawings, the coupling 36 and cap 38 are provided with respective screw-threaded portions 36 a and 38 a which engage with mating threaded portions (not shown) at opposite ends of the interior of the cylindrical portion 32 .
With the operational high rate of revolutions and the vibrations imparted thereby, heat generation has to be addressed and a plurality of cooling fins are provided to dissipate the heat generated. These cooling fins 33 are shown in FIG. 1 (but, for clarity, omitted from FIGS. 2A and 2C ) extending along the length of the cylindrical portion 32 and projecting radially therefrom with intervening spaces therebetween.
The above-described vibrator is attachable to a reinforcing bar 12 by a quick clamping mechanism which will now be described in detail.
The clamping portion 31 is best shown in FIG. 2A of the drawings and, as described in the preceding paragraphs, is preferably a unitary casting with the cylindrical portion 30 . The clamping portion 31 comprises a box-like frame having a base 40 adjacent the cylindrical portion 32 , side wall portions 41 , 42 upstanding from said base, and a top portion 43 . The base, side wall portions, and top portion are shown respectively disposed at right angles to each other and define a rectangular channel dimensioned snugly to accommodate a firm but resilient insert 44 . It will be appreciated that both the frame and the reinforcing bar are metallic and the provision of an intervening resilient insert avoids having metal on metal in an environment subjected to high frequency vibrations. The insert is preferably a molding of urethane or similar polymeric material and, in addition to being snugly seated within the channel, is preferably secured in position by fasteners 45 . In the embodiment shown in the drawings, the fasteners are bolts which extend through the side wall portions of the frame and through mating bores in the insert. It will, however, be appreciated that secure fastening could be achieved by means other than bolts extending through the side walls and could, for example, include screw-threaded fastening plugs extending through the top portion 43 into the insert 44 . Whatever the form of fasteners used to secure the insert, the insert will be interchangeable and can readily be replaced by a new insert when worn by the operational vibrations.
A slot 46 extends through the top portion 43 and down and part way through the side wall portions 41 and 42 . In the embodiment shown in the drawings, the slot 46 is shown extending at an angle across and through the top portion and, although the slot could extend transversely across the top portion (i.e., at right angles to the side portions 41 , 42 ) an angle in the range from 15 degrees to 45 degrees from the transverse is preferred, since orientation of the slot at an acute angle will reduce the extent to which the vibrator must be rotated to seat a reinforcing bar in a channel in the insert in the manner described in the following paragraphs.
The slot terminates part way through the side portions 41 and 42 and, from the lowermost extremity of the slot 46 , a further slot 47 extends longitudinally through the side wall portion 41 to the end of the rectangular channel adjacent the cap 38 and a similar slot 48 extends longitudinally through the side wall portion 42 to the end of the channel adjacent the coupling 36 .
This arrangement of slots 46 , 47 , and 48 results in the channel being longitudinally open in one direction in one side wall from one side of the slot 46 and longitudinally open in the opposite direction in the opposite side wall from the other side of the slot 46 .
The insert 44 , best shown in FIG. 2B of the drawings, is a block of material similarly configured with a slot 50 extending from one side thereof partway through the block towards the other side to intersect a channel 51 extending longitudinally through the block. That channel 51 is open in one direction to mate with the slot 47 in the side wall portion 41 of the frame and, from the slot 50 , is open in the opposite direction to mate with the slot 48 formed in the other side wall portion 42 of the frame.
The manner of attaching the vibrator to a reinforcing bar will now be described.
The vibrator 10 is attached to the flexible drive 14 by means of the coupling 36 and, with the remote end of the flexible drive 14 connected to a power source, is ready for use. An area of concrete to be set has already been prepared by assembling forming to confine the area, the reinforcing bar or grid of reinforcing bars has been assembled and emplaced within the area and liquid concrete slurry has been poured into the confined area around the reinforcing bar or bars. The area to be cast can be any typical in the construction industry including, but not limited to, a floor slab, a wall, a ramp, a step or steps, etc.
The vibrator is then mounted on a reinforcing bar, either an individual bar or a component or a grid of such bars, in the following manner. The bar or grid component does not necessarily have to be upright or transversely extending to receive the vibrator but can be oriented in any desired direction.
The hand-held vibrator is introduced to the bar by passing the bar into and through the slot 46 to lie against the bottom of the slot in the manner shown in FIG. 3 of the drawings. Thereupon, the vibrator is oriented or rotated in a clockwise direction, still with respect to FIG. 3 , in which the upper portion 12 a of the bar 12 enters and passes through the slot 48 in the side wall portion 42 of the frame and the lower portion 12 b of the bar similarly enters and passes through the slot 47 in the side wall portion 41 . FIG. 4 of the drawings shows the vibrator during this orienting or rotating step with the respective portions 12 a , 12 b of the reinforcing bar entering and passing through the slots 48 , 47 .
As the rotation of the vibrator is continued the upper portion 12 a of the reinforcing bar will pass into the channel 51 in the insert 44 which is firmly retained in the frame, and the bottom portion 12 b of the reinforcing bar will similarly pass into aligned channel 52 in the insert 44 . When the reinforcing bar portions 12 a , 12 b abut or lie along the bottoms of the respective channel portions there can be no further orientation or rotation of the vibrator which is thus firmly seated on the reinforcing bar.
It is then only necessary to ensure firm retention of the vibrator thus mounted on the reinforcing bar and ensure not only that the vibrator does not slip up or down the bar but that the retention is sufficiently firm to prevent any chatter caused by the high-frequency vibrations generated by the vibrator. This could be accomplished by providing locking means in the form of a thumbscrew extending through one of the side wall portions 41 , 42 or top portion of the frame or providing an equivalent lever operated cam locking arrangement. Although such locking means (not shown) would accomplish the desired result, the provision of such means would detract from the simplicity and easy operability of the clamping mechanism of the invention. The preferred method of firmly retaining the mounted vibrator on the reinforcing bar is by hand holding the flexible drive and applying a force to tilt the mounted vibrator away from the reinforcing bar in the manner most clearly shown in FIG. 5 of the drawings. This tilting of the mounted vibrator will cause an interference jamming by opposing side wall portions of the insert channels 51 , 52 on the reinforcing bar.
In the embodiment shown in the drawings, the channels 51 , 52 are straight-sided with rounded bottoms. The channels, however, could be keyhole-shaped in cross section or, preferably, vee-shaped. An advantage of vee-shaped channels having tapering side walls is that it can accommodated reinforcing bars of different diameters since the smaller the diameter the further the bar will penetrate the channel but will still firmly contact the tapering walls not only to provide an interference fit but also to eliminate or minimize chatter.
Although the embodiments of the clamping mechanism described and shown in the drawings have particular relevance to the clamping of a vibrator on a reinforcing bar, it will be appreciated that the “slot and channels” arrangement is suitable for use in other fields where it is designed to clamp a component on to an elongated member regardless of the orientation of such member. Thus, the member can be, for example, standing upright or lying in a transverse direction. | A clamping mechanism particularly for clamping a vibrator to a reinforcing bar. The clamping mechanism provides a slot which intersects a channel. The channel is longitudinally open in one direction at one side of said intersecting slot and longitudinally open in the opposite direction at the other side of said intersecting slot. A reinforcing bar or other member to be engaged first enters the slot then moves into the channel. Once in the channel, the bar or other member is positively retained therein. | 4 |
This invention relates to adapters for securing poles with a base to a bolt held in a concrete foundation, where the bolt arrangement does not fit the bolt hole arrangement on the pole base.
PRIOR ART
Metal utility poles, particularly light poles, have been used for years. The great volume of vehicular traffic on the world's highways has lead to the high use of artificial lighting at areas of a hazard. The lighting, on open highways and in urban districts, is normally accomplished by placing high intensity lamps on poles a substantial distance above the ground. Inveriably, accidents involving vehicles results in collisions of some of the vehicles with the light poles. One solution for alleviating damage to the vehicles, has been the use of break away mountings for the light poles so as to not compound the vehicle damage. Poles for highways have generally conformed to a standard as to all specification. Urban areas had, also, adopted the standards as an economic advantage. Thousands and thousands of poles were used over a series of years having the set design standards. Subsequent experience has demonstrated that the poles of the particular design are not suitable for the circumstances. A new set of standards was adopted, and new installations of lighting facilities use poles of the new design standards.
The old style of light poles are mounted on a concrete foundation holding a pattern of bolts arranged to fit the base of the old style pole. Replacement of the old poles with poles of the new specifications has created problems of connection of the new design base to the existing concrete bases. One method is to replace the concrete bases, however, this is expensive and wasteful.
Several methods of securing a pole base to bolts in concrete are shown in the prior art, such as U.S. Pat. No. 3,630,474 issued Dec. 23, 1971 to Minor. This patent describes a break-away support, using four break-away connectors threaded on the bolts in a concrete base. The pole base has bolt holes which mate with the bolts in the concrete foundation.
A highed pole base is shown in U.S. Pat. No. 3,311,333 issued Mar. 28, 1967 to Galloway, where the hinged base has bolt holes that mate with bolt holes on the stationary pole support plate, which has bolt holes to mate with the bolts in a concrete foundation.
U.S. Pat. No. 4,154,037 issued May 15, 1979 to Anderson has a pole base which is separable from the pole, by sliding, and base is bolted onto the bolts in the concrete.
A wooden porch column base is shown in U.S. Pat. No. 2,240,016 issued Apr. 29, 1941 to Pinney where a wooden base has bolt holes to fit three screws in a wooden porch column base. The bolts for the base are accessible from under the porch for threading into nuts, and the bolts for the wooden column are accessible from the base.
THE INVENTION
The present invention provides an adapter for bolts in particular pattern and spacing in a concrete foundation with a pole base having a different bolt hole pattern and spacing. The adapter provides a central opening for elelctric wires and cables for the luminarie mounted on a pole. The adapter includes upper and lower plates held a short distance apart for access to nuts or bolt heads between the plates, and reinforcing spacers to securely connect the two plates together.
OBJECTS AND ADVANTAGES OF THE INVENTION
Included among the objects and advantages of the invention is to provide an adapter for the bolts on a concrete foundation with bolt holes in a pole base with a low profile permitting a standard skirt for the pole base to cover the adapter.
Another object of the invention is to provide an adapter for preset bolts to preset bolt holes in a pole base, maintaining sufficient clearance for access to bolt head or nuts in the adapter, and provide sufficient strength to resist stresses placed on the adapter.
Still another object of the invention is to provide a pole base adapter arranged with a passage for electric cables and wires and with sufficient strength to withstand the stresses placed on it by the pole.
These and other objects and advantages of the invention may be ascertained by reference to the following description and appended drawings.
GENERAL DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a bolt plate for a pole base of the adapter of the invention.
FIG. 2 is a plan view of a base plate for preset bolts, of the adapter of the invention.
FIG. 3 is a side elevation of one form of the adapter of the invention.
FIG. 4 is a side elevation of a modified adapter according to the invention.
FIG. 5 is a top plan view of the assembly of one form of the adapter.
FIG. 6 is a perspective view of the assembly of FIG. 5.
DETAILED DESCRIPTION OF THE INVENTION
The adapter of the invention includes a base plate having bolt holes for the bolt pattern set in a concrete foundation and a top plate having a bolt hole pattern for the bolt hole pattern of a pole base. The plates are rigidly secured together but spaced apart, permitting access to nuts for the bolts and providing a passage for electric cables, etc.
One preferred modification illustrated in FIGS. 1-3, includes top plate 10 having a large central, circular aperture 12. The plate is essentially square with rounded-off corners and elongated bolt holes 14, 15, 16 and 17 adjacent the corners, and with the long dimension of the holes on radials from the center of the plate. A short length of pipe 18 is welded on both sides of the plate into the bore 12. A bottom plate 20, also, has a central circular bore 22 of the same size as bore 12, so that the length of pipe 18 may be welded on both sides of the plate into the bore. The plate 20 is generally square with rounded corners, and bolt holes 24, 25, 26 and 27 are formed in the plate. The bolt holes are elongated, with the long dimension on a radial from the center of the plate. Addition connectors 30, 31, 32 and 33 are welded to the edge of the top plate, centered on a side. These connectors are welded to the base plate at position in line with the in positions on the top plate.
The bottom plate is about 16 inches square, and the top plate is about 12 inches square, for luminaria poles. The bolt holes in base plate are on 16" spacings on diagonals measuring from inside edge of one hole to the inside edge of the opposite hole on the diagonal. The holes in the base plate for the bolts are conveniently made 2 inches long. The plates are made of 1 inch steel stock. The top plate, of the 1 inch stock, has its bolt holes spaced 12 inches apart on diagonals with 11/4 inch long holes. The connectors are 1 inch by 2 inch by 4 inch long steel stock spacers welded to both plates. The pipe 18 is a steel pipe 7 inches I.D. with a 3/16 inch wall.
The unit is placed on a concrete foundation having bolts in a square pattern, being spaced about 16 inches apart on diagonals. The adapter is secured down by nuts 35 on the bolt ends exposed above the concrete in the foundation. Bolts placed through the holes in the top plate may be used to bolt the base of pole (not shown) to the unit. The skirt or cover for the bases of such poles are used to cover the base and bolts. The standard skirt or cover for the pole bases cover the adapters as well as the base of the pole. The central opening is large enough for the cables needed for the luminarie.
The preferred unit of FIGS. 4-6 is similar to the unit of FIGS. 1-3, using a slightly different spacer system. The unit includes top plate 10a and bottom plate 20a, each having elongated bolt holes in a similar pattern, such as 14a, 15a, 16a and 17a, each for retaining a bolt therein. The base includes elongated bolt holes 24a, 25a, 26a and 27a. A central pipe 18a is mounted in central bores through each plate, and is welded to the plate. Support-spacers 43, 44, 45 and 46 are welded to the top and bottom plates and to the pipe.
The pipe is preferably welded at its end to the outside of the plates, at W1, FIG. 6 of the top plate, as well as the inside of the plates, as shown as at W2, FIG. 6. The spacers are preferably welded to each plate and to the pipe. This provides sufficient strength of the unit to withstand the stresses subjected on the adapter, for example, the stresses encountered when the pole is buffeted by high winds. The length of the pole induces high moment stresses on the base and the adapter. The low profile of the adapter permits it to fit within the pole base cover, without modification of the standard base covers. | An adapter for the concrete foundation mounted bolts to the bolt holes of a pole base of a different configuration, including a lower plate arranged to be secured to bolts on the concrete base, an upper plate arranged to be secured to the pole base and interconnecting braces inclusive of a central electric wire passage and supporting braces between the plates. | 4 |
TECHNICAL FIELD
This application is a continuation of U.S. application Ser. No. 09/645,262 filed Aug. 24, 2000, now U.S. Pat. No. 6,470,403, which is a continuation of and claims priority of U.S. application Ser. No. 09/119,663, filed Jul. 21, 1998 now issued as U.S. Pat. No. 6,243,770, the contents of which are incorporated herein by reference.
The present invention relates to communications within a computer. In particular, the present invention relates to the use of multiple interlocking first-in, first-out (“FIFO”) buffers.
BACKGROUND
Using a PCI bus, data transfers can be accomplished using burst transfers. There are two participates in every PCI burst transfer: the initiator and the target. The initiator is the device that initiates the transfer. The target is the device currently addressed by the initiator for the purpose of performing a data transfer. All PCI bus transactions consist of an address phase followed by one or more data phases. During the address phase, the initiator identifies the target device and the type of transaction. The data phase of a transaction is a period during which a data object is transferred between the initiator and the target. The number of data bytes to be transferred during a data phase is determined by the number of Command/Byte Enable signals that are asserted by the initiator during the data phase. Also, the number of data phases depends on how many data transfers are to take place during the overall burst transfer. Each data phase has a minimum duration of one PCI CLK. Each wait state inserted in a data phase extends it by an additional PCI CLK. The duration of a transaction is from the start of the address phase to the completion of the final data phase.
A non-pipelined bus architecture allows only a single transaction at a time, generally consisting of a request (address) phase and a response (data) phase with each response phase completing before the next address phase. A pipelined bus architecture allows multiple outstanding transaction requests (address phases) to be made prior to the completion of subsequent phases. Only one address phase may be active at one time, but there may be multiple address phases that have occurred prior to the corresponding data phases.
Currently, separate FIFO buffers are used in the implementation of a pipelined bus architecture. For instance, an implementation of a pipelined bus architecture may involve having one FIFO buffer for the address phase and one FIFO buffer for the data phase. Three of the problems faced in implementing a pipelined bus architecture having separate FIFO buffers are data overflow, data underflow, and inefficient use of memory. When implementing a pipelined bus architecture with FIFO buffers, multiple addresses may have to be written into the address FIFO buffer prior to having the corresponding data available for writing into the data FIFO buffer. However, in order to prevent data overflow that causes data to be overwritten, there must be space available in the data FIFO buffer prior to accepting an additional address into the address FIFO buffer.
Similarly, for a read operation, multiple addresses may be read from an address FIFO buffer prior to reading the corresponding data from the data FIFO buffer. In order to prevent data underflow (i.e., not having the data available for the addresses that have been read), the data corresponding to the addresses read from the address FIFO buffer must have been written into the data FIFO buffer prior to the addresses being read from the address FIFO buffer. Clearly, a FIFO buffer structure for use in a pipelined bus architecture that will prevent data underflow and data overflow would be desirable.
In implementing a pipelined bus interface, a logic state machine may be used. The logic state machine is responsible for tracking each transaction through its corresponding phase. A problem with using a logic state machine in this manner is that the machine needs to know not only the position of the read and write pointers of its corresponding FIFO buffer, but the position of the read and write pointers of other interrelated FIFO buffers in order to make decisions about the current phase. However, the logic state machine cannot determine the position or location of the pointers within the other interrelated FIFO buffers.
Implementing a pipelined bus to bus interface using separate FIFO buffers may increase storage requirements. Each phase may require access to the same data structure. For instance, such is the case when a snoop phase requires the address to present to the snooping agent and a request phase also requires the same address to present to the request agent. Using separate FIFO buffers for each phase requires storing the same information in two separate data structures. This multiple storage of the same information is an inefficient use of memory. Clearly, a FIFO buffer structure for use in a pipelined bus architecture that reduces storage requirements would be desirable.
SUMMARY
One embodiment of the present invention relates to a method for using at least two first-in, first-out (“FIFO”) buffers in a pipelined bus, comprising, interlocking the at least two FIFO buffers, wherein the act of interlocking comprises defining a transaction correspondence between the phases tracked by each of the buffers.
Another embodiment of the present invention relates to a method for identifying a status of a buffer structure having at least two first-in first-out (“FIFO”) buffers that are interlocked, with each FIFO buffer having a read pointer and a write pointer. The method comprises receiving a logic signal (i.e., a strobe) requesting the performance of an operation on the buffer structure and determining the status of the buffer structure based on the position of at least one pointer of each of the at least two FIFO buffers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows multiple, interlocked first-in, first-out (“FIFO”) buffers connected to processor interface logic.
FIG. 2 shows an embodiment of the present invention having two interlocked FIFO buffers.
FIGS. 3A and 3B are decision trees for the logic generating status of the buffer for implementing the present invention.
DETAILED DESCRIPTION
FIG. 1 is a block diagram of one embodiment of the present invention showing an implementation of multiple, interlocked FIFO buffers for use in a pipelined bus architecture. A pipelined bus architecture may have multiple phases. For instance, two common phases are a request phase or address phase and a response phase or data phase. The present invention allows for pipelining of multiple phases by referencing a common data structure, while preventing the overflow or underflow between the address an data portions of the interlocked FIFO buffers 100 . The Pentium Pro and Pentium II bus have a pipelined bus architecture that represents one example of a bus architecture to which the embodiments disclosed herein are applicable.
Interlocked FIFO Buffers
FIG. 1 shows a plurality of FIFO buffers 100 a , 100 b , 100 c operatively linked to status generation logic 102 . FIFO buffer 100 a comprises a plurality of data structures Da 1 , Da 2 , . . . Dai, . . . Dan, a read pointer 110 a , and a write pointer 112 a . Each pointer 110 a , 112 a wraps around from the last data structure Dan to the first data structure as the pointers advance. In general, the read pointer 110 a points to the next data structure Da 1 that has valid information to be read, and the write pointer 112 a points to the next available data structure Daj into which information may be written. As information is written to the FIFO buffer 100 a , the write pointer 112 a advances until it may catch up with the read pointer 110 a , at which time the FIFO buffer 100 a is full. Similarly, as information is read from the FIFO buffer 100 a , the read pointer 110 a advances until it may catch up with the write pointer 112 a , at which time the FIFO buffer 100 a is empty.
The other FIFO buffers 100 b , 100 c are structured in the same way as buffer 100 a . A buffer structure comprises at least two FIFO buffers. Each of the buffers is interlocked with the others when there exists a transaction correspondence between the phases tracked by each of the buffers. That is, the information in Da 1 corresponds to transaction-related information in Db 1 and Dc 1 . For example, Da 1 may contain address phase information for a transaction and Da 2 will contain data phase information for the same transaction. Thus, in one embodiment, the transaction correspondence is that a numbered data structure in one FIFO (e.g., Da 1 ) will have or has information that is transactionally-related to information that is contained or will be contained in the same numbered data structure (e.g., Db 1 ) in another of the interlocked FIFO buffers. However, depending on the relationship required between the buffers for a transaction, the transaction correspondence between the phases tracked by each of the buffers may be embodied differently. Continuing to refer to FIG. 1, status generation logic 102 provides a status of the interlocked FIFO buffers 100 a , 100 b , 100 c (i.e., whether the interlocked buffers are full or empty) based on the location of the pointers of the interlocked FIFO buffers. This status provided by the status generation logic 102 is communicated to a processor (not shown) via the processor interface logic 104 .
As noted, for FIFO buffers 100 a , 100 b , 100 c to be interlocked, there must be a relationship between the information in corresponding data structures in the buffers 100 . With reference to FIG. 2, a buffer structure having two interlocking FIFO buffers 120 a , 120 b will be described. This buffer structure may be used with a pipelined bus architecture. Each FIFO buffer 120 a , 120 b may correspond to a transaction phase of a pipelined bus. For instance, as shown in FIG. 2, one FIFO buffer 120 a may correspond to an address phase (“address FIFO buffer”) and the other FIFO buffer 120 b may correspond to a data phase (“data FIFO buffer”). The address FIFO buffer 120 a has an address read pointer 122 a and an address write pointer 124 a . Similarly, the data FIFO buffer 120 b has a data read pointer 122 b and a data write pointer 124 b . The address FIFO buffer 120 a and the data FIFO buffer 120 b may be interlocked, because the data corresponding to each address in each data structure Dai of the address FIFO buffer 120 a is (or when supplied, will be) contained in the corresponding data structure Dbi of data FIFO buffer 120 b . Although the present invention may be implemented in a pipelined bus architecture having two interlocked FIFO buffers 100 , a more complex implementation may have as many interlocked FIFO buffers as are required by the bus protocol that is supported.
One advantage of having interlocking FIFO buffers is that this arrangement allows sharing of a common data structure by each phase in the pipelined bus architecture, thereby reducing storage requirements when compared to implementations using separate FIFO buffers 100 . For instance, an implementation may require the address or data to be available at different phases. Thus, a single copy may be stored but read via multiple read pointers.
Status Generation Logic
As shown in FIG. 1, status generation logic 102 may be operably linked to the read and write pointers 110 a , 110 b , 110 c , 112 a , 112 b , 112 c of each interlocked FIFO buffer 100 a , 100 b , 100 c . The status generation logic 102 determines the status of the interlocked FIFO buffers in a buffer structure based on the location or position of the read and write pointers of each of the FIFO buffers that form the buffer structure. In one embodiment, the status generation logic determines the status of the buffer structure based on the position or location of at least one pointer in each of the buffers that comprise the interlocked buffer structure. Also, the status generation logic may also control the read and write pointers. That is, the status generation logic may also increment the read and write pointers as needed. In one embodiment, the status generation logic may be implemented in an Application Specific Integrated Circuit (“ASIC”).
Providing the Status of the Buffer Structure
With reference to FIGS. 3A and 3B, the status generation logic 102 will be described. In particular, FIGS. 3A and 3B are flow charts for the implementation of two interlocked FIFO buffers 120 a , 120 b shown in FIG. 2 (i.e., the address FIFO buffer 120 a and the data FIFO buffer 120 b ). FIG. 3A is a flow chart for a write operation and FIG. 3B is a flow chart for a read operation.
Write Operation
At block 200 , upon receiving a strobe or logic signal for a write operation to the address FIFO buffer 120 a , the address write pointer 124 a is incremented. At block 202 , it is determined whether the incremented address write pointer 124 a has caught up with the data read pointer 122 b for the other interlocked FIFO buffer. That is, in the case of the interlocked data and address FIFO buffers 120 b , 120 a where a strobe to write an address in the address FIFO buffer 120 a has been made, a full status (block 204 ) would be indicated when the address write pointer 124 a catches up with the data read pointer 122 b . When the address write pointer 124 a catches up with the data read pointer 122 b , the data read pointer 122 b is pointing to a data structure Dbi that needs to be read. Consequently, the data structure Dbi in the data FIFO buffer 120 b that corresponds to the data structure Dai in the address FIFO buffer 120 a does not have room for the data corresponding to the next address to be written in the address FIFO buffer 120 a . However, if the incremented address write pointer 124 a has not caught up with the data read pointer 122 b , then, as shown in block 206 , a not full status is indicated.
In short, if a data structure Dbi is available in the data FIFO structure 120 b , then subsequent writes to the address FIFO buffer 120 a are allowed by indicating a not full status (block 206 ). However, if a data structure Dbi is not available in the data FIFO buffer 120 b for the data corresponding to the address to be written by a subsequent write to the address FIFO buffer 120 a , then a full status is provided for the address FIFO buffer 120 a , even though the data structures Dai in address FIFO buffer 120 a itself are not full. This status report prevents data overflow.
Read Operation
Similarly, as shown in FIG. 3B, if a read strobe is received for the address FIFO buffer 120 a , then at block 300 , the address read pointer 122 a is incremented. Then, to determine the status of the buffer structure for purposes of the read operation, the status generation logic 102 determines whether the incremented read pointer caught up with the data write pointer 124 b . If the address read pointer 122 a has caught up with the data write pointer 124 b , then, as shown at block 304 , an empty status would be returned. The empty status is indicated because the next read address is available but the corresponding data is not yet available. However, if the address read pointer 122 a has not caught up with the data write pointer 124 b , then, as shown in block 306 , a not empty status would be returned.
In short, if the corresponding data is there in the data structure Dbi of the data FIFO buffer 120 b , the status of not empty is provided and the next address in the address FIFO buffer 120 a is available to be read. However, if the corresponding data is not written in the data FIFO buffer 120 b , then the status is indicated as empty even though the address FIFO buffer 120 a is not empty. This status report prevents data underflow.
Sample VHDL pseudo code is listed below for the implementation shown in FIG. 2 .
Data writes:
if (DATA_WR_PTR_ce = ‘1’) then
Look for a data write strobe.
DATA_WR_PTR <= NEXT_DATA_WR_PTR;
Increment the data write pointer
if (DATA_WR_PTR /= ADDR_RD_PTR) then
If the data write pointer does not catch
FIFO_EMPTY <= ‘0’;
the NEXT address read pointer,
end if;
mark the FIFO as not empty
end if;
Data reads:
if (DATA_RD_PTR_ce = ‘1’) then
Look for a data read strobe.
DATA_RD_PTR <= NEXT_DATA_RD_PTR;
Increment the data read pointer.
if (DATA_RD_PTR /= ADDR_WR_PTR) then
If the data read pointer does not catch
FIFO_FULL <= ‘1’;
the NEXT data read pointer,
end if;
mark the FIFO as full
end if;
Address reads:
if (ADDR_RD_PTR_ce = ‘1’) then
Look for a data read strobe
ADDR_RD_PTR <= NEXT_ADDR_RD_PTR;
Increment the address read pointer
if (ADDR_RD_PTR = DATA_WR_PTR) then
If the address read pointer catches
FIFO_EMPTY <= ‘1’;
the NEXT data write pointer,
end if;
Mark the FIFO as empty
The algorithm disclosed by this code is implemented in the status generation logic.
While a preferred embodiment of the present invention has been described, it should be appreciated that various modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, reference should be made to the claims to determine the scope of the present invention. | One embodiment of the present invention relates to a method for using at least two first-in, first-out (“FIFO”) buffers in a pipelined bus, comprising, interlocking the at least two FIFO buffers, wherein the act of interlocking comprises defining a transaction correspondence between the phases tracked by each of the buffers. | 6 |
This is a continuation of application Ser. No. 07/860,658, filed Apr. 30, 1992, now abandoned.
BACKGROUND OF THE INVENTION
Polyamide yarns are commonly produced by melt spinning of one or of a plurality of filaments which are wound onto a container, stored for some time, sometimes referred to as lagging time, and subsequently in a second step drawn and textured. This two-step process produces a yarn with a high crystallinity and a low shrinkage. In addition, a high percentage of the crystals in the two-step yarn are the alpha-type which are more stable than the gamma-type crystals.
One step processes, often referred to as spin-draw-texture (SDT) processes, have been developed which are more efficient but which produce yarns with lower crystallinity and higher shrinkage during the heatsetting process. In addition, these yarns contain a lower percentage of the stable alpha crystals than two-step yarns. The disadvantages of these yarns are the differing deniers of comparable heatset products.
Another disadvantage is the very smooth surface of these yarns which leads to high yarn-to-guide friction in processing the yarns into fabrics which show undesirable non-uniformities such as streaks.
To overcome this latter problem, U.S. Pat. No. 3,414,646 describes a process for the production of polycarbonamide filaments using a treatment of the filaments with steam before the drawing step.
U.S. Pat. No. 3,761,556 discloses a process for the manufacture of a crimped polyamide yarn including a two-stage steaming process prior to drawing and crimping.
In order to improve ozone fading resistance of dyed nylon yarn, U.S. Pat. No. 4,396,570 describes a continuous process for spinning and drawing nylon 6 filaments by applying steam in a chamber to the filaments before the drawing step.
An object of the present invention was to provide a continuous process for spinning and drawing polyamide for the manufacture of polyamide yarns with a high crystallinity, a higher percentage of alpha crystals, and a low shrinkage. Another object was to provide an apparatus for such a process.
SUMMARY OF THE INVENTION
The objects of the present invention could be achieved with a continuous process for spinning and drawing polyamide filaments comprising:
(a) melting a polyamide and spinning the filaments from the molten polyamide through a spinnerette;
(b) quenching the filaments;
(c) applying a yarn finish to the filaments,
(d) applying steam and heat to the filaments by a steam and heating unit comprising a steam box and at least one heated godet;
(e) drawing the filaments; and optionally
(f) texturing the filaments.
DETAILED DESCRIPTION OF THE INVENTION
Continuous processes for spinning and drawing polyamide filaments are known, for example, from U.S. Pat. Nos. 3,414,646; 3,761,556 and 4,396,570, hereby incorporated by reference.
Polyamides are well known under the generic term "nylon" and are long chain synthetic polymeric amides. Nylons are identified by the number of atoms in the diamine and dibasic acid, for example nylon 6/6, which stands for a polymer formed by the condensation of hexamethylene diamine and adipic acid. Other nylons are formed from only one reactive species such as an aminoacid or a lactam. Polyaminocaproic acid is produced by the polymerization of caprolactam and is known as "nylon 6". Commercially available and useful for the purpose of this invention are all linear melt-spinnable polyamides. Preferred for the purpose of this invention are nylon 6, nylon 66, nylon 6/10, nylon 6/12, nylon 11, nylon 12, nylon 66T, nylon 6I6T, copolymers thereof, or mixtures thereof, and especially preferred is nylon 6.
In step (a) the polyamide is melted in an extruder and spun through a spinnerette to form filaments. These filaments are quenched in step (b) with a flowing quench medium such as air.
In step (c) a yarn finish is applied to the filament as 100% oil or as an aqueous emulsion containing from 5 to 30% finish solids. The finish could be metered onto the fiber or applied with a kiss roll. Suitable finishes could contain the following components: esters, vegetable oils, alkoxylated vegetables oils, alkoxylated acids, alkoxylated diacids, alkoxylated sorbitol esters, alkoxylated sorbitans, alkoxylated alkyl phenols, and phosphate esters. Preferred finishes contain vegetable oils, alkoxylated diacids, and phosphate esters or contain esters, vegetable oils, alkoxylated vegetable oils, alkoxylated alkyl phenols, and phosphate esters.
Steam and heat are applied to the filaments in step (d) by a steam and heating unit comprising a steam box and at least one heated godet. Steam is applied to the filaments by a steam box with a steam temperature of from about 60° C. to about 180° C., preferably from about 100° C. to about 150° C. and most preferably from about 120° C. to about 140° C.
In a preferred embodiment the filaments pass the steam box on the outside, where the steam box releases the steam out of individual steam applicator jets having a diameter of from about 0.1 to about 2.0 mm, preferably from about 0.5 to about 1.0 mm.
In a preferred embodiment, the number of applicator jets corresponds with the number of steps in the stepped-out godet used in step (d).
Preferably the steam box is located between two godets.
The jets releasing the steam are preferably on both sides of the steam box, where the steam is applied to the passing filaments. For a better alignment of the filaments in order to pass the jets, the jets of the steam box are Located in slots. The advantage of this steam box is that there arise no problems with condensing water because the steam is released in the air and evaporates. The water, condensed in the steam box is separated by an exhaust pipe. In embodiments where the filaments pass inside the steam box, problems always arise with the condensation of water on the filaments.
In step (d) preferably two godets are used, at least one of which could be heated. The godets may be heated electrically or with steam to a temperature of from about 60° C. to about 180° C., preferably from about 100° C. to about 160° C. and most preferably from about 120° C. to about 160° C.
The filaments wrap from about 1 to about 50 times around the two godets and the steam box, preferably from about 5 to about 30 times, most preferably from about 10 to about 20 times.
During this heat application the filaments elongate from about 10 to about 20%. In order to adjust this elongation to the size of the godets, a preferred embodiment of this invention uses at least one stepped-out godet. The stepped-out godet has preferably as many steps as wraps of the filaments which may be from about 1 to about 50, preferably from about 5 to about 30, most preferably from about 10 to about 20 steps.
In order to reduce any kind of friction, preferably two stepped-out godets are used with a difference in diameter from step to step from about 0.2 to about 10%, or double this value in the case that only one stepped-out godet is used.
More than two godets could be used but it is less desirable. More than one steam box could be be used but this is also less desirable.
Based on a speed of the filaments of from about 5 to 40 m/s, preferably from about 10 to about 20 m/s, the residence time in the steam and heating unit is from about 1 to about 9 s, preferably from about 2 to about 4 s.
The drawing step (e) is conducted with a drawing godet which could be heated, and a draw ratio of from about 1.1 to about 5.0, preferably from about 2.0 to about 4.0.
The optional texturing step (f) is known in the art and may utilize steam, air, hot air, solvent, water, crimping rolls, and the like. Preferred is the use of a texturing jet utilizing steam or hot air.
Determining the percentages of alpha and gamma crystals in the crystalline phase of a nylon 6 fiber is known in the art, and an excellent reference is R. F. Stepaniak, A. Garton, D. J. Carisson, and E. S. Clark, Journal of Applied Polymer Science, vol. 21, p. 2341 (1977). Determining the percent crystallinity in a nylon fiber is well known in art and is typically calculated from the measured fiber density and the intrinsic density values for the amorphous and crystalline phases.
The filaments produced by this process show a Superba shrinkage, measured in a 129° C. tunnel, of from about 18 to 20% in comparison to about 25 to 28% for filaments without this steam and heating treatment. With emulsion finish and this treatment the shrinkage was reduced below 18%. Superba shrinkage measured in a 117° C. tunnel dropped from about 17-19% for the untreated filaments to about 9 to 12% for the filaments produced by the process of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic drawing of the apparatus used for the process of the present invention.
FIG. 2 is a partial schematic drawing of the steam and heating unit comprising two godets, at least one of which is heatable, and a steam box.
DETAILED DESCRIPTION OF THE DRAWINGS
In FIG. 1 the filaments 1, which have been spun by a spinnerette, pass the quenching unit 2, followed by a finish application unit 3. The filaments continue to run over a guide 4 to the steam and heating unit comprising godet 5, which could be heated, steam box 6 and the godet 7 which could be heated. The filaments may pass several wraps (18 in FIG. 2) around the two godets 5,7 and the steam box 6, before continuing to run over the guide 8 to the spinning godet 9, which could be heated and the accompanying idler roll 9a and further to the drawing godet 10, which could be heated, with the accompanying idler roll 10a.
From the drawing godet 10, the filaments continue to run to the texturing unit 11 followed by a cooling unit 12 over the take-off godet 13 to the take-up unit 14, where the filaments are taken up on a winder.
FIG. 2 illustrates the steam and heating application unit comprising the stepped-out godets 5 and 7, which could be heated and the steam box 6, all connected to the plate 15. The stepped-out godets 5 and 7 comprise the steps 5a and 7a. The steam box 6 comprises the steam applicator jets 6a which are located inside the slots 6b. The steam is fed into the steam box through pipe 6(c) and is exhausted through exhaust pipe 6(d). Preferably the steam box has the same arrangement on the other side.
EXAMPLE 1
Using the Apparatus shown in FIGS. 1 and 2, nylon 6, with relative viscosity of 2.7 (Ultramid BS-700™ from BASF) chips were melted, extruded and processed under the following conditions:
______________________________________Polymer Temp., °C. 270Mass Throughput, grams per minute 256Polymer Pressure, psig 2000Finish Type formulation of vegetable oils, alkoxylated diacids, and phosphate estersFinish Level, % 1.5Entry (first step) Speed of Godets 5 800and 7 in FIGS. 1 and 2, meters perminuteExit (last step) Speed of Godets 5 and 9367 in FIGS. 1 and 2, meters per minuteTemperature of Godets 5 and 7 in varied during testing:FIGS. 1 and 2, °C. ambient, 90, 125, 140, and 150Steam Pressure in steam box 6 in varied during testing:FIGS. 1, and 2, psig off, 53Steam Temperature in steam box 6 in varied during testing:FIGS. 1 and 2, °C. off, 140Spinning Godet Speed, MPM varied: 800 for control and 960 with steam boxSpinning Godet Temperature, °C. varied: 50 for control and 80 with steam boxDrawing Godet Speed, MPM 2400Drawing Godet Temperature, °C. 185Text. Jet Steam Temp., °C. 190Text. Jet Steam Pres., psig 85Take Off Godet Speed, MPM 2130Take Off Godet Temp., °C. ambientWinding Speed, MPM 2020Winding Tension, grams 100______________________________________
EXAMPLE 2
Like example 1 except that the finish type was an aqueous emulsion of esters, vegetable oils, alkoxylated vegetable oils, alkoxylated alkyl phenols, and phosphate esters.
EXAMPLE 3 CONTROL
Like example 1 without any steam and heat treatment.
EXAMPLE 4 CONTROL
Like example 2 without any steam and heat treatment.
EXAMPLE 5 CONTROL
Nylon 6 chips are processed in a conventional two-step spinning and drawing process.
TABLE__________________________________________________________________________PROPERTIES OF STEAM BOX TREATED SDT YARN vs. CONTROLSSTEAM/HEAT UNIT__________________________________________________________________________ GODET STEAM STEAM FINISH 5 & 7 PRESSURE TEMP. % TENACITYEXAMPLE TYPE TEMP °C. (psi) °C. DENIER ELONG (gpd)__________________________________________________________________________1 Neat 150 53 140 1272* 34.6 2.422 Emul- 150 53 140 1097 30.3 2.36 sion3 Neat -- -- -- 1111 40.0 3.36Control4 Emul- -- -- -- 1084 36.7 2.88Control sion5 Emul- -- -- -- 1111 44.0 2.05Control sion__________________________________________________________________________ TYPE OF 129° C. 117° C. DEN- CRYS- TYPE OF TOTAL % SUPER- SUPER- SITY TALS % CRYSTALS CRYSTAL-EXAMPLE BA % BA % (g/cc) ALPHA % GAMMA LINITY__________________________________________________________________________1 18 -- 1.128 85 15 432 17 10 1.133 95 5 473 25 17 1.127 63 37 42Control4 28 19 1.127 64 36 42Control5 15 6 1.141 96 4 53Control__________________________________________________________________________ *1300 denier target | A continuous process for spinning and drawing polyamide filaments with the steps of melting a polyamide and spinning the filaments from the molten polyamide through a spinnerette, quenching the filaments, applying a yarn finish to the filaments, applying steam and heat to the filaments by a steam and heating unit which consists of a steam box and at least one heated godet, drawing the filaments, and optionally texturing the filaments. The resulting filaments have low shrinkage, high crystallinity, and a high percentage of alpha crystals. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to a tool changing arrangement for a machine tool comprising an axially advanceable drive spindle provided with a holding member having a receiving part into which a tool carrier may be pushed laterally and be held thereon substantially coaxial with the spindle, and in which the drive spindle and the tool carrier are provided at facing ends thereof with centralizing parts which, during the coupling of the two members and relative movement between the drive spindle and the holding member axially align the drive spindle and the tool carrier. The arrangement includes further parts for transmitting a turning moment from the drive spindle to the tool carrier.
In a known arrangement of the aforementioned kind, the holding member is in the form of tongs located outside the spindle and movable with the same in axial direction, but not turnable relative thereto. The tool carrier must therefore be supported in a special way with respect to the holding member. The tool carrier is provided with a steep cone extending into a corresponding internal conical surface of the drive spindle to axially align these two elements with respect to each other. In order to transmit a turning moment from the spindle to the tool carrier, the spindle has to be provided with separate elements which enter into the steep cone of the tool carrier. Wear of the inter-engaging elements is thereby unavoidable, which will lead to an undesired chatter of the tool carrier and the tool carried thereby. The holding member located outside of the spindle, and hydraulically moved in axial direction relative thereto, requires considerable space and is necessarily complicated in construction. The steep cone requires a large stroke for engagement with the internal cone surface and the interengaging surfaces have to be manufactured to very close tolerances, while still not providing a perfect axial alignment of the two members. Furthermore, each tool carrier requires an expensive bearing. The tool carriers form with different tools respectively a unit, which during machining of a workpiece must usually be changed several times.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a tool changing arrangement which overcomes the abovementioneddisadvantages of such arrangements known in the art.
It is a further object of the present invention to provide a tool changing arrangement of the aforementioned kind which is of simple and compact construction, not requiring expensive bearings for the tool carrier, which provides secure means for transmitting a turning moment from the spindle to the tool carrier, which are not subjected to undue wear, and which will assure an exact and stiff alignment of the axes of spindle and tool carrier to resist axial as well as radial forces, and which, especially by automatic tool changing arrangements, permits a quick change and connection of successive tool carriers with the spindle.
With these and other objects in view, which will become apparent as the description proceeds, the tool changing arrangement according to the present invention mainly comprises a rotary drive spindle movable in axial direction between two end positions, a holding member coaxially carried by the spindle for rotation therewith and axially movable with respect thereto and having a tool carrier receiving part projecting beyond one end of the spindle, a tool carrier movable transversely to the holding member and having at one end facing the one end of the spindle a portion in which the tool carrier receiving part is inserted, when the tool holder and the spindle are substantially aligned in axial direction. The spindle and the tool carrier having at the facing ends thereof interengaging centralizing portions which, during axial movement of the holding member relative to the spindle, axially align the tool carrier and the spindle. Furthermore, the aforementioned receiving part of the holding member and the portion of the tool carrier, in which the receiving part is engaged, are provided with cooperating engaging faces for transmitting a turning moment from the spindle to the tool carrier. The receiving part of the holding member preferably comprises a crossbar extending transversely to the axis of the holding member and the portion of the tool carrier is provided with a slot for receiving the crossbar. The slot and the crossbar are further provided with faces through which forces in axial direction may be transmitted between the holding member and the tool carrier. The slot and the tool carrier receiving part are preferably of T-shaped cross section which has special advantages with regard to the manufacture and the rigidity of the arrangement.
A stationary abutment means is further provided for limiting axial movement of the holding member in one direction relative to the spindle to a position in which the tool carrier may be moved onto the holding member, respectively removed therefrom, and the drive spindle has in one of its end positions a predetermined distance from the abutment means, so that the relative axial movement of drive spindle and holding member in this end position is fixed and large enough to release parts of the tool carrier which are in the coupled condition inserted in the spindle. In order to pull the facing ends of the drive spindle and the tool carrier forcefully against each other, an energy storage is provided between the drive spindle and the holding member which, during relative movement of the drive spindle and the holding member changes its characteristic. An especially simple and properly functioning construction is derived when the energy storing means are in the form of a pack of dished spring washers held between the drive spindle and the holding member.
According to the present invention the centralizing portions of the drive spindle and the tool carrier are constituted by short interengaging cones, and at least the cone on the tool carrier is divided by cutouts into a plurality of sectors. The facing ends of the drive spindle and the tool carrier are further provided, in addition to the short cones, with contact faces to transmit axial forces between the two members. The tool carrier has elastic zones arranged so that the cone sectors, during relative movement between drive spindle and holding member, may be spread apart, when the contact faces of drive spindle and tool carrier abut against each other. In this way, the relative movement between drive spindle and holding member can be held relatively short, the interengaging cones and the position of the contact faces relative thereto may be manufactured at relatively large tolerances, while obtaining a definite axial position of the tool carrier and the drive spindle relative to each other. The unstressed position there is a small clearance between the two cones and, under the pulling force imparted to the holding member, the sectors of the cone of the tool carrier are spread apart to assure thereby a central engagement of the two cones without any play with respect to each other. An exact machining of the short cones and the contact surfaces will assure a central and axial exact connecting of the various members to each other. The tool carrier will be supported in exact axial position and perfectly central with the drive spindle, during rough machining or fine machining of the workpiece, regardless of the feeding speed, the number of revolutions and the loads applied to the tool.
The arrangement according to the present invention is especially advantageous in a machine tool with an automatic tool changing arrangement provided with a magazine, in which the tool carriers are arranged on a rail movable by a transporting system, and in which the rail, at the point of intersection with the drive spindle and at a loading station, is interrupted and in which the holding member at the interruption at the fore-mentioned point of intersection takes over the function of the rail. According to the invention the drive spindle with the holding member is arrestable in an axial end position of the spindle in such a manner that the receiving part of the holding member is exactly oriented to be aligned with the rail. The tool carrier can thereby not only without difficulties move onto the holding member, respectively be removed therefrom, but the positioning thereof can as a rule, in NC (numerically controlled) machine tools, carried out in such a manner that grooves on the workpiece during retraction of the tool can be avoided. Various possibilities for arresting the drive spindle and the holding member thereon in an exactly defined angular position are well known in the art. For transporting the tool carrier on the rail, push cylinders, transport wheels, chains, Maltese crosses or similar known arrangements may be used. Gripping systems are unnecessary, since even the release of the tool carrier from the holding member may be carried out automatically through axial movement of the holding member, respectively the drive spindle. The transport system need not exactly position the tool carrier, since the short cone will provide for a precentralizing of the same. If the rail in the magazine forms a circular path, the receiving part for the tool carrier on the holding member is preferably formed along a circular arc with the profiles of the rail and the receiving part of the holding member corresponding to each other.
The tool carrier provided with the necessary tool is moved, during tool change, radially with respect to the drive spindle onto the holding member, until the axes of drive spindle and tool carrier are substantially aligned. Subsequently thereto, the holding member is moved by means of the energy storing means in axial direction relative to the drive spindle until the contact surface of the tool carrier abuts against the contact surface of the drive spindle and the spread cone sections on the tool carrier abut tightly against the inner cone of the drive spindle. The connection between tool carrier and spindle is thus carried out without delay during the necessary fast advance of the spindle. On the other hand, at the end of the fast return of the spindle, the tool carrier is disconnected from the latter so that the transporting system can move the tool carrier out of the holding member. Due to the abutment of the contact surfaces, the axial stiffness and position of the arrangement is assured and the degree of stiffness is determined by the forces developed by the energy storing means. The magazine mounted on the spindle carrier head may contain 15 to 30 tool carriers. The time for selection of a tool carrier with a specific tool thereon may be shortened by an appropriate coding of the sequence in which the various tool carriers are arranged in the magazine. The automatic tool change requires only a time of about one second and the time in which a new tool can be brought in engagement with the workpiece is about 3 seconds.
The novel features which are considered as characteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic side view of a machine tool provided with the tool changing arrangement according to the present invention;
FIG. 2 is a front view of the machine tool shown in FIG. 2 viewed in the direction of the arrow II of FIG. 1;
FIG. 3 is a top view of the machine tool shown in FIG. 1, as viewed in the direction of the arrow III in FIG. 1;
FIG. 4 is a cross section through the drive spindle according to line IV--IV in FIG. 3 and showing the arrangement schematically and to a large scale than in FIG. 3;
FIG. 5 is a cross section taken along the line V--V of FIG. 6;
FIG. 6 is a cross section taken along the line VI--VI of FIG. 5;
FIG. 7 is a cross section taken along the line VII--VII of FIG. 6;
FIG. 8 is a cross section corresponding to that shown in FIG. 5, after coupling of drive spindle and tool carrier with each other;
FIG. 9 is a side view of a tool carrier with a tool mounted thereon; and
FIG. 10 is a side view of a tool carrier with another tool mounted thereon.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The machine tool schematically illustrated in FIG. 1 comprises an upright support 1 on which a spindle head 2 is reciprocable in vertical direction. A table 3 has an upper surface of about 1250 × 600 mm, on which the workpiece to be machined is to be mounted, and a static loadability of maximum 3000 kp. The table is movable in the usual manner along two coordinates which are normal to each other. A magazine 4, in which for instance 15 to 30 tool carriers 5 are arranged, is mounted on the bottom face of the spindle carrier 2. The tool carriers 5 are suspended on a circular rail 6 and are movable along the latter by a non-illustrated transport system, for instance a Maltese cross, to a working station 7 after the tool carriers have been moved at a loading station 8 into the magazine 4. At the working station 7 the tool carriers 5 are connectable with a hydrostatically mounted drive spindle 9. The drive spindle 9 is exactly mounted and may be driven at greatly varying speeds, for instance with 28 to 5600 rpm, so that the workpiece may be exactly machined regardless whether the workpiece is drilled, turned or provided with a thread. An arresting arrangement is provided for the drive spindle 9 in which the latter, in one of its axial end positions, as shown in FIG. 4, is arrested in a position in which the spindle has with respect to fixed points of the machine tool always the same distance and the same angular position. This arresting arrangement can be carried out in various ways and it does not form part of the present invention. All machine functions can be controlled by a three axis system in proper manner.
The drive spindle 9 is in tubular form and, as shown in FIG. 4, a holding member 11 is received in the bore 10 of the drive spindle and connected to the latter for rotation therewith by a key 13, fixed to the holding member 11 and engaging in a groove 12 of the spindle 9. This key and groove arrangement permits movement of the holding member 11 relative to the spindle in the direction of the axis 14 of the latter. The holding member 11 has substantially the form of an anchor and a crossbar 16, of a profile in form of an inverted T connected to the lower end of the cylindrical anchor shaft 15, serves as a receiving part 17 for a tool carrier 5. This receiving part 17 forms, in the region of the working station 7 in one end position of the holding member 11, respectively the drive spindle 9, part of the rail 6, that is, due to the arresting of the spindle 9 in a specific axial and angular position, the receiving part 17 is at the same level as the rail 6 and aligned with the latter. A bolt-shaped extension 18 projects from the end of the holding member, opposite the end on which the receiving part 17 is provided, and this extension 18 abuts in an axial end position of the holding member 11 against a fixed abutment 19 to thereby arrest the receiving part 17 in an exact axial position corresponding to the elevation of the rail 6. In this end position, the spindle 9 has a predetermined distance 20 from the abutment 19. Axial movement of the drive spindle 9 is carried out by means of a screw spindle 22, driven by a motor 21, and meshing with a nut 23 projecting laterally from an annular member 23', which in turn is mounted in an annular groove provided in the drive spindle 9, so that the annular member 23' and the nut 23 is axially fixed to the drive spindle 9, while the latter may rotate relative to the annular member 23'. The spindle 9 is driven about its axis by a gear 24 fixed thereto, which in turn is driven in a known manner, not shown in the drawing by a further drive mechanism. Energy storing means 25 are provided between the holding member 11 and the drive spindle 9 and this energy storing means 25 is preferably constituted by a pack of cup-shaped spring washers 26 which engages with one end of a stop 27 provided on the upper end of the bolt-shaped extension 18 and with its other end a shoulder 28 provided in the bore of the spindle 9. The pack of spring washers 26 is under pretension of about 1500 kp and the holding member 11 is drawn into the bore 10 of the drive spindle 9 with a corresponding force, when the bolt-shaped extension 18 is disassociated from the fixed abutment 19.
The tool carrier 5 (FIG. 5) is provided with a T-shaped groove, extending from the upper surface of the tool carrier into the latter. The groove has a profile which corresponds to the profile of the receiving part 17 of the holding member so that the tool carrier may be moved laterally, that is normal to the drive spindle axis 14, onto the part 17 of the holding member 11. Thereby, the tool carrier 5 abuts with a surface 31 onto a corresponding surface 32 of the part 17 and the side faces of the part 17 constitute turning moment transmitting faces 33 which cooperate with corresponding turning moment transmitting faces 34 on the tool carrier 5. The holding member 11 constitutes thereby a turning moment transmitting part 35 and the turning moment imparted to the drive spindle 9 is transmitted through the key 12 respectively the groove 13 onto the holding member 11 and from the latter over the turning moment transmitting faces 33, 34 onto the tool carrier 5.
The end face 29 of the tool carrier 5 carries a centralizing part 36 in form of a short cone 37, which is surrounded by a contact surface 38 extending normal to the tool carrier axis 39 and forming an annular surface 40. The short cone 37, as well as the annular surface 40, are interrupted by a groove 30 and by two opposite cutouts 41, 42 (FIG. 6), so that the short cone 34 is divided into four sectors 43-46.
The drive spindle 9 is likewise provided with an internal short cone 48 extending from the end face 47 into the spindle and serving as a centralizing part 49, and the conical surface is again surrounded by a contact face 50, constituted by a planar annular surface 51 normal to the axis 14 of the spindle.
The upper parts of all tool carriers 5 are constructed in the same manner for reception in the magazine 4, respectively onto the holding member 11, but the lower parts of the various tool carriers may be constructed in a different manner for the reception of specific tools. Thus, FIG. 9 illustrates a tool carrier 5 to which a tool holder 53 with a tool 52 in form of a turning bit 54 is connected. For this purpose, the tool carrier 5 is provided with a steep internal cone 55, extending centrally from the lower surface of the tool carrier 5 into the latter, into which a corresponding cone 56 of the tool holder 53 is inserted and held by means of a screw 57 in the tool carrier. In the modification of a tool carrier as shown in FIG. 10, the tool carrier 5 carries at its lower end a bolt 58, onto which a tool 52 in form of a milling cutter 59 with a bore 60 is applied and held on the tool carrier by a screw 61. In this case a considerable turning moment can be transmitted from the tool carrier 5 to the tool 52 by a key 62. The abutment face 38 of the tool carrier 5 serves as starting face 63 from which the length of the unit, comprising the tool carrier 5, the tool holder 53 and the tools 52 is determined, so that in the assembled position of the tool with the spindle, the engaging point 65 of the tool 52 is exactly determined by the axial end position of the spindle 9, the length thereof, and the distance of the point 65 from the surface 63 and the necessary programming of the movement of the spindle carrier head 2 respectively the advance of the drive spindle, can be easily carried out. In this way a loss of time for any subsequent correction of the tool length is avoided and the idle time of the machine tool correspondingly reduced.
Before the start of the machining operation, a tool carrier 5 with the desired tool 52 is brought by means of the transporting system to the working station 7, whereby the drive spindle 9, respectively the holding member 11 has the position as shown in FIG. 4, in which the crossbar 16 is axially and angularly aligned with the rail 6. The drive spindle 9 and the tool carrier have the position as shown in FIG. 5. By starting the fast advance of the spindle 9, by means of the electromotor 21 and the threaded spindle 22, the drive spindle 9 is moved in downward direction, but the holding member 11 remains still in the position as shown in FIG. 5 and the spring washer pack 26 partially expands. Subsequently thereto, the contact face 51 of the drive spindle 9 will abut against the contact face 38 of the tool carrier 5, hanging on the holding member 11, while the short cones 37 and 48 have still a small play with respect to each other. During further downward movement of the spindle 9, the holding member 11 is taken along and the upper end of the bolt-shaped extension 18 is thereby removed from the fixed abutment 19. The pretension of the energy storing means 25 will now act and move the holding member 11 and, over the abutment faces 31 and 32, the tool carrier 5 upwardly with a force corresponding to the pretension of the energy storing means. Since the contact faces 38 and 50 already abut against each other, this will cause spreading of the sectors 43-46 of the short cone 37 about elastic zones 66, so that a fully exact centralizing with the internal cone 48 will occur. The advance movement of the drive spindle is controlled in the usual manner until the machining of the workpiece is finished. Before fast return of the work spindle, the tool is disassociated from the workpiece by appropriate movement of the table 3 in connection with the arresting of the spindle 9 so that grooves on the workpiece during the return movement of the spindle are avoided. At the end of the return movement of the spindle, the extension 18 of the holding member 11 will abut the stationary abutment 19, while the upward movement of the spindle 9 proceeds during further operation of the electromotor 21, whereby the spring washer pack 27 is tensioned and the centralizing parts 36 and 49 are disassociated from each other, until the spindle stops in its predetermined end position in which the crossbar 16 of the receiving part 17 is again aligned with the rail 6 so that the tool carrier may be moved out of the working station 7 by the non-illustrated transporting system and a new tool 52 on another tool carrier may be placed on the holding member. Any idle time is thus avoided so that the change of a tool carrier can be carried out in the above-mentioned extremely short time.
While the present invention has been described in connection with an automatic tool changing arrangement, it is applicable also when the tool carrier is moved by hand onto the holding member 11 of the drive spindle 9. Thereby it is only necessary that the axes 14 and 39 are substantially aligned with each other and the precentralizing is then carried out by the short cones 37 and 48, whereas the exact centralizing is carried out by the spreading of the cone sectors 43-46.
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 tool changing arrangements for machine tools differing from the types described above.
While the invention has been illustrated and described as embodied in a tool changing arrangement for a machine tool, it is not intended to be limited to the details shown, since various modifications and structural changes may be made 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 tool changing arrangement for a machine tool comprises a rotary and axially movable drive spindle which coaxially carries a holding member rotatable therewith and movable in axial direction relative thereto. A tool carrier movable transversely to the holding member is provided at one end with a T-shaped slot into which a corresponding male portion on the holding member may be engaged, to couple the tool carrier to the holding member. The spindle and the tool carrier are provided at facing ends with interengaging centralizing portions which during axial movement of the holding member relative to the spindle axially align the tool carrier and the spindle. | 8 |
[0001] The present invention relates to compounds with α7 nicotinic acetylcholine receptor (α7 nAChR) agonistic activity, processes for their preparation, pharmaceutical compositions containing the same and the use thereof for the treatment of neurological and psychiatric diseases.
BACKGROUND OF THE INVENTION
[0002] A number of recent observations point to a potential neuroprotective effect of nicotine in a variety of neurodegeneration models in animals and in cultured cells, involving excitotoxic insults (1-5), trophic deprivation (6), ischemia (7), trauma (8), Aβ-mediated neuronal death (9-11) and protein-aggregation mediated neuronal degeneration (9;12). In many instances where nicotine displays a neuroprotective effect, a direct involvement of receptors comprising the α7 subtype has been invoked (7;11;13-16) suggesting that activation of α7 subtype-containing nicotinic acetylcholine receptors may be instrumental in mediating the neuroprotective effects of nicotine. The available data suggest that the α7 nicotinic acetylcholine receptor represents a valid molecular target for the development of agonists/positive modulators active as neuroprotective molecules. Indeed, α7 nicotinic receptor agonists have already been identified and evaluated as possible leads for the development of neuroprotective drugs (18-22). Involvement of α7 nicotinic acetylcholine receptor in inflammatory processes has also recently been described (23). Thus, the development of novel modulators of this receptor should lead to novel treatments of neurological, psychiatric and inflammatory diseases.
SUMMARY OF THE INVENTION
[0003] The invention provides compounds acting as full or partial agonists at the α7 nicotinic acetylcholine receptor (α7 nAChR), pharmaceutical compositions containing the same compounds and the use thereof for the treatment of diseases that may benefit from the activation of the alpha 7 nicotinic acetylcholine receptor such as neurological and psychiatric disorders, in particular Alzheimer's disease and schizophrenia.
DESCRIPTION OF THE INVENTION
[0004] In a first aspect, the invention provides a compound of formula I
[0000]
[0005] wherein:
[0006] Y is a group —CONH—; —NHCONH—; —NHCO—; —SO 2 NH—; —NHSO 2 —; —NHSO 2 NH—; —OCONH; —NHCOO—
[0007] Q is a 5 to 10-membered aromatic or heteroaromatic ring
[0008] R is hydrogen; halogen; linear, branched or cyclic (C 1 -C 6 ) alkyl, haloalkyl, alkoxy or acyl; hydroxy; cyano; nitro; mono- or di- (C 1 -C 6 ) alkylamino, acylamino or alkylaminocarbonyl; carbamoyl; (C 6 -C 10 ) aryl- or (C 1 -C 6 ) alkylsulphonylamino; (C 6 -C 10 ) aryl- or (C 1 -C 6 ) alkylsulphamoyl; a 5 to 10-membered aromatic or heteroaromatic ring optionally substituted with: halogen; linear, branched or cyclic (C 1 -C 3 ) alkyl, haloalkyl, alkoxy or acyl; hydroxy; cyano; nitro; amino; mono- or di- (C 1 -C 6 ) alkylamino, acylamino or alkylaminocarbonyl groups; carbamoyl; (C 6 -C 10 ) aryl- or (C 1 -C 6 ) alkylsulphonylamino; (C 6-10 ) aryl- or (C 1 -C 6 ) alkylsulphamoyl;
[0009] X is a group of formula
[0000]
[0010] wherein
[0011] R 1 represents (C 1 -C 6 ) acyl; linear, branched or cyclic (C 1 -C 6 ) alkyl; a —(CH 2 ) j —R′″ group, wherein j=0,1 and R′″ is a 5 to 10-membered aromatic or heteroaromatic ring optionally substituted with: halogen; hydroxy; cyano; nitro; (C 1 -C 6 ) alkyl, haloalkyl, alkoxy, acyl, acylamino groups;
[0012] Z is CH 2 , N or O
[0013] m is an integer from 1 to 4
[0014] n is 0 or 1;
[0015] s is 1 or 2;
[0016] p is 0, 1 or 2;
[0017] R″, independently from one another for p=2, represents hydrogen; halogen; hydroxy; cyano; nitro; linear, branched or cyclic (C 1 -C 6 ) alkyl, haloalkyl, alkoxy, acyl; a —(CH 2 ) j —R′″ group, wherein n and R′″ are as above defined; carbamoyl; (C 6 -C 10 ) aryl- or (C 1 -C 3 ) alkylsulphonylamino; (C 6 -C 10 ) aryl- or (C 1 -C 3 ) alkylsulphamoyl; mono- or di-[linear, branched or cyclic (C 1 -C 6 ) alkyl]aminocarbonyl;
[0018] A first group (Ia) of preferred compounds of formula I are those in which:
[0019] Y is —CONH—; —NHCO—; —NHCONH—
[0020] Q is a 5 to 10-membered aromatic or heteroaromatic ring;
[0021] R is selected from the group consisting of hydrogen; halogen; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy or alkylamino; trihaloalkyl; phenyl; naphthyl; pyridyl; pyrimidinyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0022] X is a group
[0000]
[0023] Z is CH 2 , N or O
[0024] m is an integer from 1 to 4
[0025] p is 0, 1 or 2
[0026] R″, independently from one another for p=2, is selected from the group consisting of hydrogen; mono- or di-[linear, branched or cyclic (C 1 -C 6 ) alkyl]aminocarbonyl; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy, acyl;
[0027] Particularly preferred compounds Ia are those where Y is —CONH(Q)-;
[0028] Q is a 5 to 10-membered aromatic or heteroaromatic ring
[0029] R is selected from the group consisting of phenyl; naphthyl; pyridyl; pyrimidinyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0030] X is a group
[0000]
[0031] where
[0032] Z is CH 2 , N or O
[0033] m is an integer from 1 to 4
[0034] p is 0, 1 or 2
[0035] R″, independently of one another for p=2, is selected from the group consisting of hydrogen; mono- or di-[linear, branched or cyclic (C 1 -C 6 ) alkyl]aminocarbonyl; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy, acyl;
[0036] Another group of particularly preferred compounds Ia are those where
[0037] Y is —NHCONH(Q)-;
[0038] Q is a 5 to 10-membered aromatic or heteroaromatic ring
[0039] R is selected from the group consisting of halogen; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy or alkylamino; haloalkyl; phenyl; naphthyl; pyridyl; pyrimidinyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0040] X is a group
[0000]
[0041] Z is CH 2 , N or O
[0042] m is an integer from 1 to 4
[0043] is 0, 1 or 2
[0044] R″, independently from one another for p=2, is selected from the group consisting of hydrogen; mono- or di-[linear, branched or cyclic (C 1 -C 6 ) alkyl]aminocarbonyl; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy, acyl;
[0045] Another group of particularly preferred compounds Ia are those where
[0046] Y=—NHCO(Q)-;
[0047] Q is phenyl
[0048] R is selected from the group consisting of phenyl; naphthyl; pyridyl; pyrimidinyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0049] X is a group
[0000]
[0050] where
[0051] Z is CH 2 , N or O
[0052] m is an integer from 1 to 4
[0053] p is 0, 1 or 2
[0054] R″, independently of one another for p=2, is selected from the group consisting of hydrogen; mono- or di-[linear, branched or cyclic (C 1 -C 6 ) alkyl]aminocarbonyl; linear, branched or cyclic (C 1 -C 6 ) alkyl, alkoxy, acyl;
[0055] A further group (Ib) of preferred compounds of formula (I) are those in which
[0056] Y is —CONH(Q)
[0057] Q is phenyl, indolyl
[0058] R is selected from the group consisting of halogen; phenyl; naphthyl; pyridyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0059] X is a group
[0000]
[0060] where R′ is a 5-10-membered aromatic or heteroaromatic ring optionally substituted with halogen or (C 1 -C 6 ) alkoxy groups;
[0061] A further group (Ic) of preferred compounds of formula (I) are those in which
[0062] Y is —NHCONH(Q)
[0063] Q is phenyl, indolyl
[0064] R is selected from the group consisting of halogen; phenyl; naphthyl; pyridyl; quinolinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0065] X is a group
[0000]
[0066] where R′ is a 6-membered aromatic or heteroaromatic ring optionally substituted with halogen or (C 1 -C 6 ) alkoxy groups;
[0067] Another group (Id) of preferred compounds of formula I are those in which
[0068] Y is —NHCO(Q);
[0069] Q is phenyl, pyridyl
[0070] R is selected from the group consisting of phenyl; naphthyl; pyridyl; quinolinyl; pyrimidinyl; isoquinolinyl; indolyl; thienyl; benzothienyl; furanyl; benzofuranyl; imidazolyl; benzoimidazolyl; pyrrolyl; optionally substituted as indicated above for the compounds of formula (I);
[0071] X is a group
[0000]
[0072] where R′ is a phenyl ring optionally substituted with halogen or (C 1 -C 6 ) alkoxy groups;
[0073] Particularly preferred are the compounds (Id) wherein
[0074] Y is —NHCO(Q);
[0075] Q is phenyl
[0076] R is selected from the group consisting of phenyl; pyridyl; indolyl; pyrimidinyl; optionally substituted with: halogen; linear, branched or cyclic (C 1 -C 3 ) alkyl, alkoxy or acyl; cyano; (C 1 -C 6 ) alkylamino; acylamino; alkylaminocarbonyl groups; carbamoyl;
[0077] X is a group
[0000]
[0078] where R′ is a phenyl ring optionally substituted with halogen or (C 1 -C 6 ) alkoxy groups
[0079] The compounds of the invention can be in the form of free bases or acid addition salts, preferably salts with pharmaceutically acceptable acids. The invention also includes separated isomers and diastereomers of compounds I, or mixtures thereof (e.g. racemic mixtures).
[0080] The compounds of Formula (I) can be prepared through a number of synthetic routes amongst which the ones illustrated in Schemes 1, 2, and 3 (see also for reference Bioorg. Med. Chem. Lett. 1995, 5 (3), 219-222).
[0000]
[0081] According to Scheme 1, a suitably activated butylphthalimide (compound 2 ) is reacted with an amine (compound 1) in an organic solvent in the presence of a base. For example, a mixture of 1 (or its hydrochloride salt) and 2 are refluxed in methylethyl ketone in the presence of alkaline carbonate until the reaction is complete, then the reaction mixture is cooled, the insoluble materials removed by filtration, the filtrate washed with CHCl 3 , and the filtrate and washings concentrated to dryness.
[0082] In the following step, the N-(4-aminobutyl)phthalimide 3 is converted into a (4-aminobutyl)amine 4, for example by refluxing a mixture of 3 and hydrazine hydrate in ethanol. Then 4 is reacted with an activated species 5 such as for example (but not limited to) an acid chloride or an isocyanate in an organic solvent in the presence of a base. For example, to a mixture of 4 and 5 in CH 2 Cl 2 triethylamine and a catalytic amount of DMAP are added, to give compounds I. Alternatively, a mixture of 4, 5, a carbodiimide or carbonyldiimidazole and DMAP are reacted to yield compounds I.
[0000]
[0083] According to Scheme 2, aminobutanol is reacted with an activated acid species or an isocyanate—for example (but not limited to) a substituted acid chloride 6 in the presence of a base—in an organic solvent like dichloromethane until the reaction is complete. The alcohol 7 thus obtained is then oxidised under standard conditions (for example Swern oxidation) and aldehyde 8 is then reacted with the suitably substituted amine 1 under standard conditions—for example with sodium triacetoxyborohydride—to afford compound Iα. In the case of R being a halogen, Iα can be further processed—for example via a cross-coupling reaction with a boronic acid—to yield compound Iβ.
[0000]
[0084] According to Scheme 3, 5-bromopentanoyl chloride is reacted with an (hetero)aromatic amine 9 in the presence of an organic base to afford a 5-bromopentanoic acid amide 10. This species is reacted with an amine 1 to displace the halogen and furnish compounds Iα. In the case of R being a halogen, Ia can be further processed—for example via a cross-coupling reaction with a boronic acid—to yield compounds Iβ.
[0085] The compounds of formula I, their optical isomers or diastereomers can be purified or separated according to well-known procedures, including but not limited to chromatography with chiral matrix and fractional crystallisation.
[0086] The pharmacological activity of a representative group of compounds of formula I was demonstrated in an in vitro assay utilising cells stably transfected with the alpha 7 nicotinic acetylcholine receptor and cells expressing the alpha 1 and alpha 3 nicotinic acetylcholine receptors and 5HT3 receptor as controls for selectivity. Neuroprotection of these compounds was demonstrated in a cell-based excitotoxicity assay utilising primary neuronal cell cultures.
[0087] According to a further aspect, the invention is therefore directed to a method of treating neurological and psychiatric disorders, which comprises administering to a subject, preferably a human subject in need thereof, an effective amount of a compound of formula I. Neurological and psychiatric disorders that may benefit from the treatment with the invention compounds include but are not limited to senile dementia, attention deficit disorders, Alzheimer's disease and schizophrenia. In general, the compounds of formula I can be used for treating any disease condition, disorder or dysfunction that may benefit from the activation of the alpha 7 nicotinic acetylcholine receptor, including but not limited to Parkinson's disease, Huntington's chorea, amyotrophic lateral sclerosis, multiple sclerosis, epilepsy, memory or learning deficit, panic disorders, cognitive disorders, depression, sepsis, arthritis, immunological and inflammatory disorders.
[0088] The dosage of the compounds for use in therapy may vary depending upon, for example, the administration route, the nature and severity of the disease. In general, an acceptable pharmacological effect in humans may be obtained with daily dosages ranging from 0.01 to 200 mg/kg.
[0089] In yet a further aspect, the invention refers to a pharmaceutical composition containing one or more compounds of formula I, in association with pharmaceutically acceptable carriers and excipients. The pharmaceutical compositions can be in the form of solid, semi-solid or liquid preparations, preferably in form of solutions, suspensions, powders, granules, tablets, capsules, syrups, suppositories, aerosols or controlled delivery systems. The compositions can be administered by a variety of routes, including oral, transdermal, subcutaneous, intravenous, intramuscular, rectal and intranasal, and are preferably formulated in unit dosage form, each dosage containing from about 1 to about 1000 mg, preferably from 1 to 600 mg of the active ingredient. The compounds of the invention can be in the form of free bases or as acid addition salts, preferably salts with pharmaceutically acceptable acids. The invention also includes separated isomers and diastereomers of compounds I, or mixtures thereof (e.g. racemic mixtures). The principles and methods for the preparation of pharmaceutical compositions are described for example in Remington's Pharmaceutical Science, Mack Publishing Company, Easton (Pa.).
DESCRIPTION OF THE FIGURES
[0090]
FIG. 1
[0091] Effect of compound from Example 64 on NMDA-induced toxicity in rat cortical neurons. Rat cortical neurons were pre-treated with the compound at the indicated concentrations 24 h before addition of NMDA and toxicity determined by lactate dehydrogenase (LDH) measurements after 24 h. Data of all experiments are normalised to 100% NMDA toxicity. Statistical analysis:
[0092] p<0.05 vs NMDA treatment; One-Way ANOVA and Tukey post test values were normalised to the level of NMDA (=100%).
[0093]
FIG. 2
[0094] Effect of sub-chronic treatment of compound from Example 1 or nicotine on number of ChAT-positive neurons in the nucleus basalis of quisqualic acid injected animals. Compounds were administered 24 h and 1 h before quisqualic acid injection and for 7 days after lesioning. Doses: compound 3 mg/kg i.p. daily or nicotine 0.3 mg/kg i.p. daily. The doses were selected on the basis of literature data and comparable effects in behavioral studies. Number of neurons is expressed as % changes vs non-injected hemisphere. Statistical analysis: ANOVA and Fisher Post-Hoc test: F(3,21)=13.00 P<0.001*P<0.05 vs quisqualic acid injected rats # P<0.05 vs nicotine treated rats.
[0095]
FIG. 3
[0096] FIG. 3 a —Results of passive avoidance test
[0097] Effect of acute administration of compound from Example 1 on scopolamine-induced amnesia in young rats in passive avoidance test and reversion by the selective alpha-7 antagonist MLA. Amnesia was induced by scopolamine 0.5 mg/kg i.p. 20 min before training trial and the compound (3 mg/kg i.p.) was injected 5 min after scopolamine. MLA (5 mg/kg i.p.) was administered 10 min before scopolamine and compound administration. Results are presented as retest latencies 24 h after the training trial.
[0098] Statistical analysis: ANOVA and Tukey Post-Hoc test: * P<0.05 vs saline and scopolamine-treated rats # P<0.05 vs saline treated rats.
[0099] FIG. 3 b —Results of object recognition test
[0100] Effect of acute administration of compound from Example 1 on scopolamine-induced amnesia in young rats. Amnesia was induced by scopolamine 0.2 mg/kg i.p. 20 min before training trial and the compound (3 mg/kg i.p.) was injected 5 min after scopolamine. Results are presented as discrimination index calculated on the exploration time of new (N) and familiar (F) objects during the test trial performed after 2 h from the training trial as follow: Discrimination index: N−F/N+F. Statistical analysis: ANOVA and Tukey Post-Hoc test: * P<0.05 scopolamine-treated rats.
EXPERIMENTAL PROCEDURES—SYNTHESIS OF COMPOUNDS
[0101] General
[0102] Unless otherwise specified all nuclear magnetic resonance spectra were recorded using a Bruker AC200 (200 MHz) or a Varian Mercury Plus 400 Mhzspectrometer equipped with a PFG ATB Broadband probe.
[0103] HPLC-MS analyses were performed with an Agilent 1100 instrument, using a Zorbax Eclipse XDB-C8 4.6×150 mm; a Zorbax CN 4.6×150 mm column or a Zorbax Extend C18 2.1×50 mm column, coupled to an atmospheric API-ES MS for the 2.5 minutes method. The 5 and 10 minute methods were run using a waters 2795 separation module equipped with a Waters Micromass ZQ (ES ionisation) and Waters PDA 2996, using a Waters XTerra MS C18 3.5 μm 2.1×50 mm column.
[0104] Preparative HLPC was run using a Waters 2767 system with a binary Gradient Module Waters 2525 pump and coupled to a Waters Micromass ZQ (ES) or Waters 2487 DAD, using a Supelco Discovery HS C18 5.0 μm 10×21.2 mm column
[0105] Gradients were run using 0.1% formic acid/water and 0.1% formic acid/acetonitrile with gradient 5/95 to 95/5 in the run time indicated.
[0106] All column chromatography was performed following the method of Still, C.; J. Org Chem 43, 2923 (1978). All TLC analyses were performed on silica gel (Merck 60 F254) and spots revealed by UV visualisation at 254 nm and KmnO4 or ninhydrin stain.
[0107] All microwave reactions were performed in a CEM Discover oven.
N-(4-(Arylpiperazin-1-yl)-butyl)phthalimides
[0108] The compounds were prepared following the general procedure outlined in Nishikawa, Y.; et al; Chem. Pharm. Bull., 1989, 37 (1), 100-105.
[0109] A mixture of N-(4-bromobutyl)-phthalimide (0.00135 mol), 1-(aryl)-piperazine hydrochloride (0.00135 mol), K 2 CO 3 (0.00270 mol), NaI (0.00186 mol) and methylethyl ketone (7 mL) was refluxed for 20 h with stirring. After the mixture was cooled, the insoluble materials were removed by filtration and washed with CHCl 3 . The filtrate and the washings were concentrated to dryness in vacuo.
[0110] The residue was subjected to chromatography on silica gel using CHCl 3 /MeOH 95/5 as eluent.
4-[4-(Aryl-piperazin-1-yl)]-butylamines
[0111] A solution of N-(4-(Arylpiperazin-1-yl)-butyl)phthalimides (0.236 mmol) and hydrazine hydrate (0.478 mmol) in ethanol (2 mL) was refluxed for 2 h with stirring. After the solution had cooled, the insoluble materials were removed by filtration and washed with EtOH. The filtrate and the washings were concentrated to dryness in vacuo. The residue was taken up with CHCl 3 . The CHCl 3 layer was washed with water, dried and concentrated to give the title amine.
4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butylamine
[0112] a) Following the general procedure, 2-methoxyphenyl-piperazine (3.4 mL, 17.7 mmol) is added to a suspension of N-(4-bromobutyl)phthalimide (5 g, 17.7 mmol), sodium iodide (1.33 g, 8.85 mmol) and potassium carbonate (3.67 g, 26.6 mmol) in 2-butanone (70 mL). The resulting suspension is stirred for 18 h at 100° C., before LC-MS check. The reaction is filtered and the solvent removed by vacuum distillation; the resulting oil is dissolved in 5% MeOH in dichloromethane, washed with water and sat. NaCl, dried over Na 2 SO 4 . The solvent is removed under reduced pressure to yield the desired product as a thick yellow oil. The residue is extracted into ethyl acetate and washed with water and then saturated brine and dried over sodium sulphate. The solvent is removed under reduced pressure to afford 5.01 g of 2-{4-[4-(2-methoxy-phenyl)-piperazin-1-yl]-butyl}-isoindole-1,3-dione used without further purification in step b) below (72%).
[0113] 2-{4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butyl}-isoindole-1,3-dione (5.01 g, 12.7 mmol) is dissolved in abs. EtOH (60 mL) and hydrazine monohydrate (2.54 mL, 26 mmol) is added dropwise. The reaction is heated at 100° C. for 1 h; the reaction is filtered, concentrated at reduced pressure and transformed into its hydrochloride salt. The salt is dissolved in 15% NaOH and extracted into ethyl acetate to yield 2.04 g of 4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butylamine as waxy solid (7.8 mmol, 61%).
[0114] C 15 H 25 N 3 O Mass (calculated) [263.39]; (found) [M+H+] 32 264.39
[0115] LC Rt=0.45, 92% (5 min method)
[0116] NMR (400 MHz, CDCl3): 1.48 (2H, m); 1.57 (2H, m); 2.42 (2H, m); 2.65 (4H, bs); 2.72 (2H, m); 3.1 (4H, bs); 3.86 (3H, s); 6.85 (1H, d); 6.97 (3H, m).
4-[4-(2,4-Difluoro-phenyl)-piperazin-1-yl]-butylamine
[0117] To a solution of N-(4-bromobutyl)phthalimide (5 g, 17.73 mmol) and 1-(2,4-difluoro-phenyl)-piperazine (17.73 mmol) in 2-butanone (100 mL), potassium carbonate (26.6 mmol) and potassium iodide (13.3 mmol) were added. The resulting mixture was heated at 90° C. overnight. After cooling the solution was filtered and evaporated to dryness. The residue was dissolved in dichloromethane (100 mL) and washed with water. The organic phase was dried over sodium sulphate and evaporated. This material was dissolved in ethanol (100 mL) and hydrazine (2 eq) was added. The solution was refluxed for 4 hours when a thick precipitate formed. Conc. HCl (5 mL) was then added and the mixture heated for a further hour. After cooling the solvent was evaporated and the residue dissolved in 2M HCl (100 mL). This solution was filtered and the aqueous filtrate evaporated again to dryness. The resulting residue was taken in isopropanol (30 mL) and filtered to give the hydrochloride salt of the required product. The salt was converted in the free amine by dissolution in NaOH (15% w/w) and extraction with dichloromethane. (2.6 g, 54%).
[0118] 1 H-NMR (CDCl 3 ) δ 1.3 (br s, 2H), 1.46-1.58 (m, 4H), 2.41 (t, 2H), 2.62 (s, 4H), 2.73 (t, 2H), 3.05 (br s, 4H), 6.77-6.83 (m, 2H), 6.87-6.94 (m, 1H) (M+1) e/z 270
4-Morpholin-4-yl-butylamine
[0119] a) Following the general procedure, morpholine (1.7 mL, 20 mmol) is added to a suspension of N-(4-bromobutyl)phthalimide (5.36 g, 20 mmol), sodium iodide (1.5 g, 10 mmol) and potassium carbonate (5.53 g, 40 mmol) in 2-butanone (80 mL). The resulting suspension is stirred for 18 h at 100° C., before LC-MS check. The reaction is filtered and the solvent removed by vacuum distillation; the resulting oil is dissolved in 5% MeOH in dichloromethane, washed with water and sat. NaCl, dried over Na 2 SO 4 . The solvent is removed under reduced pressure to yield the desired product as a thick yellow oil. The residue was extracted into ethyl acetate and washed with water and then saturated brine and dried over sodium sulphate. The solvent was removed under reduced pressure to afford 5.7 g of 2-(4-Morpholin-4-yl-butyl)-isoindole-1,3-dione used without further purification in step b) below.
[0120] C 16 H 20 N 2 O 3 Mass (calculated) [288.35]; (found) [M+H+]=289.36
[0121] Lc Rt=0.83, 95% (3 min method)
[0122] b) 4-Morpholin-4-yl-butyl-isoindole-1,3-dione (5.69 g, 19 mmol) is dissolved in abs. EtOH (95 mL) and hydrazine monohydrate (3.8 mL, 80 mmol) is added dropwise. The reaction is heated at 100° C. for 1 h; LC-MS show the reaction to be complete. The reaction is filtered, concentrated at reduced pressure and taken up with toluene and dichloromethane to remove excess phthalhydrazide; the crude amine is purified by SCX column, eluting with MeOH:dichloromethane 1:1 followed by 2 M NH3 in MeOH, to afford 1.46 g (9.2 mmol, 48%).
[0123] C 8 H 18 N 2 O Mass (calculated) [158.25]; (found) [M+H+]=159.27
[0124] LC Rt=0.29, 96% (3 min method)
[0125] NMR (400 MHz, CD3OD): 1.51 (4H, m); 2.36 (2H, m); 2.46 (4H, s); 2.64 (2H, m); 3.68 (4H, m).
[0126] 1 H-NMR (CDCl 3 ) δ 1.26 (br s, 2H), 1.44-1.57 (m, 4H), 2.35 (t, 2H), 2.44 (br s, 4H), 2.71 (t, 2H), 3.72 (m, 4H)
4-(4-Methyl-piperazin-1-yl)-butylamine
[0127] Prepared in analogous manner as 4-[4-(2,4-difluoro-phenyl)-piperazin-1-yl]-butylamine and obtained in yield=25%.
[0128] 1 H-NMR (dmso-d6+D 2 O) δ 1.53-1.61 (m, 2H), 1.66-1.74 (m, 2H), 2.80 (t, 2H), 2.85 (s, 3H), 3.17 (m, 2H), 3.38 (br s, 4H), 3.67 (br s, 4H); (M+1) e/z 172.
4-Piperidin-1-yl-butylamine
[0129] a) Following the general procedure, N-(4-bromobutyl)phthalimide (5.96 g, 20 mmol) was added to a suspension of piperidine (1.98 mL, 20 mmol), sodium iodide (1.5 g, 10 mmol) and potassium carbonate (4.15 g, 21 mmol) in 2-butanone (100 mL). The resulting suspension was stirred for 18 h at 85° C. The reaction was filtered and the solvent removed by vacuum distillation; the resulting oil was washed with water and recovered with dichloromethane. The solvent was removed under reduced pressure to afford 3.7 g of desired product as a white solid (yield: 65%).
[0130] C 17 H 22 N 2 O 2 Mass (calculated) [286.38]; (found) [M+H+]=287
[0131] Lc Rt=0.97, 95% (5 min method)
[0132] NMR (400 MHz, CDCl3) 1.41 (2H, m), 1.49-1.59 (6H, m), 1.65-1.72 (2H, m), 2.15-2.35 (6H, m), 3.69-3.73 (6H, m), 7.69-7.74 (2H, m), 7.80-7.85 (2H, m).
[0133] b) 2-(4-Piperidin-1-yl-butyl)-isoindole-1,3-dione (3.7 g, 13 mmol) was dissolved in EtOH (50 mL) and hydrazine monohydrate (1.26 mL, 26 mmol) was added dropwise. The mixture was heated at 80° C. for 4 h. The reaction was filtered, concentrated at reduced pressure and taken up with toluene and dichloromethane to remove excess phthalhydrazide by filtration; the crude amine was purified by SCX column, eluting with MeOH:dichloromethane 1:1 followed by 2 M NH3 in MeOH, to afford g (410 mg, 35%).
[0134] C 9 H 20 N 2 Mass (calculated) [156.27]; (found) [M+H+]157
[0135] LC Rt=0.31 (5 min method)
[0136] NMR (400 MHz, CD3OD): 1.45-1.62 (10 H, m), 2.30-2.43 (10 H, m), 2.64-2.67 (2H, m).
1-(4-Amino-butyl)-piperidine-3-carboxylic acid diethylamide
[0137] a) Following the general procedure, commercially available N,N-diethylnipecotamide (3.4 g, 40 mmol) was weighed, placed in a flask and dissolved in 150 mL 2-butanone. To this N-(4-bromobutyl)phthalimide (11.3 g, 40 mmol), NaI (3 g, 20 mmol) and K2CO3 (8.28 g, 60 mmol) were added. The resulting mixture was heated at 85° C. for 20 hours. The solution was dried under vacuum and the crude solution was washed twice with water and dichloromethane. The organic layer was purified by flash chromatography using dichloromethane/MeOH 96/4.
[0138] C 22 H 31 N 3 O 3 Mass (calculated) [385.50]; (found) [M+H+]=386
[0139] LC Rt=2.63, 94% (10 min method)
[0140] NMR (400 MHz, CDCl3): 1.08-1.12 (2H, m), 1.14-1.21 (2H, m), 1.52-1.76 (8H, m), 2.1 (1H, m), 2.23 (1 H, m), 2.44 (1H, m), 2.79 (1H, m), 2.94 (2H, m), 3.29-3.35 (4H, m), 3.69-3.73 (2H, m), 7.71-7.82 (2H, m), 7.82-7.86 (2H, m).
[0141] b) The phthalimide was deprotected using the general method described for the previous examples to obtain the desired product in 38% yield.
[0142] C 14 H 29 N 3 O Mass (calculated) [255.23]; (found) [M+H+] 32 256
[0143] LC Rt=0.35 (10 min method)
[0144] NMR (400 MHz, CDCl3): 1.09 (3H, m); 1.21 (3H, m); 1.50-1.60 (1H, m); 1.62-1.84 (6H, m), 2.13-2.19 (1H, m); 2.35-2.40 (1H, m); 2.46-2.50 (2H, m); 2.79-3.02 (5H, m); 3.27-3.47 (4H, m); 5.20-5.31 (3H, m).
[0145] General Procedure for the synthesis of biaryl carboxylic acids
[0146] Prepared according to the procedure outlined in Gong, Y. and Pauls, H. W. Synlett, 2000, 6, 829-831.
[0147] A catalytic amount of Pd(PPh 3 ) 4 was added to a degassed solution of 4-carboxyphenylboronic acid (0.001 mol) and arylic bromide (0.001 mol) in 0.4 M sodium carbonate solution (5 mL) and acetonitrile (5 mL).
[0148] The mixture was heated at 90° C. under N 2 for 15-20 h. The hot suspension was filtered. The filtrate was concentrated to about a half the original volume and then washed with CH 2 Cl 2 . The aqueous layer was acidified with conc. HCl and the resulting precipitate was collected.
2′-Amino-biphenyl-4-carboxylic acid
[0149] Yield: 80%
[0150] 1 H-NMR (CD 3 OD) δ (ppm): 8.10 (d, 1H); 7.50 (d, 2H); 6.94 (m, 4H)
[0151] Mass (ES) m/z %: 214 (M+1, 100%).
4-(Pyridin-2-yl)-benzoic acid
[0152] Yield: 70%;
[0153] 1 H-NMR (CD 3 OD) δ (ppm): 8.63 (d, 1H); 8.05 (m, 4H); 7.90 (m, 2H); 7.51 (m, 1H).
[0154] Mass (ES) m/z %: 200 (M+1, 100%).
4-(1-Oxy-pyridin-2-yl)-benzoic acid
[0155] Mass (ES) m/z %: 216 (M+1, 100%).
2′-Methylbiphenyl-4-carboxylic acid
[0156] Prepared with a modification of the procedure outlined in Leadbeater, N. E.; Marco, M; Org. Lett. 2002, 4 917) 2973-2976:
[0157] In a 10 mL glass tube were placed 4-carboxyphenyl boronic acid (166 mg, 1.0 mmol), 2-bromotoluene (120 μL, 1.0 mmol), Na 2 CO 3 (315 mg, 3 mmol), Pd(OAc) 2 (1 mg, 0.004 mmol), 2 mL of water and a magnetic stirbar. The vessel was sealed with a septum and placed into the microwave cavity. Microwave irradiation (maximum emitted power 200W) was used to increase the temperature to 150° C.; the reaction mixture was then kept at this temperature for 5 min.
[0158] The mixture was allowed to cool to room temperature, and the reaction mixture was filtered washing with little CHCl 3 . The aqueous layer was acidified, and the precipitate collected. The product was purified by chromatography on silica gel using Petroleum Ether/AcOEt 50/50 as eluent to give 67.8 mg of 12, yield 32%.
[0159] 1 H-NMR (CD 3 OD) δ (ppm): 8.05 (m, 2H, arom); 7,41 (m, 2H, arom); 7.21 (m, 4H, arom); 2.22 (s, 3H, C—CH 3 ).
[0160] Mass (ES) m/z %: 424 (2M, 100%).
2′-Nitrobiphenyl-4-carboxylic acid
[0161] To a stirred solution of 2′-aminobiphenyl-4-carboxylic acid (213 mg, 0.001 mol) in hexane/water/acetone (6.7:5:1, 6 mL), were added at 0° C. NaHCO 3 (400 mg) and Oxone (1.050 g). After 20 min a second portion of NaHCO 3 (400 mg) and Oxone® (1050 mg) was added and, after 20 min, a final portion of NaHCO 3 (400 mg) and Oxone® (1050 mg) was added. After 6 h the suspension was diluted with water and the organic layer was extracted with CH 2 Cl 2 . The combined organic layers were evaporated to give 2′-nitro-biphenyl-4-carboxylic acid (138.5 mg, 0.00057 mol), yield 57%.
[0162] 1 H-NMR (CD 3 OD) δ (ppm): 7.80 (m, 8H)
[0163] Mass (ES neg) m/z %: 242 (M−1, 100%); 226 (M−1-16, 70%)
2′-Methoxy-biphenyl-4-carboxylic acid
[0164] To a solution of 4-carboxyphenylboronic acid (3.32 g, 20 mmol), Fibrecat®1007 (2 g) and potassium carbonate (3.03 g, 22 mmol) in ethanol/water (20 mL/20 mL), 1-bromo-2-methoxy-benzene was added (4.11 g, 22 mmol). The reaction mixture was heated to reflux for 3 hours. After cooling, was filtered and the solution evaporated under reduced pressure. The residue was suspended in aq. citric acid (10% w/v), filtered and washed with water and diethyl ether. The resulting solid was dried under vacuum to yield the title compound (4.02 g, 88%).
[0165] 1 H-NMR (dmso-d6) δ 3.79 (s, 3H), 7.08 (m, 1H), 7.34 (m, 1H), 7.58 (d, 1H), 7.96 (d, 1H)
2′-Chloro-biphenyl-4-carboxylic acid
[0166] A mixture of 4-carboxyphenylboronic acid (3.32 g, 20 mmol), Fibrecat®1007 (1 g), potassium carbonate (3.03 g, 22 mmol) and 1-bromo-2-chloro-benzene (4.2 g, 22 mmol) were exposed to microwave irradiation in a CEM Discovery Microwave for 15 minutes up to the maximum temperature of 120° C. After cooling, the mixture was filtered and the solution evaporated under reduced pressure. The residue was suspended in 1M HCl solution, filtered and washed with water and diethyl ether. The resulting solid was dried under vacuum to yield the title compound (4.0 g, 86%).
[0167] 1 H-NMR (dmso-d6) δ 7.38-7.45 (m, 3H), 7.50-7.59 (m, 3H), 7.98-8.02 (m, 2H); (M+1) e/z 233
2′,4′-Difluoro-biphenyl-4-carboxylic acid
[0168] Prepared as outlined for 2′-chloro-biphenyl-4-carboxylic acid and obtained in yield=49%.
[0169] 1 H-NMR (dmso-d6) δ 7.24 (m, 1H), 7.42 (m, 1H), 7.62-7.60 (m, 3H), 8.04 (d, 2H); (M+1) e/z 235
2′-Carbamoyl-biphenyl-4-carboxylic acid
[0170] Prepared as outlined for 2′-chloro-biphenyl-4-carboxylic acid and obtained in yield=29%.
[0171] 1 H-NMR (dmso-d6) δ 7.33 (s, 1H), 7.40-7.52 (m, 6H), 7.70 (s, 1H), 7.95 (d, 2H); (M+1) e/z 242
2-Methyl-biphenyl-4-carboxylic acid
[0172] Prepared as outlined for 2′-chloro-biphenyl-4-carboxylic acid and obtained in yield=59%.
[0173] 1 H-NMR (dmso-d6) δ 2.29 (s, 3H), 7.31-7.50 (m, 6H), 7.83 (dd, 1H), 7.89 (s, 1H); (M+1) e/z 213
6-Phenyl-nicotinic acid
[0174] Prepared as outlined for 2′-chloro-biphenyl-4-carboxylic acid
[0175] 1 H-NMR (dmso-d6) δ 7.47-7.55 (m, 3H), 8.1 (d, 1H), 8.11-8.16 (m, 2H), 8.32 (dd, 1H), 9.13 (s, 1H), 13.39 (br s, 1H); (M+1) e/z 200
4-(5-oxo-4,5-dihydro-[1,2,4]oxadiazol-3-yl)-benzoic acid
a) 4-(N-hydroxycarbamimidoyl)-benzoic acid methyl ester
[0176] A mixture of 4-cyano-benzoic acid methyl ester (16.5 g, 102 mmol), hydroxylamine hydrochloride (102 mmol), NaHCO 3 (110 mmol) in methanol (200 mL) was stirred for 30 minutes at room temperature and heated to the reflux for a further 3 hours. After cooling, water (400 mL) was added, the precipitate collected by filtration, washed and dried in a vacuum oven at 50° C. for 8 hours to give the title compound as a white solid (16.5 g, 83%). (M+1) e/z 195
b) 4-(5-Oxo-4,5-dihydro-[1,2,4]oxadiazol-3-yl) -benzoic acid
[0177] To a solution of 4-(N-hydroxycarbamimidoyl)-benzoic acid methyl ester (5.7 g, 29.4 mmol) in dioxane (30 mL) was added CDI (1.2 eq). The reaction mixture was heated to 110° C. for 30 minutes. After cooling the solvent was evaporated, the residue suspended in water and the pH adjusted to pH=2 with aq. HCl (3M). The precipitate was collected by filtration washed with water, suspended in aqueous solution of NaOH (30 mL, 10% w/w) and methanol (50 mL) and left stirring at room temperature overnight. After evaporation of the solvents, the residue was taken in water (30 mL), pH adjusted to pH=2 adding aq. HCl (3M). The precipitate was collected by filtration, washed with water and dried under vacuum to yield the title compound as a white solid (4.1 g, 68%).
[0178] 1 H-NMR (dmso-d6) δ 2.29 (s, 3H), 7.31-7.50 (m, 6H), 7.83 (dd, 1H), 7.89 (s, 1H); (M+1) e/z 213
4-(3-Methyl-[1,2,4]oxadiazol-5-yl)-benzoic acid
a) N-(4-Methoxycarbonylbenzoyl)oxy)acetarnidine
[0179] To a solution of terephthalic acid monomethyl ester (5 g, 27.7 mmol) in dichloromethane (40 mL), CDI (27.7 mmol) was added. After 10 minutes stirring, N-hydroxy-acetamidine (27.7 mmol) was added and the resulting mixture stirred at room temperature for 3 hours. The solution was filtered and evaporated under reduced pressure to yield the title compound as a white solid (4.9 g, 75%).
[0180] (M+1) e/z 237
b) 4-(3-Methyl-[1,2,4]oxadiazol-5-yl)-benzoic acid
[0181] A mixture of N-(4-methoxycarbonylbenzoyl)oxy)acetamidine (4.9 g, 20.7 mmol) and sodium acetate (20.7 mmol) in methanol (70 mL) and water (20 mL) was heated to 90° C. for 8 hours. After cooling a solid crystallised out of solution. The solid was filtered out, suspended in aq. NaOH solution (10% w/w, 30 mL) and methanol (30 mL) and left stirring at room temperature overnight. The solution was then evaporated under reduced pressure, the pH adjusted to pH=3 adding aq. HCl (6M). A precipitated formed, which was collected by filtration, washed with water, diethyl ether and dried under vacuum to yield the title compound as a white solid (2.5 g, 44%).
[0182] 1 H-NMR (dmso-d6) δ 2.44 (s, 3H), 8.17 (m, 4H); (M+1) e/z 205
4-(1H-Tetrazol-5-yl)-benzoic acid
[0183] A mixture of 4-cyano-benzoic acid methyl ester (4.02 g, 25 mmol), sodium azide (32.5 mmol) and triethylamine hydrochloride (32.5 mmol) in toluene (40 mL) is heated at 97° C. for 7 hours. After cooling the solution, water (100 mL) was added. The aqueous phase was separated and to this solution HCl conc (7 g) was added. A precipitate formed which was isolated by filtration and washed with water. The obtained solid was suspended in aq. NaOH solution (20 mL, 10% w/w) and methanol (20 mL) and left stirring at room temperature for 2 hours. The solvent was then evaporated, water was added to the residue and the pH acidified with HCl (6M). A white precipitate formed which was isolated by filtration, washed with water and dried under vacuum to give the title compound (4.5 g, 95%).
[0184] 1 H-NMR (dmso-d6) δ 8.09-8.17 (m, 4H); (M+1) e/z 191
4-(5-Methyl-[1,2,4]oxadiazol-3-yl)-benzoic acid
[0185] To a solution of 4-(N-hydroxycarbamimidoyl)-benzoic acid methyl ester (3.88 g, 20 mmol) in dichloromethane (20 mL), acetic anhydride (40 mmol) was added. The mixture was left stirring at room temperature overnight. After 16 hours the solvent was evaporated, pyridine (30 mL) was added and the reaction mixture heated at 95° C. for 2 days. After cooling the solution a solid crystallised out of solution. To this solution, water (20 mL) was added and after 2 hours stirring at room temperature it was filtered and the solid collected. The solid was suspended in aq. NaOH (30 mL, 10% w/w) and methanol (50 mL) and left stirring at room temperature overnight. After evaporation of the solvents, the residue was taken in water (30 mL), pH adjusted to pH=2 adding aq. HCl (3M). A precipitate formed which was collected by filtration, washed with water and dried under vacuum to yield the title compound as a white solid (3.8 g, 93%). (M+1) e/z 205.
[0186] General Procedure for the Synthesis of Biaryl-Carboxylic Acid Chlorides
[0187] The biarylcarboxylic acids (0.00057 mol) were treated with 5 mL of SOCl 2 for 5 h under reflux. The excess of SOCl 2 was removed by distillation and the crude acid chloride was used in the next reaction without further purification.
[0188] General Procedure for Acid—Amine Coupling Method using Acid Chlorides
[0189] A mixture of (4-aryl-piperazin-1-yl)-alkylamine (0.3 mmol), biarylcarboxylic acid chloride (0.3 mmol), triethylamine (0.56 mmol) and a catalytic amount of DMAP in CH 2 Cl 2 was stirred at 0° C. for 10 min then at room temperature for 4 h.
[0190] The CH 2 Cl 2 layer was washed with water, dried and concentrated. The residue purified by chromatography on silica gel with CHCl 3 /MeOH 95/5 as eluent to give the title compound.
[0191] General Procedure for Acid—Amine Coupling Method using Carbodiimide
[0192] A solution of (4-aryl-piperazin-1-yl)-alkylamine (0.00014 mol) in 5 mL of dry CH 2 Cl 2 was cooled to 0° C. The carboxylic acid (0.0002 mol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (0.0002 mol) and a catalytic amount of DMAP were added and the reaction mixture was stirred at room temperature for 16 h.
[0193] The CH 2 Cl 2 layer was then washed with water, dried and concentrated in vacuo and the residue purified by chromatography eluting with a gradient CHCl3/MeOH 99:1 to 95:5.
[0194] General Procedure for Acid—Amine Coupling Method using N,N′-carbonyldiimidazole (CDI)
[0195] To the preweighed acid (0.55 mmol), dimethylformamide was added (2 mL) to dissolve, followed by N,N′-carbonyldiimidazole (CDI) (0.55 mmol). The solution was then left for 60 minutes before adding the amine (0.6 mmol) and the reaction was stirred for a further 16 hours. The solvent was removed under reduced pressure and the crude mixture was treated with 5% MeOH in dichloromethane (2 mL) and washed with 10% sodium hydroxide solution (2 mL). This mixture was passed through a column packed with 5 grams of diatomaceous earth and the eluting the product with dichloromethane. The collected organic layer, containing the desired compound, was further purified using flash chromatography eluting with 10% MeOH in dichloromethane. Fractions containing the product were combined and the solvent removed under reduced pressure.
[0196] For less reactive carboxylic acids, activation was accomplished by heating the reaction at 60° C. for 2 h before adding the amine (1 eq) (1M solution in dimethylformamide) to the reaction mixture upon cooling; the reaction is then shaken at room temperature for 18-24 h.
[0197] Alternatively, to a solution of carboxylic acid (0.3 mmol) and CDI (0.3 mmol) in acetonitrile (3 mL), the amine (0.3 mmol) was added after 10 minutes. The reaction mixture was exposed to microwave irradiation for 10 minutes at 100° C. After cooling the reaction mixture was absorbed on a SCX cartridge, eluted with dichloromethane, methanol and methanol/ammonia solution. After evaporation, the residue was purified by silica column eluting with a gradient ethyl acetate/cyclohexane (1:1)ethyl acetate→ethyl acetate/methanol (9:1). The fractions containing the product were combined and the solvent evaporated.
[0198] General Procedure for Coupling of 4-oxo-butyl-benzamides via Reductive Alkylation
a) 4-bromo-N-(4-hydroxybutyl)benzamide
[0199] A solution of 4-aminobutan-1-ol (20.71 g, 232 mmol) in dichloromethane (50 mL) was added to a stirring solution of 4-bromobenzoyl chloride (51 g, 232 mmol) in dichloromethane (250 mL). Diisopropylethylamine (40.4 mL, 232 mmol) was added and the colourless solution was stirred at room temperature. LC/MS indicated completion of the reaction after 50 mins. The solution was transferred to a separating funnel and washed with water. A white solid precipitated out which was filtered off and washed with dichloromethane to afford pure product. The filtrate was treated with H 2 O which gave rise to further precipitate. The organic layer was washed with 1M HCl and NaHCO 3 (sat), dried over MgSO 4 , filtered and concentrated in-vacuo to afford a further batch of product (total yield 57.99 g).
[0200] MS (ES) m/z 272/274 (Br)
b) 4-Bromo-N-(4-oxobutyl)-benzamide
[0201] A solution of oxalyl chloride (4.15 mL, 47.6 mmol) in dichloromethane (200 mL) was stirred under a N 2 flow at −60° C. DMSO (6.76 mL, 95.2 mmol) was added cautiously ensuring that the temperature remained below −50° C. After 15 mins a solution of 4-bromo-N-(4-hydroxybutyl)benzamide (10 g, 36.6 mmol) in a mixture of dichloromethane (20 mL), THF (40 mL) and DMSO (5 mL) was added. After 30 mins the temperature had risen to −50° C. After 1 h triethylamine (1.637 g, 16.18 mmol) was added. The mixture was allowed to warm to room temperature and stirred overnight. LC/MS indicated completion of the reaction. H 2 O (200 mL) was added to the reaction mixture. The organic layer was washed with 1M HCl, NaHCO 3 (sat) and brine, dried over MgSO 4 , filtered and concentrated in-vacuo to afford an orange oil (9.93 g).
[0202] MS (ES) m/z 270/272 (Br); 252/254 (Br)
a) 3-Bromo-N-(4-hydroxybutyl)benzamide
[0203] A solution of 4-aminobutan-1-ol (20.3 g, 228 mmol) in dichloromethane (50 mL) was added to a stirring solution of 3-bromobenzoyl chloride (50 g, 228 mmol) in dichloromethane (250 mL). DIPEA (39.6 mL, 228 mmol) was added and the colourless solution was stirred at room temperature. LC/MS indicated completion of the reaction after 50 mins. The solution was transferred to a separating funnel and washed with water. A white solid precipitated out which was filtered off and washed with dichloromethane to afford pure product. The filtrate was treated with H 2 O which gave rise to further precipitate. The organic layer was washed with 1M HCl and NaHCO 3 (sat), dried over MgSO 4 , filtered and concentrated in-vacuo to afford a further batch of product (total yield 46.82 g, 76%, 97% pure by LC/MS).
[0204] Rt=1.09; MS (ES) m/z 272/274 (Br)
b) 3-Bromo-N-(4-oxo-butyl)-benzamide
[0205] A solution of oxalyl chloride (20.85 mL, 239 mmol) in dichloromethane (900 mL) was stirred under a N2 flow at −60° C. DMSO (33.9 mL, 478 mmol) was added cautiously ensuring that the temperature remained below −50° C. After 15 mins a solution of 3-bromo-N-(4-hydroxybutyl)benzamide 1 (50 g, 184 mmol) in a mixture of dichloromethane (100 mL), THF (400 mL) and DMSO (50 mL) was added. After 30 mins the temperature had risen to −50° C. After 1 h triethylamine (96.7 g, 956 mmol) was added. The mixture was allowed to warm to room temperature and stirred overnight. LC/MS indicated completion of the reaction. H 2 O (1 L) was added to the reaction mixture. The organic layer was washed with 1M HCl, NaHCO 3 (sat) and brine, dried over MgSO4, filtered and concentrated in-vacuo to afford an orange oil (9.93 g, >100%, 97% pure by LC/MS).
[0206] Rt=1.18; MS (ES) m/z 252/254, 270/272 (Br)
Reductive alkylation on N-(4-oxo-butyl)benzamides
[0207] To the preweighed amine (1 equivalent), the aldehyde was added dissolved in anhydrous dichloromethane (1.2 eq, dichloromethane). The solution was left to mix for 90 minutes before addition of sodium triacetoxyborohydride (1.5 equivalents). The reaction was left to mix for a further 16 hours. The crude reaction was then washed with saturated NaHCO 3 (2 mL solution/reaction) and the organic layer extracted. The dichloromethane crude solution was passed through an SCX column, eluting the desired product in 20% ammonia in methanol. Fractions containing the compound were combined and the product purified further using HPLC prep.
[0208] General Procedure for Suzuki coupling of N-(4-amino)butyl-3- or 4-bromobenzamides—Exemplified in Detail for N-(4-(4-acetylpiperazin-1-yl)butyl)-4-bromobenzamide and 2-ethylphenylboronic Acid
[0209] N-(4-(4-acetylpiperazin-1-yl)butyl)-4-bromobenzamide (86 mg, 0.225 mmol) was dissolved in DME:EtOH 1:1 (20 mL) and added to a microwave tube containing 2-ethylphenylboronic acid (34 mg, 0.225 mmol). 1M Na 2 CO 3 in H 2 O was added (300 μl, 0.3 mmol) followed by Pd(PPh 3 ) 4 (26 mg, 0.0225 mmol). The tube was capped, shaken by hand and loaded into the microwave for 10 mins at 150° C. The reaction was filtered through celite and washed with MeOH. The filtrate was concentrated in-vacuo and purified by reverse phase preparative HPLC. The product was taken on directly to form the HCl salt: 200 μl 1.25 M HCl in MeOH and 800 μl dichloromethane were added to the title compound and the solution was shaken and concentrated in-vacuo to afford the hydrochloride salt (38.7 mg).
[0210] MS (ES) m/z 408
[0211] General procedures for 5-alkylaminopentanoic Acid arylamides Preparation from 5-bromopentanoyl Chloride
[0212] In dichloromethane at 0° C.-room temperature. A solution of aromatic amine (1 eq) and triethylamine (1 eq) in dichloromethane (0.2 mmol/mL) is cooled at 0° C. under nitrogen atmosphere. 5-Bromopentanoyl chloride (1 eq) in dichloromethane (0.3 mmol/mL) is slowly added and the mixture stirred at room temperature for 1.5 hr. The amine (5 eq) and triethylamine (1 eq) are added at once and the reaction is stirred at room temperature for 40 hrs. The organic solution is then washed with brine, dried and the solvent removed. The product are crystallised by hexane: diethylether 1:1 or purified by flash chromatography.
[0213] Modified room temperature conditions for array synthesis: To a solution of aniline (1 eq) and triethylamine (1 eq) in dichloromethane (2 mL) at room temperature was slowly added 5-bromo-pentanoyl chloride (1 eq) and the mixture stirred for 1.5 hr. The solution was added to a previously prepared vial containing the amine (5 eq) and triethylamine (1 eq) and the reactions were shaken at room temperature for 40 hrs. The organic solution was washed with brine, dried and the solvent removed. The products were purified by flash chromatography or by preparative HPLC.
[0214] In dichloroethane/dimethylformamide at 55° C.: A substituted aromatic amine (1 eq) and triethylamine (1 eq) are weighed in a glass vial and 1,2-dichloroethane is added to give a 1.2 M solution; 5-bromovaleryl chloride (0.95 eq) is then added dropwise as a solution in dimethylformamide (1.2 M) and the reaction is shaken at room temperature for 1 h 30 min. The amine (3 eq) and triethylamine (1 eq) are then added as a solution in DCE (amine concentration 1.8 M) and the reaction mixture shaken at 55° C. for 4 h. After this period, the reaction mixture is cooled and partitioned between water and dichloromethane; the organic layer is washed with sat. NaCl and dried over Na 2 SO 4 . The crude amides obtained after solvent evaporation at reduced pressure are purified by preparative HPLC.
5-(4-Methyl-piperazin-1-yl)-pentanoic acid (4-bromo-phenyl)-amide
[0215] Prepared according the general procedure in dichloromethane at room temperature to give 3.7 g (70%) of the title compound.
[0216] C 16 H 24 N 3 OBr Mass (calculated) [354.29]; found [M+H+]=354/356 (Br),
[0217] Lc Rt=0.58, 93%
[0218] NMR (400 MHz, DMSO): 1.43 (2H, m); 1.55 (2H, m); 2.23 (3H, s); 2.27-2.50 (12H, m); 7.44 (2H, d, J=9 Hz); 7.55 (2H, d, J=9 Hz); 10.05 (1H, s).
[0219] General Suzuki Cross-Coupling Procedure for the Synthesis of Arylamides
[0220] To a degassed mixture of 5-alkylamino-pentanoic acid bromoaryl-amide (0.1 g, 1 eq) and a substituted benzeneboronic acid (1.1 eq) in acetonitrile/sodium carbonate 0.4 M solution 1/1 (4 mL) a catalytic amount of Pd[(PPh 3 )] 4 (5 mmol %) was added. The reaction mixture was heated at 90° C. for 20 minutes under microwave irradiation (150 Watt) and then again other 20 minutes. The organic layer was separated and purified by SCX column. The solvent was removed under reduced pressure to afford the corresponding product.
[0221] General Procedure for Urea Synthesis from Isocyanates
[0222] To a cooled 0.2 M solution of amine (1 eq) in dichloromethane, 1 eq of bromophenylisocyanate was added. The mixture was left stirring at 0° C. and it was stopped when a white solid was formed (1 h), after ca. 1 hour. The product was recovered by filtration as a white solid which was used without further purification.
[0223] General Suzuki Cross-Coupling Procedure for the Synthesis of Ureas Microwave Irradiation
[0224] To a degassed 0.067 M solution of bromide (1 eq, prepared following the procedure for ureas described above) in acetonitrile/water (1/1), the appropriate boronic acid (1 eq) and Na2CO3 (3 eq) were added followed by Pd[(PPh 3 )] 4 (10% mol). The solution was irradiated under microwave conditions, using the following parameters: power=200 watt; ramp time=1 min; hold time=20 min; temp=90° C.; pressure=200 psi. The acetonitrile layer was separated and the crude mixture was purified using a SCX column washing with dichloromethane/MeOH followed by MeOH and then NH3/MeOH to elute the product. The fractions containing the desired product were combined and dried under reduced pressure.
[0225] Thermal Heating
[0226] The urea was weighted (1 eq, prepared following the procedure for ureas described above), placed in a 2-neck flask and dissolved in a degassed solution of acetonitrile/water (4/1, 0.04 M). To this solution boronic acid (1.1 eq), Na 2 CO 3 (3 eq) and Pd[(PPh 3 )] 4 (10% mmol) were added. The mixture was heated at 80° C. and stirred for 20 hours. The solution was filtered on Celite layer and purified using SCX or preparative HPLC.
EXAMPLE 1
N-{4-[4-(2,4-Dimethoxy-phenyl)-piperazin-1-yl]-butyl}-4- (pyridin-2-yl)-benzamide
a) 1-(2,4-dimethoxy-phenyl)-piperazine hydrochloride
[0227] Prepared with a modification of Pascal, J. C.; et al. Eur. J. Med. Chem., 1990, 25, 291-293: a solution of 1.48 g (0.0097 mol) of 2,4-dimethoxyaniline, 1.89 g (0.0160 mol) of bis-2-chloroethylamine hydrochloride and 2.00 g of K 2 CO 3 in 25 mL of 1-butanol was refluxed for 24 h then filtered hot.
[0228] The solvent was removed under reduced pressure and the residue triturated with acetone. The resulting powder was filtered and dried to give 1.25 g of the title compound.
[0229] 1 H-NMR (DMSO-d 6 ) δ (ppm): 9.21 (br s, 1H); 6.82 (d, 1H); 6.52 (s, 1H); 6.42 (d, 1H); 3.74 (s, 3H); 3.68 (s, 3H); 3.12 (s, 4H); 3.07 (s, 4H).
b) 2-{4-[4-(2,4-Dimethoxy-phenyl)-piperazin-1-yl]-butyl}-isoindole-1,3-dione
[0230] Prepared following the general procedure outlined in Nishikawa, Y.; et al; Chem. Pharm. Bull., 1989, 37 (1), 100-105.
[0231] A mixture of N-(4-bromobutyl)phthalimide (0.00135 mol), 1-(2′,4′-dimethoxyphenyl)-piperazine hydrochloride (0.00135 mol), K 2 CO 3 (0.00270 mol), Nal (0.00186 mol) and methylethyl ketone (7 mL) was refluxed for 20 h with stirring. After the mixture had cooled, the insoluble materials were removed by filtration and washed with CHCl 3 The filtrate and the washings were concentrated to dryness in vacuo.
[0232] The residue was purified by cromatography on silica gel with CHCl 3 /MeOH 95/5 as eluent. Yield: 68%.
[0233] 1 H-NMR (CDCl 3 ) δ (ppm): 7.73 (m, 4H); 6.82 (d, 1H); 6.40 (m, 2H); 3.79 (s, 3H), 3.73 (s, 3H), 3.65 (m, 2H); 2.98 (m, 4H); 2.61 (m, 4H); 2.41 (t, 2H); 1.66 (m, 4H).
c) 4-[4-(2,4-Dimethoxy-phenyl)-piperazin-1-yl]-butylamine
[0234] A solution of 2-{4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butyl}-isoindole-1,3-dione (0.000236 mol) and hydrazine hydrate (0.000478 mol) in ethanol (2 mL) was refluxed for 2 h with stirring. After the solution had cooled, any insoluble materials were removed by filtration and washed with EtOH. The filtrate and the washings were concentrated in vacuo to dryness. The residue was taken up with CHCl 3 . The CHCl 3 layer was washed with water, dried and concentrated to give the title amine. Yield: 50%.
[0235] 1 H-NMR (CDCl 3 ) δ (ppm): 6.85 (d, 1H); 6.41 (m, 2H); 3.81 (s, 3H); 3.75 (s, 3H); 3.01 (m, 4H); 2.63 (m, 4H); 2.40 (t, 2H); 1.35 (m, 6H).
d) N-{4-[4-(2,4-Dimethoxy-phenyl)-piperazin-1-yl]-butyl}-4-(pyridin-2-yl)-benzamide
[0236] Prepared by reaction with 4-(pyridin-2-yl)-benzoic acid according to the general procedure (acid chloride method).
[0237] Yield: 35%.
[0238] Mp 154.5-156° C. (free base); 212-216° C. (HCl salt)
[0239] 1 H-NMR (CDCl 3 ) δ (ppm): 8.66 (d, 1H); 8.02 (d, 2H); 7.85 (d, 2H); 7.75 (m, 2H); 7.23 (m, 1H); 6.96 (br s, 1H); 6.76 (d, 1H); 6.42 (d, 1H); 6.36 (dd, 1H); 3.78 (s, 3H); 3.72 (s, 3H); 3.47 (m, 2H); 2.97 (m, 4H); 2.65 (m, 4H); 2.47 (t, 2H); 1.70 (m, 4H)
[0240] Mass (ES) m/z %: 475 (M+1, 100%); 497 (M+Na, 19%)
[0241] HPLC: column Zorbax C8 MeOH 80%/H 2 O 20%, 1.0 mL/min; Rt 6.54; area=99%
EXAMPLE 2
Biphenyl-4-carboxylic acid (4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butyl}-amide
[0242] Prepared from 4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butylamine and 4-biphenylcarboxylic acid following the general procedure (acid chloride method).
[0243] Yield: 35%
[0244] 1 H-NMR (CDCl 3 ) δ (ppm): 7.82 (d, 2H); 7.5-7.6 (m, 4H); 7.48-7.5 (m, 3H); 6.89 (br s, 1H); 6.77 (d, 1H); 6.45 (d, 1H); 6.34 (dd, 1H); 3.80 (s, 3H); 3.73 (s, 3H); 3.49 (m, 2H); 2.96 (m, 4H); 2.64 (m, 4H); 2.45 (t, 2H); 1.68 (m, 4H).
[0245] Mass (ES) m/z %: 474 (M+1, 100%); 496 (M+Na, 6%).
[0246] HPLC: column: Zorbax CN AcCN 40%/H 2 O (CF 3 COOH pH=2.3) 60%, 0.8 mL/min; Rt=5.396; Area 98%
EXAMPLE 3
2′-Nitro-biphenyl-4-carboxylic acid (4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butyl}-amide
[0247] Prepared from 4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butylamine and 2′-nitrobiphenyl-4-carboxylic acid following the general procedure (acid chloride method).
[0248] Yield: 17%
[0249] 1 H-NMR (CDCl 3 ) δ (ppm): 7.7-7.9 (m, 3H); 7.45-7.55 (m, 2H); 7.3-7.4 (m, 3H); 6.84 (br s, 1H); 6.80 (d, 1H); 6.44 (d, 1H); 6.37 (dd, 1H); 3.80 (s, 3H); 3.74 (s, 3H); 3.49 (m, 2H); 2.97 (m, 4H); 2.63 (m, 4H); 2.46 (t, 2H); 1.68 (m, 4H)
[0250] Mass (ES) m/z %: 519 (M+1, 100%); 541 (M+Na, 11%)
[0251] HPLC: column Zorbax CN MeOH 50%/H 2 O (CF 3 COOH pH=2) 50%, 0.4 mL/min; Rt=17.209; Area 88%
EXAMPLE 4
2′-Fluoro-biphenyl-4-carboxylic acid (4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butyl}-amide
[0252] Prepared from 4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butylamine and 2′-fluorobiphenyl-4-carboxylic acid following the general procedure (acid chloride method).
[0253] Yield: 20%
[0254] Mp=124-125.5° C.
[0255] R t (CHCl 3 /MeOH 95/5) 0.21
[0256] 1 H-NMR (CDCl 3 ) δ (ppm): 7.81 (d, 2H); 7.56 (d, 2H); 7.1-7.4 (m, 4H); 6.99 (s br, 1H); 6.76 (d, 1H); 6.43 (d, 1H); 6.33 (dd, 1H); 3.78 (s, 3H); 3.71 (s, 3H); 3.46 (m, 2H); 2.94 (m, 4H); 2.60 (m, 4H); 2.44 (t, 2H); 1.66 (m, 4H)
[0257] Mass (ES) m/z %: 492 (M+1, 100%);
[0258] HPLC: column Zorbax CN AcCN 50%/H 2 O (CF 3 COOH pH=2,3) 50%, 0.4 mL/min; Rt=13.525; Area 96%
EXAMPLE 5
2′-Methyl-biphenyl-4-carboxylic acid (4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butyl}-amide
[0259] Prepared from 4-[4-(2,4-dimethoxy-phenyl)-piperazin-1-yl]-butylamine and 2′-methylbiphenyl-4-carboxylic acid following the general procedure (acid chloride method).
[0260] Yield: 21%
[0261] 1 H-NMR (CDCl 3 ) δ (ppm): 7.80 (d, 2H); 7.35 (d, 2H); 7.2-7.4 (m, 4H); 6.88 (br s, 1H); 6.79 (d, 1H); 6.46 (d, 1H); 6.36 (m, 1H); 3.82 (s, 3H); 3.76 (s, 3H); 3.50 (m, 2H); 2.98 (m, 4H); 2.66 (m, 4H); 2.47 (m, 2H); 2.25 (s, 3H); 1.70 (m, 4H)
[0262] Mass (ES) m/z %: 488 (M+1, 100%)
[0263] HPLC: column Zorbax C8 AcCN 40%/H 2 O (CF 3 COOH pH=2.3) 60%, 1.0 mL/min; Rt=11.748; Area 96%
EXAMPLE 6
N-{4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butyl}-4-(pyridin-2-yl)-benzamide
a) 2-{4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butyl}-isoindole-1,3-dione
[0264] Prepared According to the General Procedure
[0265] Yield: 80%
[0266] 1H-NMR (CDCl 3 ) δ (ppm): 7.72 (m, 4H); 6.89 (m, 4H); 3.81 (s, 3H); 3.69 (t, 2H); 3.15 (m, 4H); 2.60 (4H, m); 2.40 (t, 2H); 1.66 (m, 4H).
b) 4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butylamine
[0267] Prepared According to the General Procedure
[0268] Yield: 53%
[0269] 1 H-NMR (CD 3 OD) δ (ppm): 6.90 (m, 4H); 3.83 (s, 3H); 3.05 (m, 4H); 2.79 (t, 2H); 2.66 (4H, m); 2.43 (m, 2H); 1.60 (m, 4H).
[0270] Mass (ES) m/z %: 264 (M+1, 100%).
c) N-{4-[4-(2-Methoxy-phenyl)-piperazin-1-yl]-butyl}-4-(pyridin-2-yl)-benzamide
[0271] Prepared by Reaction with 4-(pyridin-2-yl)-benzoic acid According to the General Procedure—Carbodiimide Method.
[0272] Yield: 41%
[0273] Mp=152.3-154.6° C.
[0274] R t (CHCl 3 /MeOH 95/5)=0.15
[0275] 1 H-NMR (CDCl 3 ) δ (ppm): 8.66 (d, 1H); 8.00 (d, 2H); 7.84 (d, 2H); 7.70 (m, 2H); 7.21 (m, 1H); 6.8-7.0 (m, 5H); 3.80 (s, 3H); 3.44 (m, 2H); 3.03 (m, 4H); 2.62 (m, 4H); 2.43 (m, 2H); 1.65 (m, 4H).
[0276] Mass (ES) m/z %: 445 (M+1, 100%); 467 (M+Na, 78%).
[0277] HPLC: column Zorbax C8 MeOH 80%/H 2 O 20%, 0.8 mL/min; Rt=4.72; area: 99.9%.
EXAMPLE 7
1H-Indole-6-carboxylic acid (4-[4-(2,4-difluoro-phenyl)-piperazin-1-yl]-butyl}-amide
[0278] Following the general procedure, 6-indolecarboxylic acid (44 mg, 0.27 mmol) is dissolved in dimethylformamide (1 mL) and 1,1′-carbonyldiimidazole (44 mg, 0.27 mmol) is added. 4-[4-(2,4-Difluoro-phenyl)-piperazin-1-yl]-butylamine (73 mg, 0.27 mmol) dissolved in dimethylformamide (0.25 mL) is then added and the mixture is allowed to react for 18 h. Work-up followed by preparative HPLC affords the title compound (51 mg, 41%, >95% pure) as formate salt.
[0279] C 23 H 26 F 2 N 4 O Mass (calculated) [412.49]; (found) [M+H+]=413
[0280] LC Rt=3.02, 100% (10 min method)
[0281] NMR (400 MHz, CDCl3): 1.51 (4H, m); 2.34 (2H, t); 2.47 (4H, bs); 2.93 (4H, bs); 3.26 (2H, m); 6.49 (1H, s); 6.95-7.01 (2H, m); 7.12-7.17 (1H, m); 7.40 (2H, m); 7.6 (1H, dd, J=8.4, 1.2), 8.09 (1H, s); 8.17 (1H, HCOOH,s); 8.26 (1H, t); 11.27 (1H, s).
EXAMPLE 8
N-(4-Azepan-1-yl-butyl)-4-pyridin-2-yl-benzamide
a) N-(4-Hydroxy-butyl)-4-pyridin-2-yl-benzamide
[0282] CDI (4.07 g, 25 mmol) was added to a solution of 4-pyridin-2-yl-benzoic acid (5.0 g, 25 mmol) in dichloromethane and the reaction mixture stirred for 4 hours. 4-aminobutanol (3.0 mL, 30 mmol) was added and the reaction mixture stirred for 4 hours after which the solution was washed with a saturated solution of Na 2 CO 3 . The organic layer was separated, dried over MgSO 4 , filtered and the solvent removed under reduced pressure. The product was purified by column chromatography (dichloromethane, dichloromethane/MeOH 1%) to give 2.4 g of the title alcool.
[0283] LC Rt=0.98 min (5 min run)
[0284] (M+1=271)
[0285] 1H NMR (400 MHz, DMSO): 8.71-8.66 (1H,m), 8.53-8.46 (1H, m), 8.78 (2H,d, 8.1 Hz), 8.12 (1H, d, 8.3 Hz), 7.94 (2H, d, 8.1 Hz), 7.92-7.83 (1H, m), 7.46-7.36 (1H, m), 4.38 (1H, t, 6.6 Hz), 3.42 (2H, dd, 6.6 Hz, 12.0 Hz), 3.35-3.25 (2H, m), 1.60-1.42 (4H,m).
b) N-(4-Oxo-butyl)-4-pyridin-2-yl-benzamide
[0286] A solution of oxalyl chloride (42 μL, 0.48 mmol) in dichloromethane (5 mL) was stirred under N 2 at −60° C. DMSO (34 μL, 0.48 mmol) was added followed after 15 mins by a solution of alcohol (100 mg, 0.37 mmol) in dichloromethane (100 mL). After 2 h triethylamine (106 μl, 0.74 mmol) was added. The mixture was then allowed to warm to room temperature and stirred overnight. LC/MS indicated completion of the reaction. The organic layer was washed with a saturated solution of NH 4 Cl, dried over MgSO 4 , filtered and concentrated under reduced pressure to give 100 mg of a white powder (92% pure by LC/MS Rt=0.98, M+1=269) which was used in the next step without further purification.
c) N-(4-Azepan-1-yl-butyl)-4-pyridin-2-yl-benzamide
[0287] Azepane (50 μl, 0.45 mmol) was weighed into a clean glass vial. To this, the crude N-(4-oxo-butyl)-4-pyridin-2-yl-benzamide (100 mg, 0.37 mmol) was added, dissolved in 2 mL of anhydrous dichloromethane. The reaction was left to mix for 90 minutes before addition of sodium triacetoxyborohydride (118 mg, 0.56 mmol), after which it was stirred for 16 hours at room temperature before washing the crude reaction with saturated NaHCO 3 (2 mL solution) and extracting the organic layer. The dichloromethane crude solution was passed through an SCX column, eluting the desired product in 20% ammonia in methanol. Fractions containing the compound were combined and the product purified further using HPLC prep to yield N-(4-Azepan-1-yl-butyl)-4-pyridin-2-yl-benzamide as the formate salt (47 mg, 36% yield).
[0288] 1 H NMR (CDCl 3 ) 8.08 (m, 4H), 7.77 (m, 3H), 7.27 (m, 1H), 3.54 (m, 2H), 3.10 (m, 6H), 1.89 (m, 6H), 1.73 (m, 6H)
EXAMPLE 9
5-Piperidin-1-yl-pentanoic acid (3-chloro-phenyl)-amide
[0289] Following the general procedure in dichloroethane/dimethylformamide at 55° C., 3-chloroaniline (76 mg, 0.6 mmol) and triethylamine (60 mg, 0.6 mmol) are dissolved in dimethylformamide (0.5 mL) and 5-bromovaleryl chloride (113 mg, 0.57 mmol) in dimethylformamide (0.5 mL) is added dropwise. After 1 h 30 min, piperidine (153 mg, 1.8 mmol) and triethylamine (60 mg, 0.6 mmol) in dimethylformamide (0.5 mL) and the reaction mixture heated at +55° C. for 4 h. Wok-up followed by preparative HPLC affords the title compound (118 mg, 67%) as a white solid as formate salt.
[0290] C 16 H 23 C 1 N 2 O Mass (calculated) [294.82]; (found) [M+H+]=295
[0291] LC Rt=1.78, 100% (10 min method)
[0292] NMR (400 MHz, dmso-d6): 1.48 (2H, m); 1.52 (6H, m); 2.31 (2H, t); 2.48 (6H, m); 7.05 (1H, dd, J=8, 1.2); 7.30 (1H, m); 7.41 (1H, dd, J=8.4, 0.8); 7.80 (1H, s); 8.21 (1H, HCOOH,s); 10.1 (1H, bs).
EXAMPLE 10
5-morpholin-4-yl-pentanoic acid (4-bromo-phenyl)-amide
[0293] Prepared according the general procedure in dichloromethane at room temperature to give 6.4 g (93%) of the title compound.
[0294] C 15 H 21 N 2 O 2 Br Mass (calculated) [341.24]; found [M+H+]=341/343 (Br)
[0295] Lc Rt=2.30, 100%
[0296] NMR (400 MHz, DMSO): 1.44 (2H, m); 1.57 (2H, m); 2.29 (8H, m), 3.54 (4H, m), 7.44 (2H, d, J=7 Hz), 7.54 (2H, d, J=7 Hz).
EXAMPLE 11
5-Piperidin-1-yl-pentanoic acid (3-bromo-phenyl)-amide
[0297] Prepared according the general procedure in dichloromethane at room temperature to give 1.7 g (33%) of the title compound.
[0298] C 16 H 23 N 2 OBr Mass (calculated) [339.28]; found [M+H+]=339/341 (Br),
[0299] Lc Rt=1.86, 98%
[0300] NMR (400 MHz, DMSO): 1.51-1.64 (10H, m); 2.34 (2H, m); 2.23 (2H, m); 2.76 (4H, m); 2.97 (2H, m); 7.12-7.264 (2H, m); 7.48 (2H, br d, J=8 Hz); 7.97 (1H, s).
EXAMPLE 12
5-Morpholin-4-yl-pentanoic acid (2′-trifluoromethyl-biphenyl-4-yl)-amide
[0301] Prepared according the general procedure in dichloromethane at room temperature followed by Suzuki coupling to give 0.1 g (92%) of the title compound.
[0302] C 22 H 25 N 2 O 2 F 3 Mass (calculated) [406.44]; (found) [M+H+]=407
[0303] Lc Rt=3.36, 98%
[0304] NMR (400 MHz, DMSO): 1.45 (2H, m); 1.6 (2H, m); 2.3 (8H, m); 3.55 (4H, m); 7.21 (2H, d, J=8.4 Hz); 7.36 (1H, d, J=7.3 Hz); 7.56 (1H, m); 7.63 (2H, d, J=8.4 Hz); 7.68 (1H, m); 7.79 (1H, d, J=7.7 Hz)
EXAMPLE 13
4′-[5-(4-Methyl-piperazin-1-yl)-pentanoylamino]-biphenyl-3-carboxylic acid amide
[0305] Prepared according the general procedure in dichloromethane at room temperature followed by Suzuki coupling to give 0.07 g (63%) of the title compound.
[0306] C 23 H 30 N 4 O 2 Mass (calculated) [394.51]; (found) [M+H+]=395
[0307] Lc Rt=1.06, 100%
[0308] NMR (400 MHz, DMSO): 1.43 (2H, m); 1.58 (2H, m); 2.10 (3H, s); 2.12-2.44 (12H, m); 7.40 (1H, s); 7.49 (1H, m); 7.68 (4H, m); 7.78 (2H, m); 8.06 (1H, s); 8.11 (1H, s); 9.97 (1H, s).
EXAMPLE 14
5-(4-Acetyl-piperazin-1-yl)-pentanoic acid (2′-methoxy-biphenyl-4-yl)-amide
[0309] Prepared according the general procedure in dichloromethane at room temperature followed by Suzuki coupling to give 46 mg (51%) of the title compound.
[0310] C 24 H 31 N 3 O 3 Mass (calculated) [409.53]; (found) [M+H+]=410
[0311] LC Rt=2.21, 100% (10 min method)
[0312] NMR (400 MHz, CD3OD): 1.62 (2H, m); 1.74(2H, m); 2.07 (3H, s); 2.41-2.49 (8H, m); 3.53 (2H, m); 3.58 (2H, m); 3 . 78 (3H, s); 6.98 (1H, m); 7.04 (1H, d, J=8); 7.27 (2H, m); 7.43 (2H, d, J=8.8); 7.56 (2H, d, J=8.8)
EXAMPLE 15
4-Acetyl-1-[4-(2′,3′-difluoro-biphenyl-4-ylcarbamoyl)-butyl]-[1,4]diazepan-1-ium formate
[0313] Prepared according the general procedure in dichloromethane at room temperature followed by Suzuki coupling to give 0.04 g (37%) of the title compound.
[0314] C 24 H 29 N 3 O 2 F 2 HCO 2 H Mass (calculated) [429.51/46.01]; (found) [M+H+]=430.28
[0315] Lc Rt=2.98, 100%
[0316] NMR (400 MHz, DMSO): 1.44 (2H, m); 1.58 (2H, m); 1.66 (1H, m); 1.75 (1H, m); 1.96 (3H, s), 2.32 (2H, m); 2.42 (2H, m); 2.52 (3H, m); 2.62 (1H, m); 3.54 (4H, m), 7.24-7.42 (3H, m); 7.5 (2H, d, J=9 Hz); 7.7 (2H, d, J=9 Hz); 8.16 (1H, s); 10.03 (1H, s)
EXAMPLE 16
5-Piperidin-1-yl-pentanoic acid (3′-hydroxy-biphenyl-3-yl)-amide
[0317] Prepared according the general procedure in dichloromethane at room temperature followed by Suzuki coupling to give 0.06 g (58%) of the title compound.
[0318] C 22 H 28 N 2 O 2 Mass (calculated) [352.47]; (found) [M+H+]=353.32
[0319] Lc Rt=1.90, 99%
[0320] NMR (400 MHz, DMSO): 1.34 (2H, m); 1.40-1.47 (6H, m); 1.57 (2H, m); 2.19-2.33 (8H, m); 6.73 (1H, d, J=8 Hz); 6.95 (1H, s); 6.99 (1H, d, J=7 Hz); 7.23 (2H, m); 7.32 (1H, m); 7.51 (1H, d, J=9 Hz); 7.87 (1H, s); 9.56 (1H, br s); 9.94 (1H, s).
EXAMPLE 17
1-(2′-Chloro-biphenyl-4-yl)-3- (4-morpholin-4-yl-butyl)-urea
[0321] 1-(4-Bromo-phenyl)-3-(4-morpholin-4-yl-butyl)-urea was weighed (0.8 g, 0.22 mmol), placed in 2 necks flask and dissolved in a degassed solution of acetonitrile (4 mL) and water (1 mL). 2-Chloro-phenylboronic acid (0.33 g, 0.24 mmol) and Na2CO3 (0.65 g, 0.6 mmol) and a catalytic amount of Pd[(PPh 3 )] 4 werer then added in sequence and the mixture was heated at 80° C. and stirred for 20 hours. The solution was filtered on Celite layer and purified using preparative HPLC.
[0322] C 21 H 26 C 1 N 3 O 2 Mass (calculated) [387.91]; (found) [M+H+]=388
[0323] Lc Rt: 3.20 (96%)
[0324] NMR (400 MHz, MeOH): 1.56-1.58 (2H, m), 1.71 (2H, m), 2.94-2.98 (2H, m), 3.06-3.22 (4H, m), 3.22-3.25 (2H, m), 3.8 (4H, m), 7.24-7.29 (5H, m), 7.37-7.42 (3H, m), 8.31 (1H, s)
TABLE 1-EXAMPLES 18-254
[0325] Table 1 shows a selection of the compounds synthesised, which were prepared according to the method indicated in the last column of the table and discussed in detail in the Experimental Procedures with the synthesis of Examples 1-17. When the compound is indicated as the HCl salt, the salt was formed by dissolution of the free base in methanol and addition of 1 eq 1M HCl in ether followed by evaporation of the solvents. When the compound is indicated as HCOOH (formic acid) salt, the compound was purified by preparative HPLC.
[0000]
Example
Structure
Salt
Parent Formula
8
HCOOH
C22H29N3O
9
HCOOH
C16H23N2OCl
10
C15H21N2O2Br
11
HCOOH
C16H23N2OBr
12
C22H25N2O2F3
13
C23H30N4O2
14
C24H31N3O3
15
HCOOH
C24H29N3O2F2
16
C22H28N2O2
17
HCOOH
C21H26N3O2Cl
18
HCl
C29H38N4O2
19
HCl
C27H36N3O2Cl
20
HCl
C29H39N3O3
21
HCl
C28H36N3O2F3
22
HCl
C25H35N3O2S
23
HCl
C27H35N3O2F2
24
HCl
C29H42N4O2
25
HCl
C29H41N3O2
26
HCl
C23H29N3O2
27
HCl
C23H28ClN3O2
28
HCl
C23H28N3OF3
29
HCl
C24H33N3O
30
HCl
C22H27N3OF2
31
HCl
C22H28N3OCl
32
HCl
C23H27N2OF3
33
HCl
C22H28N3OCl
34
HCl
C23H30N2O2
35
HCl
C23H27N3O2F2
36
C23H27N3O
37
HCl
C24H32N2O
38
HCl
C28H31F2N3O2
39
HCl
C28H32ClN3O2
40
HCl
C22H26N2OF2
41
HCl
C31H35N5O3
42
HCl
C28H36N4O2
43
HCl
C30H31N5O2
44
HCl
C28H31N5O2
45
HCl
C28H31N2O2Cl
46
HCl
C27H35N3O2F2
47
HCl
C28H32N3O2Cl
48
HCl
C22H27N2OCl
49
HCl
C23H29N3O2
50
HCl
C24H31N3O2
51
HCl
C29H34N4O3
52
HCl
C23H31N3O2
53
HCl
C20H26N2OS
54
HCl
C22H27N2OCl
55
HCl
C22H28N4O2
56
HCl
C22H28N3OCl
57
HCl
C23H28N3O2Cl
58
HCl
C27H32N4O2
59
HCl
C27H36N3O2Cl
60
HCl
C21H27N3O2S
61
HCl
C21H28N4O
62
HCl
C23H31N3O2
63
HCl
C21H27N3O
64
HCl
C21H27N3O
65
HCl
C27H32N4O2
66
HCl
C29H40N4O3
67
HCl
C24H32N4O2
68
HCl
C24H31N3O2
69
HCl
C21H27N3O
70
HCl
C16H23N2OBr
71
HCl
C23H27N3O2F2
72
HCl
C2H26N2OF2
73
HCl
C20H26N2OS
74
HCl
C20H27N3OS
75
HCl
C23H27N3O2F2
76
HCl
C23H29N3O2
77
HCl
C24H31N3O3
78
HCl
C24H31N3O3
79
HCl
C29H34N4O3
80
HCl
C22H27N3OF2
81
HCl
C24H33N3O
82
HCl
C24H32N2O
83
HCl
C22H26N2OF2
84
HCl
C25H32N4O3
85
HCl
C23H28N3O2Cl
86
HCl
C22H27N3OF2
87
HCl
C23H30N2O2
88
C23H30N2O2
89
HCOOH
C25H27N3O
90
HCl
C27H29N3O2
91
HCl
C25H33N3O3
92
HCl
C24H30N3O2Cl
93
C28H34N4O3
94
C29H34N3O3Cl
95
C16H23N2OBr
96
HCOOH
C25H32N4O3
97
HCOOH
C25H32N4O3
98
C15H22N3O2Br
99
C27H33N5O2
100
C29H36N4O3
101
C21H27N3O
102
C16H24N3OBr
103
HCl
C30H37N5O3
104
HCOOH
C28H33N4O2Cl
105
C26H29N5OF2
106
HCOOH
C28H35N5O3
107
C22H28N4O3
108
C22H29N3O3
109
C20H26N4O2
110
C21H25N3O2F2
111
C23H30N4O3
112
C24H32N2O
113
C25H34N2O2
114
C22H28N2O2
115
C23H27N2OF3
116
C22H25N2OF3
117
C21H26N2O2
118
HCOOH
C17H23N3O2
119
C17H23N3O2
120
HCOOH
C17H23N3O2
121
HCOOH
C24H30N4O2
122
C24H30N4O2
123
HCOOH
C23H26N4OF2
124
HCOOH
C23H34N4O2
125
C23H29N3O2
126
C22H27N3O2
127
C21H24N2OF2
128
C21H25N2OCl
129
C22H28N2O2
130
C15H21N2OBr
131
C24H32N2O2
132
C21H24N2OF2
133
C23H30N2O2
134
C24H32N2O3
135
C21H24N2O2F2
136
C21H26N2O3
137
C21H25N2O2Cl
138
C23H29N3O3
139
C20H25N3O2
140
C21H24N2O2F2
141
C22H27N3O3
142
C22H28N2O3
143
C24H31N5O3
144
C23H31N3O2
145
HCOOH
C24H32N4O3
146
C30H38N4O4
147
C23H29N4O2Cl
148
HCl
C22H29N5O2
149
HCl
C31H39N5O4
150
HCl
C24H32N4O2
151
HCl
C25H33N5O3
152
HCOOH
C22H29N3O3
153
HCl
C29H33N5O2F2
154
HCOOH
C20H25N3O
155
HCOOH
C22H28N2O2
156
HCOOH
C17H25N4O2Br
157
C21H33N4O2Br
158
C27H33N5O3
159
C30H34N4O3
160
C31H38N4O4
161
C23H27N3O
162
C28H36N4O2
163
C28H36N4O2
164
C29H40N4O3
165
C24H28N4O2
166
HCOOH
C23H30N2O
167
HCOOH
C22H28N2O3
168
HCOOH
C25H30N3O2F3
169
HCOOH
C26H35N3O2
170
HCOOH
C27H37N3O3
171
HCOOH
C24H31N3O3
172
HCOOH
C24H30N3O2Cl
173
HCOOH
C26H34N4O3
174
HCOOH
C24H29N3O2F2
175
HCOOH
C25H32N4O3
176
HCOOH
C25H33N3O3
177
HCOOH
C25H33N3O3
178
C23H32N4O2
179
HCOOH
C23H32N4O2
180
HCOOH
C22H29N4OCl
181
C24H33N5O2
182
HCOOH
C28H39N5O3
183
HCOOH
C28H40N4O3
184
C28H40N4O3
185
C27H37N4O2Cl
186
HCOOH
C26H37N5O2
187
C29H41N5O3
188
C27H36N4O2F2
189
C22H27N3OF2
190
C23H28N4O2F2
191
HCOOH
C23H31N3O2
192
HCOOH
C22H28N3OCl
193
C18H28N2O
194
C20H32N2O2
195
HCOOH
C23H28N3OF3
196
HCOOH
C24H33N3O
197
HCOOH
C25H35N3O2
198
HCOOH
C22H27N3OF2
199
C22H29N3O2
200
C23H31N3O2
201
C23H27N2OF3
202
C25H34N2O2
203
C22H26N2OF2
204
HCOOH
C23H30N2O2
205
C15H21N2OCl
206
C16H23N2OCl
207
C19H30N2O2
208
C19H30N2O3
209
C17H26N2O2
210
HCOOH
C18H28N2O2
211
HCOOH
C19H30N2O
212
HCOOH
C19H31N3O
213
HCOOH
C20H33N3O
214
HOOH
C18H26N2O3
215
C17H25N2OBr
216
C17H25N2OBr
217
HCOOH
C20H25N3O
218
HCOOH
C20H25N3O2
219
HCOOH
C16H21N2OF3
220
HCOOH
C17H23N2OF3
221
HCOOH
C16H21N2OF3
222
HCOOH
C16H21N2O2F3
223
HCOOH
C17H23N2OF3
224
HCOOH
C15H21N2OBr
225
HCOOH
C15H21N2O2Br
226
HCOOH
C17H23N3O2
227
HCOOH
C18H25N3O
228
HCOOH
C18H23N3O2
229
HCOOH
C19H25N3O
230
HCOOH
C17H23N3O
231
HCOOH
C18H25N3O
232
HCOOH
C20H32N2O
233
HCOOH
C21H33N3O2
234
HCOOH
C17H25N2OCl
235
HCOOH
C18H25N3O2Cl
236
HCOOH
C20H33N3O2
237
HCOOH
C21H33N3O3
238
HCOOH
C21H34N2O2
239
HCOOH
C21H34N4O2
240
HCOOH
C21H34N4O2
241
HCOOH
C21H35N3O
242
HCOOH
C22H36N4O2
243
HCOOH
C19H28N2O3
244
C26H35N3O3
245
C24H28N3O2F3
246
C23H27N3O2F2
247
C23H29N3O3
248
HCOOH
C24H32N2O2
249
HCOOH
C26H36N2O2
250
HCOOH
C24H29N2OF3
251
HCOOH
C23H28N2OF2
252
C23H30N2O2
253
HCOOH
C24H31N3O2
254
HCOOH
C25H33N3O2
LC
Parent
LC purity
method
Example
MW
Mass found
%
LC Rt
(min)
Synthetic Method
8
351.49
352
100
1.79
10
acid-amine coupling
with CDI, room temp.
9
294.82
295
100
1.78
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
10
341.24
341, 343
100
2.3
10
from 5-bromopentanoyl
chloride, 0 0 C.-rt
11
339.27
339, 341
100
1.96
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
12
406.44
407
98
3.36
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
13
394.51
395
100
1.06
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
14
409.52
410
100
2.21
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
15
429.50
430
100
2.98
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
16
352.47
353
99
1.9
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
17
387.90
388
98
3.2
10
urea synthesis followed
by Suzuki under thermal
heating
18
474.64
475
98
1.35
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
19
470.05
470
97
1.34
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
20
477.64
478
94
1.18
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
21
503.60
504
99
1.42
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
22
441.63
442
100
1.29
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
23
471.58
472
98
1.37
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
24
478.56
479
96
1.37
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
25
463.65
464
100
1.46
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
26
379.50
380
100
1.12
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
27
414.00
414, 416
100
1.17
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
28
419.48
420
100
1.22
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
29
379.54
380
100
1.29
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
30
387.47
388
100
1.16
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
31
385.93
386
100
1.2
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
32
404.47
405
92
1.65
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
33
385.93
386
100
1.25
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
34
366.50
367
100
1.55
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
35
415.48
416
100
1.15
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
36
361.48
362
100
2.69
10
acid-amine coupling
with CDI, room temp.
37
364.52
365
100
1.75
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
38
479.60
480
97
1.55
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
39
478.00
478, 480
95
1.55
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
40
372.45
373
98
1.63
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
41
525.64
526
100
1.16
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
42
460.61
461
100
1.24
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
43
493.60
494
100
1.33
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
44
469.58
470
100
1.09
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
45
463.01
462, 464
91
1.1
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
46
472.58
472
91
1.45
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
47
478.03
478
98
1.63
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
48
370.92
370, 372
100
1.8
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
49
379.50
380
100
1.21
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
50
393.52
394
92
2.63
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
51
486.61
487
96
1.23
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
52
381.51
382
100
1.25
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
53
342.50
343
100
1.68
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
54
370.92
370, 372
100
1.79
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
55
380.48
381
93
0.87
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
56
385.93
385, 387
100
1.29
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
57
413.94
413, 415
97
1.24
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
58
444.57
445
99
1.23
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
59
470.05
469, 471
94
1.47
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
60
385.52
386
91
1.15
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
61
352.47
353
100
0.92
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
62
381.51
382
93
1.21
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
63
337.46
338
100
1.3
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
64
337.46
338
99
0.65
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
65
444.57
445
96
1.31
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
66
492.65
493
100
1.11
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
67
408.54
409
100
0.93
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
68
393.52
394
98
1.32
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
69
337.46
338
100
1.35
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
70
339.27
339, 341
100
1.49
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
71
415.48
416
95
1.23
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
72
372.45
373
100
1.74
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
73
342.50
343
100
1.67
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
74
357.51
358
95
1.19
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
75
415.48
416
98
1.22
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
76
379.50
380
99
2.41
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
77
409.52
410
94
1.18
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
78
409.52
410
92
1.19
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
79
486.61
487
96
1.19
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
80
387.47
388
93
1.22
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
81
379.54
380
91
1.4
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
82
364.52
365
100
1.9
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
83
372.45
373
100
1.73
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
84
436.55
437
92
0.98
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
85
413.94
413, 415
98
1.27
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
86
387.47
388
100
1.24
2.5
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
87
366.50
367
100
1.69
2.5
rom 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
88
366.50
367
99
2.42
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
89
385.50
386
94
2.06
10
acid-amine coupling
with CDI, room temp.
90
427.54
428, 485
100
1.29
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
91
423.55
424
100
1.17
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
92
427.97
428, 430
95
1.24
2.5
reductive alkylation on
N-(4-oxo-
butyl)bromobenzamide
followed by Suzuki
coupling
93
474.59
475
98
3.7
10
acid-amine coupling
with CDI, room temp.
94
508.05
508
98
4.31
10
acid-amine coupling
with CDI, room temp.
95
339.27
339, 341
99
2.74
10
from 5-bromopentanoyl
chloride, 0 C.-rt
96
436.55
437
100
2.74
10
acid-amine coupling
with CDI, 60 C.
97
436.55
437
100
2.86
10
acid-amine coupling
with CDI, 60 C.
98
356.26
356/358
100
1.54
10
urea synthesis
99
459.58
460
95
1.21
10
urea synthesis followed
by cross-coupling in
microwave
100
488.62
489
97
2.69
10
urea synthesis followed
by cross-coupling in
microwave
101
337.46
338
100
2.25
10
reductive alkylation of
4-oxobutylbenzamide
102
354.29
356
100
1.73
10
urea synthesis
103
515.65
516
100
2.22
10
urea synthesis followed
by cross-coupling in
microwave
104
493.04
493
93
3.77
10
urea synthesis followed
by cross-coupling in
microwave
105
465.54
466
100
2.39
10
urea synthesis followed
by cross-coupling in
microwave
106
489.61
490
92
2.3
10
urea synthesis followed
by Suzuki under thermal
heating
107
396.48
397
92
2.27
10
urea synthesis followed
by cross-coupling in
microwave
108
383.48
384
98
3.01
10
urea synthesis followed
by cross-coupling in
microwave
109
354.45
355
100
0.58
10
urea synthesis followed
by cross-coupling in
microwave
110
389.44
390
100
3.15
10
urea synthesis followed
by cross-coupling in
microwave
111
410.51
411
90
2.5
10
urea synthesis followed
by cross-coupling in
microwave
112
364.52
365
100
3.63
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
113
394.55
395
100
3.64
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
114
352.47
353.39
98
2.7
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
115
404.47
405
98
3.54
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
116
390.44
391
98
3.48
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
117
338.44
339.35
100
2.65
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
118
301.38
302
98
2.37
10
acid-amine coupling
with CDI, 60 C.
119
301.38
302
99
2.00/2.07
10
acid-amine coupling
with CDI, 60 C.
120
301.38
302
100
1.79
10
acid-amine coupling
with CDI, 60 C.
121
406.52
407
100
2.90
10
acid-amine coupling
with CDI, 60 C.
122
406.52
407
95
2.76
10
acid-amine coupling
with CDI, 60 C.
123
412.48
413
100
2.89
10
acid-amine coupling
with CDI, 60 C.
124
398.54
399
100
2.89
10
acid-amine coupling
with CDI, 60 C.
125
379.50
380
99
1.61
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
126
365.47
366
99
1.37
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
127
358.42
359
97
2.41
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
128
356.89
357
95
2.49
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
129
352.47
353
98
2.25
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
130
325.24
325, 327
99
1.71
10
from 5-bromopentanoyl
chloride, 0 C.-rt
131
380.52
381
98
3.45
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
132
358.42
359
100
3.19
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
133
366.50
367
99
3.39
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
134
396.52
397
99
3.44
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
135
374.42
375
95
3.19
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
136
354.44
355.34
99
2.48
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
137
372.89
373
96
3.2
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
138
395.49
396
97
2.49
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
139
339.43
340
99
double
10
from 5-bromopentanoyl
peak
chloride 0 C.-rt, followed
0.57-
by Suzuki coupling
1.19
140
374.42
375
97
3.14
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
141
381.47
382
95
2.29
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
142
368.47
369
100
3.05
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
143
437.53
438
100
1.95
10
urea synthesis followed
by cross-coupling in
microwave
144
381.51
382
96
2.99
10
urea synthesis followed
by cross-coupling in
microwave
145
424.54
425
92
2.7
10
urea synthesis followed
by cross-coupling in
microwave
146
518.65
519
94
3.33
10
urea synthesis followed
by cross-coupling in
microwave
147
428.95
429
100
2.97
10
urea synthesis followed
by cross-coupling in
microwave
148
395.50
396
95
0.52
10
urea synthesis followed
by cross-coupling in
microwave
149
545.67
546
96
2.87
10
urea synthesis followed
by cross-coupling in
microwave
150
408.54
409
96
2.37
10
urea synthesis followed
by cross-coupling in
microwave
151
451.56
452
92
2.16
10
urea synthesis followed
by cross-coupling in
microwave
152
383.48
384
100
3.05
10
urea synthesis followed
by cross-coupling in
microwave
153
521.60
522
100
3.27
10
urea synthesis followed
by cross-coupling in
microwave
154
323.43
324
99
0.55
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
155
352.47
353
99
2.91
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
156
397.31
399
100
2.39
10
urea synthesis
157
453.42
455
100
2.74
10
urea synthesis
158
475.58
476
96
2.51
10
acid-amine coupling
with CDI, room temp.
159
498.62
499
100
3.18
10
acid-amine coupling
with CDI, room temp.
160
530.66
531, 266
100
2.81
10
acid-amine coupling
with CDI, room temp.
161
361.48
362
100
2.66
10
acid-amine coupling
with CDI, room temp.
162
460.61
461
100
2.84
10
acid-amine coupling
with CDI, room temp.
163
460.61
461
100
2.88
10
acid-amine coupling
with CDI, room temp.
164
492.65
493
100
2.58
10
acid-amine coupling
with CDI, room temp.
165
404.50
405
99
2.35
10
acid-amine coupling
with CDI, room temp.
166
350.50
351
98
3.25
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
167
368.47
369
94
3.01
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
168
461.52
462.3
100
3.07
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
169
421.58
422.33
100
3.23
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
170
451.60
452.35
100
3.14
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
171
409.52
410.31
96
2.19
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
172
427.97
428.25
95
2.98
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
173
450.47
451.31
99
2.2
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
174
429.50
430.3
100
2.89
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
175
436.55
437.32
100
2
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
176
423.55
424.37
99
2.77
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
177
423.55
424.33
100
2.85
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
178
396.53
397
93
2.4
10
urea synthesis followed
by cross-coupling in
microwave
179
396.53
397
100
2.39
10
urea synthesis followed
by cross-coupling in
microwave
180
400.94
401
99
2.54
10
urea synthesis followed
by cross-coupling in
microwave
181
423.55
424
100
1.85
10
urea synthesis followed
by cross-coupling in
microwave
182
493.64
494
100
2.39
10
urea synthesis followed
by cross-coupling in
microwave
183
480.64
481
96
3.05
10
urea synthesis followed
by cross-coupling in
microwave
184
480.64
481
91
3.19
10
urea synthesis followed
by cross-coupling in
microwave
185
485.06
485
96
3.38
10
urea synthesis followed
by cross-coupling in
microwave
186
451.60
452
100
1.64
10
urea synthesis followed
by cross-coupling in
microwave
187
507.67
508
97
2.64
10
urea synthesis followed
by cross-coupling in
microwave
188
486.60
487
95
3.4
10
urea synthesis followed
by cross-coupling in
microwave
189
387.47
388
96
3.08
10
urea synthesis followed
by cross-coupling in
microwave
190
430.49
431
97
2.89
10
urea synthesis followed
by cross-coupling in
microwave
191
381.51
382
98
2.9
10
urea synthesis followed
by cross-coupling in
microwave
192
385.93
386
99
3.08
10
urea synthesis followed
by cross-coupling in
microwave
193
288.43
289
100
2.10
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
194
332.48
333
100
2.35
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
195
419.48
420
100
2.13
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
196
379.54
380
100
2.2
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
197
409.56
410
100
2.18
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
198
387.47
388
100
1.95
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
199
367.48
369.32
100
1.29
10
from 5-bromopentanoyl
468
chloride 0 C.-rt, followed
by Suzuki coupling
200
381.51
382
100
1.83
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
201
404.47
405
97
2.69
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
202
394.55
395
97
2.75
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
203
372.45
373
100
2.49
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
204
366.50
367
100
2.35
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
205
280.79
281
100
1.67
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
206
294.82
295
100
1.78
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
207
318.45
319
100
2.24
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
208
334.45
335
100
2.18
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
209
290.40
291
100
1.27
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
210
304.43
305
100
1.99
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
211
302.45
303
100
2.24
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
212
317.47
318
100
0.38
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
213
331.50
332
100
0.40
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
214
318.41
319
100
1.24
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
215
353.30
353, 355
100
1.97
10
from 5-bromopentanoyl
chloride - array
conditions
216
353.30
353, 355
100
1.95
10
from 5-bromopentanoyl
chloride - array
conditions
217
323.43
324
100
0.85
10
reductive alkylation of
4-oxobutylbenzamide
218
339.43
340
100
0.79
10
reductive alkylation of
4-oxobutylbenzamide
219
314.35
315
100
2.10
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
220
328.37
329
100
1.98
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
221
314.35
315
100
2.18
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
222
330.35
331
100
2.05
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
223
328.37
329
100
2.09
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
224
325.24
325, 327
100
1.83
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
225
341.24
341, 343
100
1.63
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
226
301.38
302
100
double
10
from 5-bromopentanoyl
peak
chloride in DCM/DMF,
0.42/0.69
55 C.
227
299.41
300
95
1.14
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
228
313.39
315
100
0.36
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
229
311.42
312
100
0.38
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
230
285.38
286
97
0.94
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
231
299.41
300
97
1.17
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
232
316.48
317
100
2.26
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
233
359.51
360.44
100
1.82
10
from 5-bromopentanoyl
chloride - array
conditions
234
308.85
309
100
1.81
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
235
351.87
352.32
100
1.28
10
from 5-bromopentanoyl
chloride - array
conditions
236
347.50
348
100
1.44
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
237
375.51
376
100
2.02
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
238
346.51
347
95
2.30
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
239
374.52
375.43
100
0.29
10
from 5-bromopentanoyl
chloride - array
conditions
240
374.52
375.
100
0.29
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
241
345.52
346
100
0.32
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
242
388.55
389.41
100
0.30
10
from 5-bromopentanoyl
chloride - array
conditions
243
332.44
333
100
1.34
10
from 5-bromopentanoyl
chloride in DCM/DMF,
55 C.
244
437.57
438
96
2.55
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
245
447.49
448
98
2.49
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
246
415.48
416
100
2.33
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
247
395.49
396.40
100
1.70
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
248
380.52
381
100
2.54
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
249
408.58
409
100
2.93
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
250
418.50
419
100
2.91
10
from 5-bromopentanoyl
chloride 0 C.-45, followed
by Suzuki soupling
251
386.48
387
100
2.74
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
252
366.50
367.42
100
2.05
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
253
393.52
394
100
1.77
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
254
407.55
408
100
2
10
from 5-bromopentanoyl
chloride 0 C.-rt, followed
by Suzuki coupling
[0326] Biological Activity
[0327] Cloning of alpha7 nicotinic acetylcholine receptor and generation of stable recombinant alpha7 nAChR expressing cell lines
[0328] Full length cDNAs encoding the alpha7 nicotinic acetylcholine receptor were cloned from a rat brain cDNA library using standard molecular biology techniques. Rat GH4C1 cells were then transfected with the rat receptor, cloned and analyzed for functional alpha7 nicotinic receptor expression employing a FLIPR assay to measure changes in intracellular calcium concentrations. Cell clones showing the highest calcium-mediated fluorescence signals upon agonist (nicotine) application were further subcloned and subsequently stained with Texas red-labelled a-bungarotoxin (BgTX) to analyse the level and homogeneity of alpha7 nicotinic acetylcholine receptor expression using confocal microscopy. Three cell lines were then expanded and one characterised pharmacologically (see Table 2 below) prior to its subsequent use for compound screening.
[0000]
TABLE 2
Pharmacological characterisation of alpha7 nAChR stably
expressed in GH4C1 cells using the functional FLIPR assay
Compound
EC 50 [microM]
Acetylcholine
3.05 ± 0.08 (n = 4)
Choline
24.22 ± 8.30 (n = 2)
Cytisine
1.21 ± 0.13 (n = 5)
DMPP
0.98 ± 0.47 (n = 6)
Epibatidine
0.012 ± 0.002 (n = 7)
Nicotine
1.03 ± 0.26 (n = 22)
[0329] Development of a Functional FLIPR Assay for Primary Screening
[0330] A robust functional FLIPR assay (Z′=0.68) employing the stable recombinant GH4C1 cell line was developed to screen the alpha7 nicotinic acetylcholine receptor. The FLIPR system allows the measurements of real time Ca 2+ -concentration changes in living cells using a Ca 2+ sensitive fluorescence dye (such as Fluo4). This instrument enables the screening for agonists and antagonists for alpha 7 nAChR channels stably expressed in GH4C1cells.
[0331] Cell Culture
[0332] GH4C1 cells stably transfected with rat-alpha7-nAChR (see above) were used. These cells are poorly adherent and therefore pretreatment of flasks and plates with poly-D-lysine was carried out. Cells are grown in 150 cm 2 T-flasks, filled with 30 ml of medium at 37° C. and 5% CO 2 .
[0333] Data Analysis
[0334] EC 50 and IC 50 values were calculated using the IDBS XLfit4.1 software package employing a sigmoidal concentration-response (variable slope) equation:
[0000] Y =Bottom+((Top-Bottom)/(1+((EC 50 /X ) ̂ HillSlope))
[0335] Assay Validation
[0336] The functional FLIPR assay was validated with the alpha7 nAChR agonists nicotine, cytisine, DMPP, epibatidine, choline and acetylcholine. Concentration-response curves were obtained in the concentration range from 0.001 to 30 microM. The resulting EC 50 values are listed in Table 2 and the obtained rank order of agonists is in agreement with published data (Quik et al., 1997).
[0337] The assay was further validated with the specific alpha7 nAChR antagonist MLA (methyllycaconitine), which was used in the concentration range between 1 microM to 0.01 nM, together with a competing nicotine concentration of 10 microM. The IC 50 value was calculated as 1.31±0.43 nM in nine independent experiments.
[0338] Development of Functional FLIPR Assays for Selectivity Testing
[0339] Functional FLIPR assays were developed in order to test the selectivity of compounds against the alpha1 (muscular) and alpha3 (ganglionic) nACh receptors and the structurally related 5-HT3 receptor. For determination of activity at alpha1 receptors natively expressed in the rhabdomyosarcoma derived TE 671 cell line an assay employing membrane potential sensitive dyes was used, whereas alpha3 selectivity was determined by a calcium-monitoring assays using the native SH-SY5Y cell line. In order to test selectivity against the 5-HT3 receptor, a recombinant cell line was constructed expressing the human 5-HT3A receptor in HEK 293 cells and a calcium-monitoring FLIPR assay employed.
[0340] Screening of Compounds
[0341] The compounds were tested using the functional FLIPR primary screening assay employing the stable recombinant GH4C1 cell line expressing the alpha7 nAChR. Hits identified were validated further by generation of concentration-response curves. The potency of compounds from Examples 1-254 as measured in the functional FLIPR screening assay was found to range between 10 nM and 30 microM, with the majority showing a potency ranging between 10 nM and 10 microM.
[0342] The best exemplified compounds were also demonstrated to be selective against the alpha1 nACh, alpha3 nACh and 5HT3 receptors.
[0343] Cell based Assay of Neuroprotection
[0344] Neuroprotective activity of selected compounds was analyzed in an established cell-based assay of excitotoxicity induced by NMDA in mixed primary rat cortical neurons as described previously (Stevens et al, 2003). In brief, test compounds were added 24 h before NMDA application. Incubation with NMDA lasted 10 min or 24 h and cell mortality was assessed 24 h after application of the excitotoxic stimulus (see FIG. 1 ). Selected compounds (at concentrations ranging from 0.1 to 10 microM) reduced mortality on average by 50% and in some experiments a maximum of 80% neuroprotection was observed.
[0345] In vivo Neuroprotection Assay
[0346] Neuroprotective activity of compounds was analyzed in an in vivo animal model of cholinergic degeneration induced by quisqualic acid injection in the nucleus basalis of rats. Subchronic treatment i.p. daily, for 7 days, with the compound at a dose of 3 mg/kg resulted in 60% reduction in the degeneration of cholinergic neurons as demonstrated by determination of the number of ChAT-positive neurons (a representative result is shown in FIG. 2 ).
[0347] Cognitive Behaviour
[0348] Cognitive behaviour was studied for selected compounds from example using the passive avoidance (PA) and object recognition (ORT) tests in order to test the capability to reverse scopolamine-induced amnesia in rats. The compounds showed mild to good cognitive improvement of short term-working and episodic memory by inducing significant reversion of scopolamine-induced amnesia in one or both tests (a representative result is shown in FIG. 3 ).
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[0365] 18. Jonnala, R. R., Terry, A. V., Jr., Buccafusco, J. J. (2002) Nicotine increases the expression of high affinity nerve growth factor receptors in both in vitro and in vivo. Life Sci. 70, 1543-1554.
[0366] 19. Bencherif, M., Bane, A. J., Miller, C. H., Dull, G. M., Gatto, G. J. (2000) TC-2559: a novel orally active ligand selective at neuronal acetylcholine receptors. Eur.J.Pharmacol. 409, 45-55 Ref Type: Journal.
[0367] 20. Donnelly-Roberts, D. L., Xue, I. C., Arneric, S. P., Sullivan, J. P. (1996) In vitro neuroprotective properties of the novel cholinergic channel activator (ChCA), ABT-418. Brain Res. 719, 36-44.
[0368] 21 Meyer, E. M., Tay, E. T., Zoltewicz, J. A., Meyers, C., King, M. A., Papke, R. L., De Fiebre, C. M. (1998) Neuroprotective and memory-related actions of novel alpha-7 nicotinic agents with different mixed agonist/antagonist properties. J. Pharmacol.Exp.Ther. 284, 1026-1032.
[0369] 22. Stevens, T. R., Krueger, S. K., Fizsimonds, R. M. and Picciotto, M. R. (2003) Neuroprotection by nicotine in mouse primary cortical cultures involves activation of calcineurin and L-type calcium channel inactivation. J. Neuroscience 23, 10093-10099.
[0370] 23. Wang H, Yu M, Ochani M, Amella C A, Tanovic M, Susarla S, Li J H, Wang H, Yang H, Ulloa L, Al-Abed Y, Czura C J, Tracey K J: Nicotinic acetylcholine receptor alpha7 subunit is an essential regulator of inflammation. Nature 2003, 421:384-388. | The present invention relates to compounds with α7 nAChR agonistic activity, processes for their preparation, pharmaceutical compositions containing the same and the use thereof for the treatment of neurological, psychiatric, cognitive, immunological and inflammatory disorders. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to wheelchairs and more specifically to adjustable wheelchair arm pads. In even more detail, the present invention relates to an apparatus and system for mounting a wheelchair arm pad to the horizontal or vertical tube of a wheelchair armrest that provides adjustability in four dimensions. The mounting apparatus and system of the present invention is also adjustable so as to precisely fit a wide variety of existing wheelchairs.
BACKGROUND OF THE INVENTION
[0002] People using a wheelchair are affected by many conditions including cerebral palsy, quadriplegia, paraplegia, stroke, kyphosis, scoliosis, old age, multiple sclerosis and head injuries, among other debilitating physical conditions. These individuals often suffer from edema (pooling of fluid in areas of poor vascular flow), loss of memory, subluxation of the shoulder, trunk control, limited range of motion, and many safety concerns.
[0003] One of the most common complaints of wheelchair occupants is that of pain that is directly related to their use of a wheelchair. Unfortunately, at least some of the problems faced by wheelchair users are further exacerbated by the failure of current designs of wheelchair armrest pads and armrest pad systems to properly position a wheelchair occupant. An armrest pad that can be adjusted to meet the individual needs of people that have a variety of disabilities is needed.
[0004] For example, some stroke patients need to have an armrest pad adjusted to maintain the correct pressure on the shoulder joint to prevent subluxation of the humeral head, which can lead to irreversible damage and shoulder pain. Stroke patients may need their arm to be in their field of view as a cognitive reminder of its existence, which can help prevent them from hitting their arm on door frames or from falling into the wheels of a wheelchair. Depending on the user's post-stroke stage, whether flaccid or spastic, a properly adjusted armrest will help maintain shoulder integrity and prevent the spine from flexing laterally by compensating for loss of righting muscles.
[0005] Proper arm support also improves shoulder girdle stability. Stability of the shoulder girdle allows for an upright trunk which facilitates an upright and vertical head position. Armrests can help many cerebral palsy patients and others without trunk and head control perform activities of daily living. For example, it is very difficult to maintain one's head in the correct position, as it is a large mass connected with a series of intricate structural and muscular systems. When a person has any type of structural, muscular or nervous system disability, frequently, proper head position is difficult to maintain, which can cause further health problems. Maintaining proper shoulder girdle alignment is the first step to maintaining proper head alignment.
[0006] Proper positioning of an armrest can also help maintain upper extremity range of motion and prevent contracture. Many quadriplegic, paraplegic, and other disabled patients may have limited or no use of their arms and shoulders. An armrest can help prevent contracture, that is, prevent the muscles in the arm and hand from contracting. It is imperative to treat patients at risk of contracture early and to maintain a regimented schedule of therapy. Once the arm is in contracture, it is difficult to restore the arm to a “normal” position.
[0007] An additional problem exists relative to hand position. An open hand position is important for two reasons: hygiene and protection of the hand muscle and tissue. If the hand is permitted to close, it will often overheat and cause other hygiene issues. Additionally, it is difficult for care givers to open and clean a hand in contracture. Further, when the hand is closed tightly, finger nails will often dig into the palm thereby damaging or degrading the muscle and or tissue in the palm. Contracture and an open hand position can be controlled when the arm is properly positioned with an armrest.
[0008] Yet another problem is edema, which is pooling of the fluid in the body, often as a result of surgery or trauma. Elevating the hand above the elbow can help prevent fluid build up. However, effective edema prevention requires elevation of the entire extremity above the heart. Simply elevating the hand provides only temporary protection. In such cases, the fluid will most likely remain in the arm, not the hand, where circulation is typically better.
[0009] An additional problem users face is that of safety. Door frames and other obstacles can pose significant hazards to wheelchair users who are unable to move their arms out of harm's way during wheelchair movement.
[0010] A further problem with current wheelchair armrest systems is the variability between commercially available wheelchairs. In particular, the armrest tubes of the wheelchair, often differ in configuration between wheelchairs. Specifically, in the inventor's experience, the diameter of the wheelchair armrest tubes may vary from between ⅝″ to 1.0″.
[0011] Problems with existing armrests also include excessive stack height between the wheelchair armrest tube and the armrest pad. As the armrest tube height is a fixed distance, increasing that height of the armrest tube by adding a bulky mechanism increases the stack height, which, for smaller users, can raise the armrest beyond a useable range. Additionally, if the armrest hardware elevates the pad, it may push the shoulder girdle out of alignment causing structural asymmetries and potential loss of head and trunk control.
[0012] Another problem with existing armrests is the location of the axis of rotation. The axis of rotation for the elevating and articulating functions should be anatomically correct, that is, variable to accommodate the various users of wheelchairs to prevent unwanted side effects during the treatment process.
[0013] Accordingly, what is required is an arm pad and mounting apparatus that can elevate the hand about the elbow axis, articulate about the humerus axis, slide forward to accommodate varying chest trunk thicknesses, and adjust to accommodate varying chest trunk widths. The arm pad and mounting apparatus should be adjustable while the user is seated and from the outside of the wheelchair, thereby helping to protect the patient by reducing transfers into and out of the wheelchair. Providing for adjustability while the user is seated also expedites the fitting process and allows the therapist to spend more time fine tuning the fit.
[0014] Further requirements include a wheelchair armrest and mounting apparatus that is adaptable to wheelchairs having an armrest tube, having a wide variety of different diameters configurations. There is also a need to provide a wheelchair arm mounting apparatus and system that provides a wide variety of adjustability so that it can fit all shapes and sizes of people. Lastly, such an armrest mounting apparatus must help accommodate patients with a wide variety of disabilities.
SUMMARY OF THE INVENTION
[0015] The claimed invention provides an apparatus and system for mounting a wheelchair armrest that provides a high degree of support and adjustability such that it can be used with wheelchairs from a wide variety of different manufacturers. This adjustability is also beneficial to the occupant of the wheelchair, as the adjustability can provide a wide variety of people with a more custom fit. In order to provide this custom fit, the claimed invention provides for elevation, articulation, depth, and width adjustability.
[0016] The claimed mounting device and system also provides for an effective single point mounting system. Therefore, the mounting device of the present invention provides a high degree of adjustability with respect to the angle that it can be inclined or declined with respect to prior systems. Additionally, use of a single point mounting system is particularly important with wheelchairs having short armrests and other designs as it allows for a single assembly to fit the majority of wheelchair styles.
[0017] The foregoing and other features of the device and system of the present invention will be apparent from the description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is an exploded view of the apparatus for mounting a wheelchair arm pad.
[0019] FIG. 2A is a top plan view of the armrest back clamp.
[0020] FIG. 2B is a side elevational view of the armrest back clamp.
[0021] FIG. 3A is a bottom plan view of the armrest clamp.
[0022] FIG. 3B is a side elevational view of the armrest clamp.
[0023] FIG. 3C is a side and top perspective view of the armrest clamp.
[0024] FIG. 4A is a perspective view showing the inside of the depth adjustment bracket.
[0025] FIG. 4B is an elevational view showing the inside of the depth adjustment bracket.
[0026] FIG. 5A is a side elevational view of the angle adjustment base.
[0027] FIG. 5B is a perspective view of the inside face of the angle adjustment base.
[0028] FIG. 6A is a top and side perspective view of the angle adjustment bracket.
[0029] FIG. 7 is a top and side elevational view of the sliding nut used to attach the depth adjustment bracket to the angle adjustment base.
DETAILED DESCRIPTION
[0030] Now referring to the drawings in detail wherein like reference numerals refer to like elements throughout, FIG. 1 shows an exploded view of the armrest pad 9 and the armrest attachment hardware 1 used to attach the armrest pad 9 to the wheelchair armrest tube 3 .
[0031] As shown in FIG. 1 , the armrest hardware 1 is attached to the wheelchair armrest tube 3 via an armrest clamp back 11 and an armrest clamp 21 . As seen in more detail in FIG. 2 , the armrest back clamp 11 has a radius surface 13 and a pair of apertures 15 through the armrest back clamp 11 on either side of the radius surface 13 .
[0032] The armrest back clamp 11 mates with the armrest clamp 21 which is shown in more detail in FIG. 3 . The armrest clamp 21 has a radius surface 23 that is similar to the radius surface 13 of the armrest clamp 11 . On either side of the radius surface 23 are threaded apertures 25 . Bolts 17 , preferably socket head screws, are inserted through the apertures 13 in the armrest back clamp 11 and into the threaded apertures 25 of the armrest clamp 21 and tightened to clamp the armrest back clamp 11 to the armrest clamp 21 around a wheelchair armrest tube 3 . The armrest hardware 1 can be moved along the armrest tube 3 to obtain a proper fit for the wheelchair occupant.
[0033] Referring again to FIG. 3 , the armrest clamp 21 has a geared face 29 generally opposite the radius surface 23 and a central aperture 27 . The geared face 29 of the armrest clamp 21 is attached to the geared face 49 of the depth adjustment bracket 41 . As seen in FIG. 1 , the geared face 29 of the armrest clamp 21 is attached to the geared face 49 of the depth adjustment bracket 41 using a toggle assembly 51 . The toggle assembly 51 comprises a nut 53 and washer 55 used to secure the geared face 29 of the armrest clamp 21 to the geared face 49 of the depth adjustment bracket 41 by inserting the threaded stud 57 of the toggle assembly 51 through the aperture 47 in the geared face 49 of the depth adjustment bracket 41 and the aperture 27 in the geared face 29 of the armrest clamp 21 . A spring 59 is used to bias the geared face 29 of the armrest clamp 21 away from the geared face 49 of the depth adjustment bracket 41 . The toggle assembly 51 then provides a toggle 63 that, when disengaged, permits the spring 59 to bias the geared face 49 of the depth adjustment bracket 41 away from the geared face 29 of the armrest clamp 21 such that the angle of the depth adjustment bracket 41 can be changed relative to the wheelchair armrest tube 3 , such as when it is desired to elevate the hand of a wheelchair occupant. Engaging the toggle switch 63 operates a cam 65 , as shown in FIG. 1 , in the toggle to effectively secure the depth adjustment bracket 41 to the armrest clamp 21 at the appropriate angle.
[0034] In order to accommodate the various wheelchairs on the market, many of which have varying diameter armrest tubes, the radius surface 13 of the armrest back clamp and the radius surface 23 of the armrest clamp 21 are designed with a “double hump” fixture that permits variance in the size of the wheelchair armrest tube 3 .
[0035] As shown in FIG. 4 , the depth adjustment bracket 41 is provided primarily to accommodate individuals of varying trunk sizes so that the armrest 9 can be positioned precisely for a particular user. As shown in more detail in FIG. 4 , the geared face 49 of the depth adjustment bracket 41 gives way to a depth adjustment section 43 having a depth adjustment slot 45 .
[0036] An angle adjustment base 81 is attached to the depth adjustment bracket 41 via sliding nut 71 . As shown in FIG. 1 , and in more detail in FIG. 7 the sliding nut 71 comprises a longitudinal ridge 73 and a threaded aperture 75 . A bolt 77 is used to secure the angle adjustment base 71 to the sliding nut 71 via an aperture 82 in the angle adjustment base 81 . Other attachment means are possible, but socket head cap screws are preferred. The longitudinal ridge 73 fits within the depth adjustment slot 45 on the depth adjustment bracket 41 .
[0037] As seen in more detail in FIG. 5 , the angle adjustment base 81 further comprises a geared face 83 , the geared face having an aperture 85 therethrough. The geared face 83 of the angle adjustment base 81 interfaces with the geared face 93 of the angle adjustment bracket 91 . As seen in more detail in FIG. 6 , the angle adjustment bracket 91 comprises a geared face 93 , the geared face 93 having an aperture 95 therethrough. The geared face 83 of the angle adjustment base 81 is attached to the geared face 93 of the angle adjustment bracket 91 via a toggle assembly 101 comprising a toggle 103 , a threaded stud 105 attached to the toggle 103 , a washer 107 and a nut 109 . The threaded stud 105 is inserted through the aperture 85 in the angle adjustment base 81 and the aperture 95 in the angle adjustment bracket 91 and secured by the washer 107 and nut 109 . A spring 106 is provided to bias the geared face 83 of the angle adjustment base 81 away from the geared face 93 of the angle adjustment bracket 91 . As such, when the toggle 103 is engaged, it actuates the cam 111 to press the geared faces 83 , 93 of the angle adjustment base 81 and the angle adjustment bracket 91 to secure them together at an appropriate angle. When the toggle 103 is disengaged, the spring 106 separates the geared faces 83 , 93 enough such that angle adjustment of the armrest is possible.
[0038] Users of inventions such as that claimed herein come in a wide range of shapes and sizes and adjustability is a key concern. As seen in FIG. 6 , the angle adjustment bracket 91 provides for adjustment in an additional dimension, that is, trunk width, in the form of width adjustment slots 97 . The arm pad 9 is secured to the width adjustment slots 97 by a pair of bolts, preferably socket head cap screws (not shown), although other attachment means are possible.
[0039] Although I have very specifically described the preferred embodiments of the invention herein, it is to be understood that changes can be made to the improvements disclosed without departing from the scope of the invention. Therefore, it is to be understood that the scope of the invention is not to be overly limited by the specification and the drawings, but is to be determined by the broadest possible interpretation of the claims. | The claimed invention provides an apparatus and system for mounting a wheelchair arm pad to a wheelchair that provides a high degree of support and adjustability such that it can be used with wheelchairs from a wide variety of different manufacturers. In order to provide this custom fit, the claimed invention provides for a single point mounting system having elevation, articulation, depth, and width adjustability. | 0 |
TECHNICAL FIELD OF THE INVENTION
[0001] The present invention is generally related to a temporary shelter device and in particular a temporary shelter that may be erected to protect field equipment from harsh weather conditions.
BACKGROUND OF THE INVENTION
[0002] Temporary shelters are commonly used for outdoor activities, such as camping, trade shows, military field events, etc. Using a temporary shelter provides a quick and inexpensive way to protect persons and goods from natures elements (i.e., sun exposure, rain, snow, excessive heat, cold, etc.). The majority of temporary shelters are used to protect people while they work and/or sleep. However, temporary shelters may also be used to protect equipment from unnecessary weather damage and premature operation failure.
[0003] Different equipment requires different types of temporary shelters. However, unlike a person the equipment may be affixed to the temporary shelter to maintain stability and provide increased protection. Also, equipment may be heavy and must be properly setup prior to entering the temporary shelter.
SUMMARY OF THE INVENTION
[0004] Example embodiments of the present invention provide a temporary shelter structure that may include a structure body that includes a plurality of walls and a plurality of supporting rods providing support for the plurality of walls. The structure body may include a removable entrance portion permitting access to the inside of the structure body and a bottom portion that is contiguous with the ground surface. The structure body may also include a removable portion affixed to the bottom portion, the removable portion occupying a portion of the total surface area of the bottom portion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 illustrates an example of a temporary shelter according to example embodiments of the present invention.
[0006] FIG. 2 illustrates another example of a temporary shelter according to example embodiments of the present invention.
[0007] FIG. 3A illustrates an example of a exterior temperature conditioning vent configuration according to an example embodiment.
[0008] FIG. 3B illustrates another example of a exterior temperature conditioning vent configuration according to another example embodiment.
[0009] FIG. 3C illustrates an example of a interior temperature conditioning vent configuration according to an example embodiment.
[0010] FIG. 4A illustrates a bottom portion of the temporary shelter according to example embodiments.
[0011] FIG. 4B illustrates a removed portion of the temporary shelter corresponding to a bottom portion of the temporary shelter according to example embodiments.
[0012] FIG. 5A illustrates an example removed portion of the temporary shelter with a first securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments.
[0013] FIG. 5B illustrates an example removed portion of the temporary shelter with a second securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments.
[0014] FIG. 5C illustrates an example removed portion of the temporary shelter with a third securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments.
[0015] FIG. 6A illustrates an example removed portion of the temporary shelter corresponding to a bottom portion of the temporary shelter with an example hardware device according to example embodiments.
[0016] FIG. 6B illustrates an example removed portion of the temporary shelter corresponding to a bottom portion of the temporary shelter with an example hardware device according to example embodiments.
[0017] FIG. 7A is a schematic diagram of the bottom portion of a temporary shelter according to example embodiments.
[0018] FIG. 7B is a schematic diagram of the bottom portion of another temporary shelter according to example embodiments.
DETAILED DESCRIPTION
[0019] It will be readily understood that the components of the present invention, as generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of an apparatus, as represented in the attached figures, is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention.
[0020] The features, structures, or characteristics of the invention described throughout this specification may be combined in any suitable manner in one or more embodiments. For example, the usage of the phrases “example embodiments”, “some embodiments”, or other similar language, throughout this specification refers to the fact that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present invention. Thus, appearances of the phrases “example embodiments”, “in some embodiments”, “in other embodiments”, or other similar language, throughout this specification do not necessarily all refer to the same group of embodiments, and the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0021] FIG. 1 illustrates an example of a temporary shelter according to example embodiments of the present invention. Referring to FIG. 1 , the example shelter structure 100 may be an even-sided (i.e., length and width are equivalent or near equivalent) and four-side structure. The wall portion 110 of the structure may be an arc or substantially straight portion of material. The structure material may be any or more of a cloth, plastic, canvas, screen, rubber, poly-plastic, or other suitable and flexible material. The material may also be a radio frequency (RF) permeable material that a radio signal may penetrate without any measurable interference. Alternatively, the top portion of the structure may be an RF permeable material while the bottom portion of the structure is made of a different material.
[0022] In FIG. 1 , an air pocket or air flap 170 may be engaged by loosening an affixing mechanism (i.e., zipper, snap, Velcro®, magnet, etc.). The affixing mechanism of the airflow pocket may be otherwise maintaining the air flow pocket 170 against the surface of the structure material. The airflow pocket may be located at the topmost portion of the structure. Structure supports or rods 120 may be erected by a series of connected shorter rods that are inserted into holding slots to form one large rod 120 . There may be two, four or more rods used to hold the structure up and support the structure against the ground. Additional supporting features may include a series of strings or ropes 140 / 142 used to keep a certain degree of tension against the structure at various locations around the body of the structure. The ropes 140 may be a shorter rope use to support tension from the lower portion of the structure while the longer ropes 142 may be used to support tension from the upper portion of the structure. The ropes may be anchored into the ground to maintain a secure position independent of rain or wind or other external sources of movement and agitation.
[0023] An entrance or removable portion 130 of the structure may be included on one or more sides of the structure 100 to allow a person to unzip, unsnap, undo, etc., the removable portion 130 and enter the structure. There are a plurality of openings 150 which may traverse the entire structure to offer vents or passages for forced air to enter the structure by auxiliary air vents powered by an electronic air handler or air conditioning unit.
[0024] Ground securing flaps 160 may be rolled-up and tucked into the body of the structure and secured by securing coils 162 (elastic rope, snaps, Velcro®, etc.) used to wrap around the securing flap 160 or snap into a button hole on the reverse side of the securing flap 160 . The securing structure rods 120 may have a bottom portion 164 that is anchored into the ground or secured into a corner flap to provide constant tension to the body of the structure 100 .
[0025] FIG. 2 illustrates another example temporary shelter 200 which is larger than the example shelter of FIG. 1 . Referring to FIG. 2 , the large structure 200 includes various elements that are similar to FIG. 1 . For instance, a series of rods may be setup to create one large rod 220 which traverses the exterior surface of the structure and which is secured under a designated area of the structure material. One, two or more large rods 220 may be used to maintain the structure in an upright position. A set of supporting strings or ropes 240 may be used to maintain a certain amount of tension necessary to keep the structure taught and upright.
[0026] The ground securing flaps 260 operate by providing a surface that may be unrolled from the body of the structure and secured to the ground via weights that are added to the surface of the flaps 260 or by one or more stakes that are driven into the ground through a designated portion of the ground securing flaps 260 . The ground securing flaps 260 may be rolled-up and tucked into the body of the structure and secured by securing coils 262 (elastic rope, snaps, Velcro®, etc.) used to wrap around the securing flap 260 or snap into a button hole on the reverse side of the securing flap 260 . The securing structure rods 220 may have a bottom portion 264 that is anchored into the ground or secured into a corner flap to provide constant tension to the body of the structure 100 .
[0027] An entrance or removable portion 230 of the structure may be included on one or more sides of the structure 200 to allow a person to unzip, unsnap, undo, etc., the removable portion 230 and enter the structure. There are a plurality of openings 250 which may traverse the entire structure to offer vents or passages for forced air to enter the structure by auxiliary air vents powered by an electronic air handler or air conditioning unit.
[0028] FIGS. 3A and 3B illustrate examples of exterior access to a ventilation sleeve and hole configuration of the temporary shelter according to example embodiments. Referring to FIG. 3A , an example of a exterior temperature conditioning vent configuration 300 is illustrated as having a vent cover 330 that is lined with a securing mechanism 332 (i.e., Velcro®). However, other securing mechanisms may also be used, such as, buttons, magnets, a zipper, etc. The securing mechanism may also have a receiving side 334 on the surface of the shelter body. Under the vent cover 330 are two different sized ventilation holes and sleeves including the larger hole 310 and the smaller hole 320 . Both holes have a tightening mechanism 336 , such as a drawstring rope that is used to tighten around an external air channel that is introduced into one or more of the ventilation holes. The larger and smaller holes may be used to accommodate different sized air handling configurations depending on the external devices introduced to provide forced warm or cold air into the temporary shelter. Also, one hole may be used to introduce forced air into the shelter while the other hole is used to remove air from the shelter by a fan or suction mechanism.
[0029] FIG. 3B illustrates another example of a exterior temperature conditioning vent configuration according to another example embodiment. Referring to FIG. 3B , an example of a exterior temperature conditioning vent configuration 350 is illustrated as having a vent cover that is lined with a securing mechanism 362 (i.e., Velcro®). However, other securing mechanisms may also be used, such as, buttons, magnets, a zipper, etc. The securing mechanism may also have a receiving side 364 on the surface of the shelter body. Under the vent cover 360 is one ventilation hole and corresponding sleeve 360 . The hole has a tightening mechanism 366 , such as a drawstring rope that is used to tighten around an external air channel that is introduced into one or more of the ventilation holes.
[0030] FIG. 3C illustrates an example of a interior temperature conditioning vent configuration according to an example embodiment. Referring to FIG. 3C , the interior vent configuration 370 is comparable to the inside view of the vent configuration of FIG. 3A . The sleeves may be operated and tightened allowing the user to access the ventilation sleeves inside or outside the shelter. Either sleeve size 372 and/or 382 may be used to allow airflow to enter and/or leave the shelter via external air handling devices. The sleeves may be tightened by corresponding drawstrings 374 and 284 , respectively.
[0031] FIG. 4A illustrates a bottom portion of the temporary shelter according to example embodiments. In this configuration, the bottom portion of the shelter 400 is a circular shaped removable section 410 that corresponds to a removable portion 450 of FIG. 4B . The removable section 460 may be a same or different type of material than the remaining structure 400 . The removable section 460 may be affixed to the shelter structure 400 via a fastening or securing mechanism.
[0032] In operation, upon desiring to setup an hardware device inside the shelter (i.e., mobile communication transceiver, etc.), the removable portion may be removed and set on the ground outside the standing shelter structure. Next, the hardware device may be placed on the removable portion 460 and affixed to the removable portion 460 via a securing mechanism described in detail below. Next, the shelter 400 may be placed on top of the removable portion 460 (as illustrated in FIG. 4B ) and affixed to the larger shelter structure 400 . Additional securing measures may be performed to ensure the stability of the structure and the safety of the hardware device now located inside the structure.
[0033] FIG. 5A illustrates an example removed portion of the temporary shelter with a first securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments. Referring to FIG. 5A , the removable portion 500 of the temporary shelter represents a circular portion of the bottom of the temporary shelter. The removable portion 500 may include a fastening mechanism along the perimeter or circumference of the removable portion 500 . In FIG. 5A , the removable portion 500 includes a zipper 510 along the are of the perimeter. The zipper 520 may be used to secure the removable portion 500 to the bottom of the temporary structure.
[0034] FIG. 5B illustrates an example removed portion of the temporary shelter with a second securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments. Referring to FIG. 5B , the removable portion 520 of the temporary shelter represents a circular portion of the bottom of the temporary shelter. The removable portion 520 may include a fastening mechanism along the perimeter or circumference of the removable portion 520 . In FIG. 5B , the removable portion 520 includes Velcro® 530 along the area of the perimeter. The Velcro® 530 may be used to secure the removable portion 520 to the bottom of the temporary structure.
[0035] FIG. 5C illustrates an example removed portion of the temporary shelter with a third securing mechanism corresponding to a bottom portion of the temporary shelter according to example embodiments. Referring to FIG. 5C , the removable portion 540 of the temporary shelter represents a circular portion of the bottom of the temporary shelter. The removable portion 540 may include a fastening mechanism along the perimeter or circumference of the removable portion 540 . In FIG. 5B , the removable portion 540 includes button snaps 550 along the area of the perimeter. The button snaps 550 may be used to secure the removable portion 540 to the bottom of the temporary structure.
[0036] FIG. 6A illustrates an example removed portion of the temporary shelter corresponding to a bottom portion of the temporary shelter with an example hardware device according to example embodiments. Referring to FIG. 6A , the configuration 600 provides a hardware device 610 , which illustrates an example of field equipment often used by military services deployed in remote locations. The field equipment 610 may be a heavy, fragile, expensive piece of equipment that could utilize shelter from wind, rain and other outdoor conditions to maximize its life span and maintain its proper operating conditions. The removable portion 620 of the shelter structure may be removed and placed outside the structure to provide an opportunity to place the hardware 610 on top of the removable portion 620 .
[0037] FIG. 6B illustrates an example removed portion of the temporary shelter corresponding to a bottom portion of the temporary shelter with an example hardware device according to example embodiments. Referring to FIG. 6B , the hardware device is affixed to the removable portion via a plurality of fastening straps or pockets 664 which provide a stopping force to reduce movement of the legs of the hardware device on the removable portion. A plurality of securing lines may also be used to ensure the hardware device is stabilized inside the shelter 650 . The securing lines 662 may be affixed to wall fasteners 660 that are stitched or glued onto the wall portions of the shelter. The wall fasteners 660 provide an added measure of stability to the hardware inside the structure.
[0038] FIG. 7A is a schematic diagram of the bottom portion of a temporary shelter according to example embodiments. Referring to FIG. 7A , the schematics may correspond to a smaller temporary structure, such as the example in FIG. 1 . The removable portion 710 may be approximately 36-60 inches or in this example 48 inches across in diameter. The bottom portion of the temporary structure 724 may include ground fastening flaps 722 which are approximately 24 inches long and 11 inches wide. The overall length of the side of the bottom portion of the structure 724 may be between 48 and 72 inches.
[0039] FIG. 7B is a schematic diagram of the bottom portion of another temporary shelter according to example embodiments. Referring to FIG. 7B , the schematics may correspond to a larger temporary structure, such as the example in FIG. 2 . The removable portion 760 may be approximately 60-108 inches or in this example 96 inches across in diameter. The bottom portion of the temporary structure 772 may include ground fastening flaps 774 which are approximately 28 inches long and 11 inches wide. The overall length of the side of the bottom portion of the structure 772 may be between 8 and 12 feet.
[0040] It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reading and understanding the above description. Although the present invention has been described with reference to specific exemplary embodiments, it will be recognized that the invention is not limited to the embodiments described, but can be practiced with modification and alteration within the spirit and scope of the appended claims. Accordingly, the specification and drawings are to be regarded in an illustrative sense rather than a restrictive sense. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. | A temporary shelter structure is disclosed which includes a structure body including walls and supporting rods providing support for the walls. The structure also includes a removable entrance portion permitting access to the inside of the structure body and a bottom portion that is contiguous with the ground surface. The bottom portion has a section which is removable. The removable portion is affixed to the bottom portion of the shelter and occupies a portion of the total surface area of the bottom portion. The removable bottom provides a way to place field equipment on the removable portion prior to setting the shelter over the field equipment for protection against the elements of nature. | 4 |
This is a continuation application of copending application Ser. No. 075,848, filed July 20, 1987, which was a continuation of Ser. No. 918,577 filed Oct. 10, 1986, now abandoned, which was a continuation of application Ser. No. 811,956 filed Dec. 20, 1985, now abandoned, which was a continuation of application Ser. No. 719,444 filed Apr. 2, 1985now abandoned, which was a continuation of application Ser. No. 443,134 filed Nov. 19, 1982, now abandoned, which was a divisional of application Ser. No. 383,269 filed May 28, 1982 which issued as U.S. Pat. No. 4,520,468 which was a continuation of Ser. No. 068,526 filed Aug. 21, 1979, now abandoned, which was a continuation-in-part of Ser. No. 857,677 filed Dec. 5, 1977, now abandoned.
FIELD OF THE INVENTION
This invention generally pertains to measurements while drilling a bore hole in the earth and more particularly pertains to systems, apparatus, and methods utilizing hydraulic shock waves in the drilling mud column for transmission of signals representing one or more downhole parameters to the earth's surface. It also pertains to systems and methods for detecting those signals in the presence of interfering noise.
DESCRIPTION OF THE PRIOR ART
This invention relates to data transmission systems for use in transmitting data from the bottom of a well bore to the surface while drilling the well.
It has been long recognized in the oil industry that the obtaining of data from downhole during the drilling of a well would provide valuable information which would be of interest to the drilling operator. Such information as the true weight on the bit, the inclination and the bearing of the borehole, the tool face, fluid pressure, and temperature at the bottom of the hole and the radioactivity of substances surrounding or being encountered by the drill bit would all be expressed by quantities of interest to the drilling operator. A number of prior art proposals to measure these quantities while drilling and to transmit these quantities to the surface of the earth have been made. Various transmission schemes have been proposed in the prior art for so doing. For a description of prior art see for instance U.S. Pat. No. 2,787,795 issued to J. J. Arps, U.S. Pat. No. 2,887,298 issued to H. D. Hampton, U.S. Pat. No. 4,078,620 issued to J. H. Westlake et al., U.S. Pat. No. 4,001,773 issued to A. E. Lamel et al., U.S. Pat. No. 3,964,556 issued to Marvin Gearhart et al., U.S. Pat. No. 3,983,948 issued to J. D. Jeter, and U.S. Pat. No. 3,791,043 issued to M. K. Russell. All of the above listed patents are incorporated in this specification by reference.
Perhaps the most promising of these prior art proposals in a practical sense has been that of signalling by pressure pulses in the drilling fluid. Various methods have been suggested in the prior art to produce such mud pulsations either by a controlled restriction of the mud flow circuit by a flow restricting valve appropriately positioned in the main mud stream or by means of a bypass valve interposed between the inside of the drill string (high pressure side) and the annulus around the drill string (low pressure side).
It has been suggested in the prior art to produce mud pressure pulses by means of valves that would either restrict the mud flow inside the drill string or bypass some flow to the low pressure zone in the annulus around the drill string. Such valves are of necessity slow because when used inside the drill string the valve must control very large mud volumes, and when used to control a by-pass, because of the very high pressure differences, the valve was of necessity also a slow motorized valve. For example, such a motorized valve, interposed between the inside of the drill string and the annulus produced in response to a subsurface measurement slow descreases and slow increases of mud pressure. These were subsequently detected at the surface of the earth.
t c .sup.(v) =OC 1 was the time at which the valve started to close;
t d .sup.(v) =OD 1 was the time at which the valve was fully closed.
The time interval:
T.sub.a.sup.(v) =t.sub.b.sup.(v) -t.sub.a.sup.(v) =t.sub.d.sup.(v) -t.sub.c.sup.(v) ( 2)
T a .sup.(v) will be referred to as the "time of opening or closing of the valve". The time interval
T.sub.b.sup.(v) =t.sub.c.sup.(v) -t.sub.b.sup.(v) ( 3)
T b .sup.(v) will be referred to as the "time of open flow". Thus, the total period of the actuation of the valve was
T.sub.t.sup.(v) =2T.sub.a.sup.(v) +T.sub.b.sup.(v) ( 4)
In the above attempts one had T a .sup.(v) =1 second, T b .sup.(v) =2 seconds and consequently the total time of the actuation of the valve was T t .sup.(v) =4 seconds. These relatively slow openings and closings of the valve produced correspondingly slow decreases and increases of mud pressure at the surface of the earth (see FIG. 1B).
It can be seen that the mud pressure decreased from its normal value of for example, 1000 psi (when the valve was closed) to its lowest value of 750 psi (when the valve was open). The times involved in these observed pressure variations were as follows:
t 1a .sup.(s) =OE 1 was the time at which the mud pressure starts to decrease from its normal level at 1000 psi;
t 1b .sup.(s) =OF 1 was the time at which the mud pressure attained its lowest level at 750 psi and was maintained at this level until time t 1c .sup.(s) =OG 1 ;
t 1c .sup.(s) =OG 1 was the time at which the mud pressure starts to increase;
t 1d .sup.(s) =OH 1 was the time at which the mud pressure attained its normal level at 1000 psi.
Thus, the pressure decreased during the time interval T 1 .sup.(s) =t 1b .sup.(s) -t 1a .sup.(s), then it remained constant during the interval T 2 .sup.(s) =t 1c .sup.(s) -t 1b .sup.(s), and then it rose from its depressed value to the normal level during the time interval T 3 .sup.(s) =t 1d .sup.(s) -t 1c .sup.(s). Thus, the total time of the mud flow through the bypass valve for a single actuation of the valve was
T.sub.t.sup.(s) =T.sub.1.sup.(s) +T.sub.2.sup.(s) +T.sub.3.sup.(s) ( 5)
I have designated quantities in FIG. 1A (such as t a .sup.(v), t b .sup.(v), t c .sup.(v), t d .sup.(v), T a .sup.(v), T b .sup.(v) and T t .sup.(v) with superscript "v" to indicate that these quantities relate to the operation of the valve which is below the surface of the earth. On the other hand the quantities t 1a .sup.(s), t 1b .sup.(s), t 1c .sup.(s), t 1d .sup.(s), T 1 .sup.(s), T 2 .sup.(s). T 3 .sup.(s) and T t .sup.(s) in FIG. 1B are designated with superscript "s" to indicate that these quantities relate to measurements at the surface of the earth. This distinction between the quantities provided with superscript "v" and those with superscript "s" is essential in order to fully understand some of the novel features of my invention. It is essential in this connection to distinguish between the cause and the effect, or in other words, between the phenomena occurring downhole, in the proximity of the valve and those at the detector at the surface of the earth.
The regime of slow pressure variation as suggested in the prior art was not suitable for telemetering in measurement while drilling operations, particularly when several down hole parameters are being measured. By the time a first parameter has been measured, encoded, transmitted to the surface and then decoded, the well bore can have been deepended and the second parameter may no longer be available for measurement. Relatively long time intervals were required for the conversion of the measured data into a form suitable for detection and recording. The entire logging process was lengthy and time consuming. Furthermore various interfering effects such as pulsations due to the mud pump and noise associated with various drilling operations produced additional difficulty. A slow acting motorized valve, such as that suggested in the prior art, is believed to be inadequate to satisfy current commercial requirements.
SUMMARY OF THE INVENTION
Some of the objectives of my invention are accomplished by using hydraulic shock waves for telemetering logging information while drilling is in process. These shock waves are produced by a very rapidly acting (for all practical purposes almost instantaneously acting) bypass valve interposed between the inside of the drill string and the annulus around the drill string. When the bypass valve suddenly opens, the pressure in the immediate vicinity of the valve drops and then returns to normal almost instantaneously and a sharp negative pulse is generated, and conversely, when the bypass valve suddenly closes, a sharp positive pulse is generated. Elasticity of mud column is employed to assist in the generation and transmission of such shock waves. The phenomenon is analogous to the well known water hammer effect previously encountered in hydraulic transmission systems. (See for instance John Parmakian on "Water Hammer Analysis", Prentice Hall, Inc., New York, N.Y. 1955 or V. L. Streeter and E. B. Wylie on "Hydraulic Transients" McGraw-Hill Book Co., New York, N.Y.)
By providing a regime of hydraulic shock waves, I obtained a telemetering system by means of which large amounts of information can be transmitted per unit of time. Such a system is considerably better adapted to satisfy current commercial requirements than the one which is based on the regime of slow variations of pressure.
The valve, in accordance with my invention, is operated by the output of one or more sensors for sensing one or more downhole parameters in the earth's subsurface near the drill bit. One single measurement of each parameter is represented, by a succession of valve wavelets. Each valve wavelet corresponds to a single opening and closing of the valve.
The novel features of my invention are set forth with particularity in the appended claims. The invention both as to its organization and manner of operation with further objectives and advantages thereof, may best be presented by way of illustration and examples of embodiments thereof when taken in conjunction with the accompanying drawings.
FIG. 1 schematically and generally illustrates a well drilling system equipped to simultaneously drill and to make measurements in accordance with some aspects my invention.
FIG. 2 shows schematically a portion of the subsurface equipment including a special telemetry tool in accordance with my invention;
FIG. 3 shows schematically a portion of the arrangement of FIG. 2.
FIG. 4 shows, schematically and more in detail, the electronic processing assembly comprised within the dotted rectangle in FIG. 2.
FIG. 5 shows schematically a power supply including a capacitor charging and discharging arrangement for providing the required power and energy for actuating the valve of the special telemetry tool.
It should be noted that identical reference numerals have been applied to similar elements shown in some of the above figures. In such cases the description and functions of these elements will not be restated in so far as it is unneccessary to explain the operation of these embodiments.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
I. General Description of Apparatus for Data Transmission While Drilling
FIG. 1 illustrates a typical layout of a system embodying the principles of this invention. Numeral 20 indicates a standard oil well drilling derrick with a rotary table 21, a kelly 22, hose 23, and standpipe 24, drill pipe 25, and drill collar 26. A mud pump or pumps 27 and mud pit 28 are connected in a conventional manner and provide drilling mud under pressure to the standpipe. The high pressure mud is pumped down the drill string through the drill pipe 25 and the standard drill collars 26 and then through the special telemetry tool 50 and to the drill bit 31. The drill bit 31 is provided with the usual drilling jet devices shown diagramatically by 33. The diameters of the collars 26 and the telemetry tool 50 have been shown large and out of proportion to those of the drill pipe 25 in order to more clearly illustrate the mechanisms. The drilling mud circulates downwardly through the drill string as shown by the arrows and then upwardly through the annulus between the drill pipe and the wall of the well bore. Upon reaching the surface, the mud is discharged back into the mud pit (by pipes not shown) where cuttings of rock and other well debris are allowed to settle and to be further filtered before the mud is again picked up and recirculated by the mud pump.
Interposed between the bit 33 and the drill collar 26 is the special telemetering transmitter assembly or telemetry tool designated by numeral 50. This special telemetering transmitter assembly 50 includes a housing 250 which contains a valve assembly, or simply a valve 40, an electronic processing assembly 96, and sensors 101. The valve 40 is designed to momentarily by-pass some of the mud from the inside of the drill collar into the annulus 60. Normally (when the valve 40 is closed) the drilling mud must all be driven through the jets 33, and consequently considerable mud pressure (of the order of 2000 to 3000 psi) is present at the standpipe 24. When the valve 40 is opened at the command of a sensor 101 and electronic processing assembly 96, some mud is bypassed, the total resistance to flow is momentarily decreased, and a pressure change can be detected at the standpipe 24. The electronic processing assembly 96 generates a coded sequence of electric pulses representative of the parameter being measured by a selected sensor 101, and corresponding openings and closings of the valve 40 are produced with the consequent corresponding pressure pulses at the standpipe 24.
Numeral 51 designates a pressure transducer that generates electric voltage representative of the pressure changes in the standpipe 24. The signal representative of these pressure changes is processed by electronic assembly 53, which generates signals suitable for recording on recorder 54 or on any other display apparatus. The chart of recorder 54 is driven by a drive representative of the depth of the bit by means well known (not illustrated).
II. General Description of Special Telemetering Transmitter
FIG. 2 shows certain details of the special telemetering transmitter 50. Certain of these and other details have also been described in the above referred to co-pending application Ser. No. 857,677 filed by S. A. Scherbatskoy now abandoned, of which this application is a division of continuation in part. FIG. 2 is diagrammatic in nature. In an actual tool, the housing 250, which contains the valve 40, the electronic processing assembly 96, and the sensors 101, is divided into two sections 250a and 250b. The upper portion 250a (above the dottd line 249) contains the valve assembly 40 and associated mechanisms and, as will be pointed out later in the specification, is of substantially larger diameter than 250b. The lower section 250b (below the dotted line 249) contains the electronic processing assembly 96, sensors 101, and associated mechanisms, and as will be explained later in the specification, has a substantially smaller diameter than the upper section 250a. As shown in FIG. 2, the drilling mud circulates past the special telemetry tool 250a, 250b downwardly (as shown by the arrows 65) through the bit nozzle 33 and then back (as shown by the arrows 66) to the surface in annulus 60 and to the mud pit 28 by pipe means not shown. The valve assembly 40 comprises valve stem 68 and valve seat 69. The valve stem and seat are constructed in such manner that the cross sectional area of the closure A is slightly larger than the cross sectional area B of the compensating piston 70. Thus, when the pressure in chamber 77 is greater than that in the chamber 78, the valve stem 68 is forced downwardly; and the valve 40 tends to close itself more tightly as increased differential pressure is applied.
The fluid (mud) pressure in chamber 77 is at all times substantially equal to the fluid (mud) pressure inside the drill collar, designated as 26 in FIG. 1 and 50 in FIG. 2, because of the opening 77a in the wall of the assembly 250. A fluid filter 77b is interposed in passageway 77a in order to prevent solid particles and debris from entering chamber 77. When the valve 40 is closed, the fluid (mud) pressure in chamber 78 is equal to the fluid (mud) pressure in the annulus 60. When the valve 40 is open and the pumps are running mud flow occurs from chamber 77 to chamber 78 and through orifice 81 to the annulus 60 with corresponding pressure drops.
Double acting electromagnetic solenoid 79 is arranged to open or close valve 40 in response to electric current supplied by electric wire leads 90.
Let P 60 indicate the mud pressure in the annulus 60, P 77 the pressure in chamber 77, and P 78 the pressure in chamber 78. Then, when valve 40 is closed, one has P 78 =P 60 . When the pumps 27 are running and valve 40 is "closed", or nearly closed, and P 77 >P 78 the valve stem 68 is urged towards the valve seat 69. When valve 40 is in the "open" condition (i.e., moved upwardly in the drawing) flow of mud from chamber 77 to the annulus 60 results; and because of the resistance to flow of the orifice 81 (FIG. 2), one has the relationship P 77 P 78 >P 60 . Chambers 83 and 84 are filled with a very low viscosity oil (such as DOW CORNING 200 FLUID, preferably of viscosity 5 centistokes or less) and interconnected by passageway 86. Floating piston 82 causes the pressure P 83 in the oil filled chamber 83 to be equal at all times to P 78 . Thus, at all times P 78 =P 83 = P 84 . Therefore, when the valve 40 is "open", since P 78 =P 84 and P 77 >P 84 , the valve 40 is urged towards the "open" position by a force F=(area B)(P 77-P 84 ). The valve 40 can therefore be termed bistable; i.e., when "open" it tends to remain "open" and when "closed" it tends to remain "closed". Furthermore, when nearly open it tends to travel to the open condition and when nearly closed, it tends to travel to the closed condition. The valve 40 can therefore be "flipped" from one state to the other with relatively little energy. The valve action can be considered the mechanical equivalent of the electric bi-stable flip-flop well known in the electronics art.
FIG. 3 shows the valve 40 in the open condition; whereas, in FIG. 2 it is closed.
Referring again to FIG. 2, numeral 91 indicates an electric "pressure switch" which is electrically conductive when P 77 >P 78 (pump running) and electrically non-conductive when P 77 =P 78 (pumps shut down--not running). Wire 92 running from pressure switch 91 to power supply 93 can, therefore, turn the power on or off. Also, by means of electronic counter 94 and electromagnetic sequence switch 95, any one of the four sensors 101 can be operatively connected to the electronic processing assembly 96 by sequentially stopping and running the mud pumps 27 or by stopping then running the pumps in accordance with a predetermined code that can be interpreted by circuitry in element 94.
III. Description of Electronic Processing Assembly Portion of Special Telemetry Tool
We have described the operation of the bi-stable valve 40 and the sequence switch 95 which makes the selective electrical connection of the various sensors 101 to the electronic processing assembly 96.
For further details of the electronic processing assembly 96 reference is made to FIG. 4, where like numbers refer to like numbers of FIG. 2.
Various types of sensors that generate electric signals indicative of a downhole parameter are well known. Examples are gamma ray sensors, temperature sensors, pressure sensors, gas content sensors, magnetic compasses, strain gauge inclinometers, magnetometers, gyro compasses, and many others. For the illustrative example of FIG. 4, I have chosen a gamma ray sensor such as an ionization chamber or geiger counter or scintillation counter (with appropriate electronic circuitry). All these can be arranged to generate a DC voltage proportional to the gamma ray flux which is intercepted by the sensor.
It is understood that the switching from one type sensor to another as accomplished by switch mechanism 95 of FIG. 2 is well within the state of the art, (electronic switching rather than the mechanical switch shown is preferable in most cases). Consequently, in FIG. 4 for reasons of clarity of description, only a single sensor 101 has been shown. Also, the power supply 93 and mud pressure actuated switch 91 of FIG. 2 are not illustrated in FIG. 5A.
In FIG. 2, the sensor 101 is connected in cascade to A/D convertor 102, processor 103, and power drive 104. The power drive 104 is connected to windings 105 and 106 of the double acting solenoid designated as solenoid 79 in FIG. 2. The power drive 104 may be similar to that shown by FIG. 3E of the parent application. The operation is as follows: the sensor 101 generates an output electric analog signal as represented by the curve 101a shown on the graph immediately above the sensor rectangle 101. The curve shows the sensor output as a function of the depth of the telemetering transmitter 50 in the borehole. The A/D converter converts the analog signal of 101 into digital form by measuring in succession the magnitude of a large number of ordinates of curve 101a and translating each individual ordinate into a binary number represented by a binary word. This process is well known in the art and requires no explanation here. It is important, however, to realize that whereas graph 101a may represent the variation of the signal from the transducer in a matter of hours, the graph 102a represents one single ordinate (for example, AB of the curve 101a). Thus, the time scale of the axis of absissas on graph 102a would be in seconds of time and the whole graph 102a represents one binary 12 bit word, and in actuality represents the decimal number 2649. Thus, each 12 bit word on graph 102a represents a single ordinate such as the ordinate AB on the graph 101a. The usual binary coding involves time pauses between each binary word. After the pause a start up or precursor pulse is transmitted to indicate the beginning of the time interval assigned to the binary word. This precursor pulse is not part of the binary word but serves to indicate that a binary word is about to commense. The binary word is then transmitted which is an indication of the value of an ordinate on graph 101a; then a pause (in time) followed by the next binary word representing the magnitude of the next ordinate, and so on, in quick succession. The continuous curve of graph 101a is thus represented by a series of binary numbers or words each representing a single point on the graph 101a. It is important to understand here that between each binary word there is always a pause in time. This pause (during which no signals are transmitted) is frequently several binary words long, and the pause will be employed for an important purpose which will be explained later in the specification. In order to permit decoding at the surface, the clock No. 1 must be rigorously constant (and in synchronism with 9 corresponding clock located at the surface), and it generates a series of equally timed spaced pulses in a manner well known in the art of electronics.
The graph 103a represents a single bit of the binary word 102a, and the axis of abcissas here again is quite different from the previous graphs. The time on graph 103a is expressed in milliseconds since graph represents only a single bit. Each single bit is translated into two electric pulses each of time duration t x and separated by a time interval t y . Graph 104a is a replica of 103a, which has been very much amplified by the power drive 104. Electric impulse 104b is applied to solenoid winding 105 (which is the valve "open" winding), and electric impulse 104c is applied to solenoid winding 106 (which is the valve "close" winding). The valve 40 of FIG. 2 thus is opened by pulse 104b and closed by pulse 104c and, therefore, the valve 40 remains in the "open" condition for approximately the time t y . The times t x are adjusted to be proper for correct actuation of the solenoid windings and the time t y is proportioned to open the valve 40 for the correct length of time. Both of these times are determined and controlled by the clock ♯2.
In telemetering information from a sensor to the earth's surface, I provide appropriate pauses between transmission of successive binary words. Because of these pauses, it is possible to store in an appropriate electronic memory at the surface equipment the noise caused by the drilling operation alone (without the wavelet). The necessary arrangements and procedures for doing this will be described later in this specification.
IV. Description of Power Supply for Special Telemetering Transmitter
As was pointed out previously, the valve 40 of FIG. 2 must be very fast acting, and to drive it fast requires considerable power. (It has been determined as a result of appropriate testing that such a valve requires about 1/2 to 3/4 horsepower to operate at the necessary speed).
Although this power is very substantial, it is applied only very briefly, and consequently requires only small energy per operation.
In actual operation during tests, it was found that 1/2 horsepower applied for about 40 milliseconds provided the required energy to produce a satisfactory single valve actuation. This energy can be calculated to be about 15 Joules. A battery pack can provide approximately 4 million Joules, without requiring recharge or replacement. The system is therefore capable of generating 130,000 complete valve operations (open plus close). In actuality the energy consumption is less than 15 Joules per operation. The inductance, the Q, and the motional impedance of the solenoid winding cause the current build up to be relatively slow. Thus the total energy per pulse is substantially less than 15 Joules and has been measured at 9 Joules thus providing a capability of 216,000 complete valve actuations. From the above, it can be seen that providing the necessary downhole energy from batteries for a practical telemetry tool is quite feasible. Providing the necessary very large power (1/2 horsepower), however, presents difficult problems.
It was clear that the solution to such a problem would involve the storage of energy in a mechanism that could be caused to release it suddenly (in a short time) and thus provide the necessary short bursts of high power. One such mechanism was "hammer action" which was utilized in the tool disclosed in my co-pending application, but which has been found to be sometimes insufficient. Other mechanisms considered early were the use of compressed air, compressed springs and others. Capacitor energy storage systems required large values of capacitance: The energy stored in a capacitor varies as the first power of the capacitance and as the square of the stored voltage, and since low inductance, fast acting, solenoid drive windings are required, the necessity of low voltage devices becomes apparent, initial calculation indicated that unduly large capacitors would be required.
After further evaluation, it appeared that an operable system might be feasible. By mathematical analysis and by experiments and tests it was determined that a set of optimum circuit parameters would be as follows:
1. Inductance of solenoid winding: 0.1 henrys when in the actuated position and 0.07 henrys when in the non-actuated position (i.e., a tapered armature solenoid).
2. Resistance of solenoid winding: 4.5 ohms.
3. Voltage at which energy is stored: 50 volts.
4. Magnitude of storage capacitor: 10,000 mfd.
5. Currrent capability of drive circuit: 10 amperes.
It was determined that in order to have fast solenoid action, low inductance windings are desirable. It was also determined that current capabilities of electronic drive circuits can be increased well beyond 10 amperes. Low voltage, however, requires unduly large values of capacitance.
Recent advances in so called molten salt batteries have produced energy sources of very good compactness. The same recent technology has also developed capacitors of extraordinarily high values, 10 farads in as little space as 1 cubic inch. These were unacceptable because the required heating to a high temperature (500° C.) which was deemed impractical; and the cost was prohibitive. Consequently, still further efforts were required. Following a thorough and lengthy investigation, finally it was discovered that a tantalum slug capacitor made in accordance with the latest developments would meet the specifications if the other parameters and factors outlined above were optimized to match the characteristics of such capacitors.
From the above it can be seen that at least 216,000 complete valve operations can be realized from one battery charge. Assuming that the telemetry system can provide adequate continuous data by transmitting five pulses per minute, the system is capable of operating continuously in a bore hole for a period of 440 hours. It must be pointed out however that continuous operation is often not necessary. The tool can be used only intermittently on command by the circuitry controlled by switch 91 and elements 94 and 95 of FIG. 2.
There is another parameter to be determined: the proper recharging of the capacitor after discharge. The capacitor can be charged through a resistor connected to the battery, (or other energy source) but this sometimes proved to be slow because as the capacitor became partially charged, the current through the resistor diminished, and at the end of the charge cycle, the charging current approached zero. If the ohmic valve of the resistor is made small, the batteries would be required to carry excessive momentary current because the initial current surge during the charging cycle would exceed the value for maximum battery life. The best method is to charge the capacitor through a constant current device. The capacitor would then be charged at an optimum charging current corresponding to the optimum discharge current for the particular type of battery for maximum energy storage. By correctly determining the charging current, a substantial increase (sometimes a factor of 2 or 3) in the amount of energy that is available from a given battery type can be achieved. Constant current devices are well known and readily available electronic integrated circuits, and are available for a wide range of current values.
FIG. 5 shows schematically a power supply which may be incorporated in the power drive 104 of FIG. 4A including a capacitor charging and discharging arrangement for providing the required power and energy for the windings of solenoid 79. In FIG. 5B, 450 indicates a battery or turbo generator or other source of direct current electric potential, 451 the contant current device, and 452 the capacitor. The capacitor is charged through the constant current device 451 and discharged via lead 453. The lead 454 provides the regular steady power required for the balance of the downhole electronics. | A measurement while drilling apparatus for transmitting information carrying signals by fluid pressure changes in a borehole fluid circulation system having a flow restriction causing a high pressure zone and a low pressure zone, the apparatus having a passageway interconnecting the zones and a solenoid actuated valve interposed in the passageway, a sensor for sensing the magnitude of downhole measurements and for generating a succession of electric voltage changes indicative of the magnitude, a capacitor and a source of electric current for charging the capacitor, a circuit responsive to the sensor electric voltage changes for initiating successive discharges of the capacitor, which discharges are applied to the valve solenoid to produce successive openings and closings of the passageway thereby generating pressure changes in the borehole fluid circulation system. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. § 119(a) from Korean Patent Application No. 10-2008-0069275 filed on Jul. 16, 2008, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present general inventive concept relates to a humanoid robot. More particularly, the present general inventive concept relates to a humanoid robot capable of improving power transmission efficiency and movement displacement by modifying a wrist joint of the humanoid robot.
[0004] 2. Description of the Related Art
[0005] Robots are extensively used in various industrial and domestic fields. As a result, research and development concerning humanoid robots has accelerated in recent years. In order to enable a humanoid robot to perform housework in a manner done by a human hand, for example, a humanoid robot must be able to safely and rapidly grip and handle various objects of varying sizes used by human beings.
[0006] Since the size of a robot hand is limited in a humanoid robot, many motors having large capacity may not be installed for the hand of the humanoid robot. For this reason, the robot hand tends to represent relatively low gripping force as compared with the gripping force of a human hand. In addition, since there are structural limitations in the use of a robot hand, the degree of freedom of movement of the robot hand has been very low as compared with the gripping force of the human hand.
[0007] In order to increase the gripping force of a robot hand, a motor can be installed in an arm part near the forearm, apart from the robot hand, to transfer a driving force of the motor to the fingers using wires. The wires extend by passing through a wrist joint that connects the hand to the forearm part. In order to reduce friction when the wires pass through the wrist joint, the wires are supported by two pulleys.
[0008] However, if the wrist joint is moved, the two pulleys are also moved, so that the length of the wires supported by the two pulleys may be altered. If the length of the wires are changed, the fingers may not be precisely controlled by the wires. Since the movement of the wrist joint exerts an influence upon the length of the wires, the motor driving the wires must be thus controlled in relation to the movement of the wrist joint. As a result, the driving mechanism of the motor for controlling the fingers may be hindered due to the movement of the wrist joint.
[0009] To solve the above problem, there has been suggested a driving mechanism capable of preventing the length of the wire from being changed even if the wrist joint is moved. In such a driving mechanism, the wire passing through the wrist joint, which connects the robot hand to the forearm part, is inserted into a tube, so that the length of the wire can be constantly maintained even if the wrist joint is moved. The tube serves to keep the length of the wire unchanged regardless of the movement of the wrist joint. Since the length of the wire is not changed even if the wrist joint is moved, it is not necessary to control the motor driving the wire to compensate for the length of the wire.
[0010] However, one problem with the above solution is that friction may occur between the tube and the wire inserted into the tube. Such friction may cause a great loss in the driving force of the motor, and this loss may become increased as movement displacement of the wrist joint is increased. If the movement displacement of the wrist joint is increased, the tube is excessively bent so that friction between the wire and the tube is further increased. When this happens, power transmission efficiency of the motor is remarkably lowered. To solve this problem, the movement displacement of the wrist joint must be restricted.
SUMMARY OF THE INVENTION
[0011] The present general inventive concept provides a humanoid robot having a robot hand, capable of improving power transmission efficiency of a motor and ensuring movement displacement of a wrist joint by modifying the structure of the wrist joint serving as a passage for a wire.
[0012] Additional features and/or utilities of the present general inventive concept will be set forth in part in the description which follows and, in part, will be apparent from the description herein, or may be learned by practice of the general inventive concept.
[0013] An embodiment of the present general inventive concept provides a humanoid robot comprising a wrist joint connecting a robot arm to a hand body, a first actuator and a first power transmission device that drive the wrist joint to rotate the hand body relative to the robot arm, finger members comprising finger joints and knuckles, wherein the finger members are connected to the hand body, and a second actuator and a second power transmission device that drive the finger joints to rotate the finger members relative to the hand body, wherein the second power transmission device includes connection members connecting the finger joints to the second actuator, and guide members for guiding the connection members, wherein the guide members include a first guide member coupled with the robot arm and a second guide member coupled with the hand body, and wherein the connection members are alternately wound around the first and second guide members.
[0014] Lengths of the connection members provided between the first and second guide members are constantly maintained even if the second guide member is shifted from the first guide member. The robot arm includes a first contact section making contact with the hand body, the hand body includes a second contact section making contact with the first contact section, and the second contact section is configured to slide on the first contact section. The first power transmission device includes a support member connecting the robot arm to the hand body and a belt for rotating the support member.
[0015] The support member may include a first rotating section rotatably installed in the robot arm and a second rotating section rotatably installed in the hand body. The first guide member is rotatably coupled with the first rotating section and the second guide member is rotatably coupled with the second rotating section.
[0016] The first contact section has a circular shape having a first radius, a second contact section has a circular shape having a second radius, wherein the first radius has the same length as the second radius.
[0017] A ratio of the first radius to the second radius can be identical to a radius ratio of the first guide member to the second guide member when the first radius is different from the second radius.
[0018] The first contact section has a planar shape, and the second contact section has a circular shape having a second radius about the second rotating section. A radius of the second guide member is the same length as the second radius of the second contact section.
[0019] The first power transmission device includes a first rotating section rotatably inserted into the hand body and a belt for moving the first rotating section. The humanoid robot may further include a slot for guiding the first rotating section and a belt support member having a reel that supports the belt to allow the belt to guide the first support member along the slot.
[0020] The hand body includes a pivot shaft rotatably coupled to the robot arm. The first power transmission device includes the pivot shaft and a belt for rotating the pivot shaft. A first reel is fitted around the pivot shaft and a second reel is coupled with the first actuator.
[0021] The robot arm includes a first support member, to which the first guide member is rotatably coupled, and the hand body includes a second support member, to which the second guide member is rotatably coupled. The second support member rotates together with the pivot shaft.
[0022] Portions of the connection members aligned between the first and second guide members are positioned in line with the pivot shaft rotatably coupled to the robot arm.
[0023] Embodiments of the present general inventive concept provide a humanoid robot comprising a robot arm, a hand body connected to the robot arm through a wrist joint, finger members connected to the hand body through finger joints, a first actuator and a first power transmission device that drive the wrist joint to rotate the hand body relative to the robot arm, and a second actuator and a second power transmission device that drive the finger joints to rotate the finger members relative to the hand body, wherein the first power transmission device driving the wrist joint operates independently from the second power transmission device driving the finger joints.
[0024] The second power transmission device includes connection members connecting the second actuator to the finger joints and guide members for guiding the connection members, wherein friction between the connection members and the guide members are constantly maintained when the wrist joint is driven by the first actuator and the first power transmission device. The guide members include a first guide member coupled to the robot arm and a second guide member coupled to the hand body, and the connection members are alternately wound around the first and second guide members. Lengths of the connection members provided between the first and second guide members are constantly maintained even if the second guide member is shifted from the first guide member. The connection members include wires and the guide members include pulleys.
[0025] Embodiments of the present general inventive concept provide a humanoid robot including a robot arm, a hand body connected to the robot arm through a wrist joint, finger members comprising finger joints and knuckles, wherein the finger members are connected to the hand body, a first actuator and a first power transmission device that drive the wrist joint to rotate the hand body relative to the robot arm; and a second actuator and a second power transmission device that drive the finger joints to rotate the finger members relative to the hand body, wherein the second power transmission device includes connection members connecting the second actuator to the finger joints and guide members for guiding the connection members, and wherein the length of the connection members, which connects the actuator to the finger members, can be constantly maintained, so that the finger joints can move with sufficient movement displacement.
[0026] The humanoid robot may also include a support member that connects the hand body to the robot arm, wherein the support member comprises a first rotating section inserted into the robot arm, a second rotating section inserted into the hand body; and a leg section connecting the first rotating section to the second rotation section.
[0027] The humanoid robot may also include a first reel installed at the support member, a second reel installed adjacent the first actuator; and a belt that is wound around the first and second reels, wherein a driving force of the first actuator is transferred to the support member through the belt.
[0028] According to the humanoid robot of the present general inventive concept, connection members are alternately wound around the first and second guide members, so that driving force of the actuator can be efficiently transferred to the finger joints.
[0029] The length of the connection members, which connects the actuator to the finger members, can be constantly maintained, so that the finger joint can move with sufficient moving angle (or movement displacement).
[0030] Further, the humanoid robot according to the present general inventive concept can be used as medical equipment, such as a surgery robot and an endoscope, a probe robot, and a working robot in dangerous fields to transfer power to an end effecter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] These and/or other features and utilities of the present general inventive concept will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
[0032] FIG. 1 is a schematic perspective view showing a joint structure of a humanoid robot according to the present general inventive concept;
[0033] FIG. 2 is a perspective view showing a robot hand and a robot arm according to the present general inventive concept;
[0034] FIG. 3 is a front view showing a robot hand and a robot arm according to the present general inventive concept;
[0035] FIG. 4 is a side sectional view showing a wrist joint of a humanoid robot according to the present general inventive concept;
[0036] FIG. 5 is a side sectional view showing a hand body, which is bent to the right, according to the present general inventive concept;
[0037] FIG. 6 is a side sectional view showing a hand body, which is bent to the left, according to the present general inventive concept;
[0038] FIG. 7 is a perspective view showing a robot hand and a robot arm according to a second embodiment of the present general inventive concept;
[0039] FIG. 8 is a side sectional view showing a robot hand and a robot arm according to a second embodiment of the present general inventive concept;
[0040] FIG. 9 is a side sectional view showing a hand body, which is bent to the right, according to the present general inventive concept;
[0041] FIG. 10 is a side sectional view showing a hand body, which is bent to the left, according to the present general inventive concept;
[0042] FIG. 11 is a perspective view showing a robot hand and a robot arm according to a third embodiment of the present general inventive concept;
[0043] FIG. 12 is a front view showing a wrist joint according to a third embodiment of the present general inventive concept;
[0044] FIG. 13 is a side sectional view showing a wrist joint according to a third embodiment of the present general inventive concept;
[0045] FIG. 14 is a side sectional view showing a hand body, which is bent to the right relative to a robot arm, according to the present general inventive concept; and
[0046] FIG. 15 is a side sectional view showing a hand body, which is bent to the left relative to a robot arm, according to the present general inventive concept.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0047] Reference will now be made in detail to the embodiments of the present general inventive concept, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The embodiments are described below to explain the present general inventive concept by referring to the figures.
[0048] As shown in FIGS. 1 and 2 , a robot arm of the humanoid robot according to an embodiment of the present general inventive concept includes a shoulder joint 1 , an elbow joint 2 and a wrist joint 3 . The shoulder joint 1 includes a first joint 4 rotating about an X axis, a second joint 5 rotating about a Y axis, and a third join 6 rotating about a Z axis. The shoulder joint 1 having the first to third joints 4 to 6 having three degrees of freedom, or the 3-DOF.
[0049] The elbow joint 2 includes a fourth joint 7 rotating about the Y axis. The fourth joint 7 allows the robot arm to be folded. The elbow joint 2 having the fourth joint 7 has one degree of freedom, or 1-DOF.
[0050] The wrist joint 3 includes a fifth joint 8 rotating about the X axis, a sixth joint 9 rotating about the Y axis, and a seventh joint 10 rotating about the Z axis. The wrist joint 3 having the fifth to seventh joints 8 to 10 has the 3-DOF. In particular, the sixth joint 9 rotating about the Y axis and the seventh joint 10 rotating about the Z axis allow a robot hand 12 to be bent relative to a robot arm 11
[0051] As shown in FIGS. 2 and 3 , the humanoid robot according to the present general inventive concept includes the robot arm 11 and the robot hand 12 connected to the robot arm 11 through a wrist joint 15 .
[0052] A hand body 13 is connected to the robot arm 11 by a support member 20 such that the hand body 13 can rotate relative to the robot arm 11 . The support member 20 includes a first rotating section 21 inserted into the robot arm 11 , a second rotating section 22 inserted into the hand body 13 , and a leg section 23 connecting the first rotating section 21 to the second rotating section 22 . In addition, a first reel 24 is installed at the support member 20 and a second reel 26 is installed adjacent a first actuator 27 so that driving force of the first actuator 27 can be transferred to the support member 20 through a belt 25 that is wound around the first and second reels 24 and 26 . Since the first reel 24 that is installed at the support member 20 is positioned on the first rotating section 21 , the support member 20 rotates about the first rotating section 21 . The support member 20 and the belt 25 constitute a first power transmission device to transfer a driving force of the first actuator 27 to the wrist joint 15 .
[0053] The robot hand 12 includes a hand body 13 and finger members 14 connected to the hand body 13 . The finger members 14 include a plurality of finger members and a thumb member, collectively referred to as finger members. Each finger member 14 includes a plurality of knuckles 17 wherein finger joints 16 are provided between the knuckles 17 .
[0054] In operation, if the knuckles 17 are rotated by the finger joints 16 , the finger members 14 can grip articles. The finger members 14 must reliably grip the articles. If the finger members 14 drop the articles due to the lack of gripping force, accident may occur. In order to increase the gripping force of the finger members 14 , an actuator having a large capacity can be installed to provide a great driving force to the finger members 14 . However, if the driving force of the actuator is increased, the size of the actuator is enlarged so that such an actuator is not suitable for the robot hand 12 .
[0055] For this reason, as shown in FIG. 2 , a second actuator 43 is installed in the robot arm 11 and connection members 40 are provided to transfer driving force of the second actuator 43 to the finger joints 16 . The connection members 40 connect the second actuator 43 to the finger members 14 . The connection members 40 include wires and the number of connection members 40 corresponds to the number of finger members 14 .
[0056] In the present embodiment, the finger joints 16 driven by the second actuator 43 can be operated independently from the wrist joint 15 that is driven by the first actuator 27 . In particular, when the robot hand 12 is folded due to the driving of the wrist joint 15 by the first actuator 27 , the length of the connection members 40 , which connects the finger members 14 to the second actuator 43 , must be constantly maintained.
[0057] Guide members 30 are provided in the wrist joint 15 to guide the connection members 40 . The guide members 30 include first guide members 31 rotatably installed on the first rotating section 21 and second guide members 32 rotatably installed on the second rotating section 22 . The number of first and second guide members 31 and 32 correspond to the number of finger members 14 . The first and second guide members 31 and 32 may include pulleys.
[0058] As shown in FIG. 4 , the robot arm 11 and the hand body 13 of the humanoid robot according to the present embodiment are adjacent to each other. The robot arm 11 includes a first contact section 61 , and the hand body 13 includes a second contact section 62 . The first contact section 61 makes slide-contact with the second contact section 62 . The first contact section 61 has a first radius R 1 about the first rotating section 21 , and the second contact section 62 has a second radius R 2 about the second rotating section 22 .
[0059] A radius R 3 of the first guide member 31 and a radius R 4 of the second guide member 32 may vary depending on the first radius R 1 of the first contact section 61 and the second radius R 2 of the second contact section 62 . That is, if the first radius R 1 of the first contact section 61 has the same length as the second radius R 2 of the second contact section 62 , the radius R 3 of the first guide member 31 has the same length as the radius R 4 of the second guide member 32 . In contrast, if the first radius R 1 of the first contact section 61 is different from the second radius R 2 of the second contact section 62 , then the ratio of the first radius R 1 to the second radius R 2 (that is, R 1 /R 2 ) will be equal to the ratio of the radius R 3 of the first guide member 31 to the radius R 4 of the second guide member 32 (that is, R 3 /R 4 )
[0060] A second power transmission device includes the guide members 30 and the connection members 40 that transfer a driving force of the second actuator 43 to the finger joints 16 . The connection members 40 may include first connection members 41 that are used to fold the finger members 14 and second connection members 42 that are used to unfold the finger members 14 . The connection members 40 are alternately wound around the first and second guide members 31 and 32 . That is, the first connection members 41 are alternately wound around a left portion of the first guide member 31 and a right portion of the second guide member 32 . In contrast, the second connection members 42 are alternately wound around a right portion of the first guide member 31 and a left portion of the second guide member 32 . This configuration enables the length of the first and second connection members 41 and 42 , which connect the finger members 14 to the second actuator 43 , can be constantly maintained even if the robot hand 12 is folded due to the driving of the wrist joint 15 . Since the first and second connection members 41 and 42 have the same structure, the following description will be made with reference to the first connection members 41 .
[0061] FIG. 4 shows the hand body 13 before the hand body 13 is bent relative to the robot arm 11 , and FIG. 5 shows the hand body 13 that is bent to the right relative to the robot arm 11 at an angle of 90 degrees. In FIG. 4 , a contact point between the first and second contact sections 61 and 62 will be referred to as a first contact point 63 . In FIG. 5 , a contact point between the first and second contact sections 61 and 62 will be referred to as a second contact point 64 . When the support member 20 (see, FIGS. 2 and 3 ) rotates about the first rotating section 21 , the hand body 13 rotates relative to the robot arm 11 . In this case, the first contact section 61 slides on the second contact section 62 while the contact point between the first and second contact sections 61 and 62 is being shifted from the first contact point 63 of FIG. 4 to the second contact point 64 of FIG. 5 . Thus, the length of the first connection member 41 extending from first guide members 31 to second guide members 32 may not deviate from the distance between the first and second guide members 31 and 32 . Therefore, even if the hand body 13 is bent relative to the robot arm 11 due to the driving of the wrist joint 15 , the length of the first connection member 41 that connects the finger members 14 to the second actuator 43 can be constantly maintained.
[0062] FIG. 6 is a side sectional view showing a hand body, which is bent to the left, according to the present invention. FIG. 6 shows the hand body 13 that is bent to the left relative to the robot arm 11 at an angle of 90 degrees. In FIG. 6 , a contact point between the first and second contact sections 61 and 62 will be referred to as a third contact point 65 . In this configuration, the first contact section 61 slides on the second contact section 62 while the contact point between the first and second contact sections 61 and 62 is being shifted from the first contact point 63 of FIG. 4 to the third contact point 65 of FIG. 6 . At this time, the length of the first connection member 41 between the first and second guide members 31 and 32 may not deviate from the distance between the first and second guide members 31 and 32 . Therefore, as mentioned above, the length of the first connection member 41 that connects the finger members 14 to the second actuator 43 can be constantly maintained even if the hand body 13 is bent relative to the robot arm 11 due to the driving of the wrist joint 15 . In this way, the movement of the wrist joint does not exert an influence upon the length of the wires. Therefore, the finger members are more precisely controlled and the gripping force of the robot hand is improved.
[0063] Referring to FIGS. 4 and 6 , the second actuator 43 and the second power transmission device can operate the finger members 14 independently from the first actuator 27 and the first power transmission device. In addition, since the length of the first connection member 41 wound around the first and second guide members 31 and 32 can be constantly maintained, friction between the guide members 30 and the connection members 40 can be constantly maintained. That is, a power transmission efficiency of the second power transmission device may not be lowered even if the hand body 13 is bent relative to the robot arm 11 .
[0064] FIG. 7 is a perspective view showing the robot hand and the robot arm according to the second embodiment of the present invention, and FIG. 8 is a side sectional view showing the robot hand and the robot arm according to a second embodiment of the present invention.
[0065] As shown in FIGS. 7 and 8 , the robot hand 12 of the humanoid robot includes a first rotating section 71 rotatably installed in the robot arm 11 and a second rotating section 72 rotatably installed in the hand body 13 . In addition, the first guide member 31 is rotatably installed around the first rotating section 71 and the second guide member 32 is rotatably installed around the second rotating section 72 .
[0066] A belt support member 73 is provided in the robot arm 11 . The belt support member 73 has reels 74 which are positioned opposite to each other on either side of the second rotating section 72 . The first actuator 27 also has a reel 76 . A belt 75 is coupled with the second rotating section 72 , so that when the first actuator 27 is driven, the second rotating section 72 is moved together with the belt 75 . The second rotating section 72 , the belt 75 and the belt support member 73 constitute the first power transmission device.
[0067] FIG. 8 shows the robot arm 11 and the hand body 13 are adjacent to each other. The robot arm 11 includes the first contact section 61 , and the hand body 13 includes the second contact section 62 . The first contact section 61 makes slide-contact with the second contact section 62 . If the second rotating section 71 moves together with the belt 75 , the second contact section 62 slides on the first contact section 61 . The second contact section 62 has a second radius R 2 about the second rotating section 72 . The first contact section 61 has a planar shape.
[0068] In FIG. 8 the first guide member 31 is rotatably installed around the first rotating section 71 and the second guide member 32 is rotatably installed around the second rotating section 72 . The radius R 3 of the second guide member 32 is the same length as the second radius R 2 of the second contact section 62 .
[0069] The second power transmission device includes the guide member 30 and the connection member 40 . The connection member 40 may include a first connection member 41 used to fold the finger members 14 and a second connection member 42 used to unfold the finger members 14 . The first connection member is alternately wound around the first and second guide members 31 and 32 . That is, the first connection member 41 is alternately wound around a left portion of the first guide member 31 and a right portion of the second guide member 32 . In contrast, the second connection member 42 is alternately wound around a right portion of the first guide member 31 and a left portion of the second guide member 32 . The length of the first and second connection members 41 and 42 , which connect the finger members 14 to the second actuator 43 , can be constantly maintained even if the robot hand 12 is folded due to the driving of the wrist joint 15 . Since the first and second connection members 41 and 42 have the same structure, the following description will be made with reference to the first connection member 41 .
[0070] FIG. 8 shows the hand body 13 before the hand body 13 is bent relative to the robot arm 11 , and FIG. 9 shows the hand body 13 that is bent to the right relative to the robot arm 11 at an angle of 90 degrees. In FIG. 8 , a contact point between the first and second contact sections 61 and 62 will be referred to as a first contact point 63 . In FIG. 9 , a contact point between the first and second contact sections 61 and 62 will be referred to as a second contact point 64 . When the belt 75 (see, FIG. 7 ) moves together with the second rotating section 72 , the hand body 13 rotates relative to the robot arm 11 . In this case, the first contact section 61 slides on the second contact section 62 while the contact point between the first and second contact sections 61 and 62 is being shifted from the first contact point 63 of FIG. 8 to the second contact point 64 of FIG. 9 . Thus, the length of the first connection member 41 between the first and second guide members 31 and 32 can be constantly maintained. Therefore, even if the hand body 13 is bent relative to the robot arm 11 due to the driving of the wrist joint 15 , the length of the first connection member 41 that connects the finger members 14 to the second actuator 43 can be constantly maintained. In this way, the movement of the wrist joint does not exert an influence upon the length of the wires. Therefore, the finger members are more precisely controlled and the gripping force of the robot hand is improved.
[0071] FIG. 10 shows the hand body 13 that is bent to the left relative to the robot arm 11 at an angle of 90 degrees. In FIG. 10 , a contact point between the first and second contact sections 61 and 62 will be referred to as a third contact point 65 . The first contact section 61 slides on the second contact section 62 while the contact point between the first and second contact sections 61 and 62 is being shifted from the first contact point 63 of FIG. 8 to the third contact point 65 of FIG. 10 . As a result, the length of the first connection member 41 between the first and second guide members 31 and 32 can be constantly maintained.
[0072] FIG. 11 is a perspective view showing the robot hand and the robot arm according to the third embodiment of the present invention, FIG. 12 is a front view showing the wrist joint according to the third embodiment of the present invention, and FIG. 13 is a side sectional view showing the wrist joint according to the third embodiment of the present invention.
[0073] As shown in FIGS. 11 to 13 , the robot hand 12 of the humanoid robot according to another embodiment of the present general inventive concept includes a pivot shaft 80 rotatably coupled to the robot arm 11 . A first reel 84 is fitted around the pivot shaft 80 and a second reel 86 is coupled with the first actuator 27 . The first actuator 27 rotates the pivot shaft 80 using the belt 85 . The pivot shaft 80 and the belt 85 constitute the first power transmission device.
[0074] A first support member 81 , to which the first guide member 31 is rotatably coupled as shown in FIGS. 12 and 13 , is installed in the robot arm 11 , and a second support member 82 , to which the second guide member 32 is rotatably coupled, is installed in the hand body 13 . The second support member 82 is connected to the pivot shaft 80 , so that the second support member 82 rotates together with the pivot shaft 80 . The number of first and second guide members 31 corresponds to the number of second guide members 32 and corresponds to the number of finger members 14 .
[0075] The connection members 40 are alternately wound around the first and second guide members 31 and 32 to transfer the driving force of the second actuator 43 to the finger members 14 . The connection members 40 include a first connection member 41 used to fold the finger members 14 and a second connection member 42 used to unfold the finger members 14 . For instance, the first connection member 41 is wound around the left portion of the second guide member 32 and then wound around the right portion of the first guide member 31 .
[0076] According to this embodiment, a portion of the connection members 40 aligned between the first and second guide members 31 and 32 is positioned on the same line with the pivot shaft 80 . In this case, the length of the connection members 40 aligned between the first and second guide members 31 and 32 can be constantly maintained even if the hand body 13 is bent relative to the robot arm 11 .
[0077] FIG. 14 is a side sectional view showing the hand body, which is bent to the right relative to the robot arm, according to this embodiment, and FIG. 15 is a side sectional view showing the hand body, which is bent to the left relative to the robot arm, according to this embodiment.
[0078] FIG. 13 shows the hand body 13 before the hand body 13 is bent relative to the robot arm 11 , and FIG. 14 shows the hand body 13 that is bent to the right relative to the robot arm 11 at an angle of 90 degrees. In addition, FIG. 15 shows the hand body 13 that is bent to the left relative to the robot arm 11 at an angle of 90 degrees. As shown in FIGS. 13 to 15 , the first connection member 41 is provided on the same line with the pivot shaft 80 , so that the length of the first connection member 41 between the first and second guide members 31 and 32 can be constantly maintained even if the hand body 13 is bent relative to the robot arm 11 .
[0079] Although few embodiments of the present general inventive concept have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the claims and their equivalents. | Disclosed is a humanoid robot capable of improving power transmission efficiency of a wire and movement displacement of a wrist joint by modifying the structure of the wrist joint serving as a passage for wires. The humanoid robot includes a robot hand including a power transmission device for transferring gripping force to finger members. The power transmission device includes connection members connecting an actuator to finger joints and guide members for guiding the connection members. The guide members include a first guide member coupled to a robot arm and a second guide member coupled to a hand body. The connection members are alternately wound around the first and second guide members. The gripping force is enhanced whereby a length of the connection members provided between the first and second guide members is constantly maintained even if the second guide member is shifted from the first guide member. | 8 |
TECHNICAL FIELD
[0001] This patent disclosure relates generally to a hydraulic system and, more particularly, to a hydraulic system for use in a machine that employs an implement.
BACKGROUND
[0002] Many machines use hydraulic actuators to accomplish a variety of tasks, such as moving an implement. Examples of such machines include, without limitation, dozers, loaders, excavators, motor graders, and other types of heavy machinery. The hydraulic actuators in such machines are linked via fluid flow lines to a pump associated with the machine to provide pressurized fluid to the hydraulic actuators. Chambers within the various actuators receive the pressurized fluid in controlled flow rates in response to operator demands or other signals. The pump can be a load-sense hydraulic pump that, in response to the magnitude of the load acting on the implement, automatically varies the flow rate of the pressurized fluid. For example, when the implement encounters a heavy load, the load-sense hydraulic pump provides a correspondingly high flow rate to the hydraulic actuators. Likewise, when the implement encounters a small or light load, or when no load acts on the implement, the load-sense hydraulic pump provides a correspondingly low flow rate to the hydraulic actuators.
[0003] Oftentimes, after completing a task and when no load is acting on the implement, an operator may desire to dislodge dirt, mud, clay, or debris from the implement. To do so, the operator may quickly cycle a control lever back and forth, causing the hydraulic actuators to expand and retract, thereby moving the implement back and forth in rapid succession. This is sometimes referred to as rapid shakeout, or rapid sharing of the implement. However, because rapid shakeout is desired and typically occurs when no load is acting on the implement, e.g., when the bucket is substantially empty and when the load-sense pump is providing pressurized fluid to the actuators at a low flow rate, the actuators can respond slowly to the operator's commands.
[0004] Several known hydraulic systems having a load-sense pump have been adapted for accommodating rapid shakeout. One exemplary fluid system is disclosed in U.S. Pat. No. 5,235,809 for a Hydraulic Circuit for Shaking a Bucket on a Vehicle, filed on Sep. 9, 1991, and issued to Robert G. Farrell on Aug. 17, 1993 (“Farrell”). Fluid systems, such as disclosed in Farrell, include an implement such as a bucket operated by a hydraulic actuator, a directional valve for controlling fluid flow from a load sensing variable displacement pump, and a hydraulic bucket shake circuit. In this type of system, when an operator desires a rapid shakeout, the operator manually activates the hydraulic bucket shale circuit, which forces the pump to a maximum displacement condition. In this condition, the pump provides standby pressure and fluid flow to the hydraulic actuator by way of the directional valve so that the hydraulic actuator can rapidly expand and retract to rapidly shaking the bucket. However, it is a shortcoming to this system that manual activation is required for operation of the hydraulic bucket shake circuit. An additional shortcoming is that the hydraulic bucket shake circuit is a binary circuit that is either off or on for forcing the pump to a maximum displacement condition. This design can waste fuel and subjects the machine, including the pump and the engine, to unnecessary wear.
[0005] It should be appreciated that the foregoing background discussion is intended solely to aid the reader. It is not intended to limit the disclosure or claims, and thus should not be taken to indicate that any particular element of a prior system is unsuitable for use, nor is it intended to indicate any element to be essential in implementing the examples described herein, or similar examples.
BRIEF SUMMARY
[0006] The disclosure describes, in one aspect, a fluid system for use with a machine that employs an actuator that provides for rapid shaking of an implement. The fluid system includes a source for providing fluid flow to the actuator and an operator input device for enabling an operator to control the movement of the implement by inputting a plurality of commands that specify movement of the implement. A controller is provided for monitoring the commands received from the operator input device and entering a mode for controlling the displacement of the source when the controller detects a pattern of commands that indicates an operator-request for rapid movement of the implement.
[0007] The disclosure describes, in another aspect, a method of controlling the displacement of a source in a machine for providing a fluid flow to an actuator that provides for rapid movement of an implement. The method includes establishing an indicator characterized by a pattern of input commands that indicate a request for rapid movement of the implement. The method also includes monitoring a user-input device for the indicator and, after identifying the indicator, initiating a mode to control the displacement of the source for providing the fluid flow to the actuator that provides for rapid movement of the implement.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a schematic side view of an exemplary machine;
[0009] FIG. 2 is a schematic illustrating an exemplary hydraulic system for use in a machine such as illustrated in FIG. 1 ;
[0010] FIG. 3 is a graph illustrating an exemplary mode executed by a controller of the hydraulic system of FIG. 2 ; and
[0011] FIG. 4 is a graph illustrating another exemplary mode executed by the controller of the hydraulic system of FIG. 2 .
DETAILED DESCRIPTION
[0012] This disclosure relates to a system and method for controlling a flow of hydraulic fluid in a hydraulic system of a machine. In particular, a controller applies one or more modes to control a rate of flow of hydraulic fluid to an actuator in the machine when an operator requests rapid shaking of an implement. This rapid shaking can, for example, dislodge mud, dirt, clay or debris from the implement.
[0013] FIG. 1 illustrates an exemplary machine 10 . The machine 10 may be a fixed or mobile machine that performs an operation associated with an industry such as, for example mining, construction, farming, or transportation. For example, the machine 10 may be an earth moving machine such as an excavator, a dozer, a loader, a backhoe, a motor grader, or any other earth moving machine. The machine 10 may include a linkage system 12 , an implement 14 attachable to linkage system 12 , one or more hydraulic actuators 16 a - c interconnecting the linkage system 12 , an operator interface 18 , a power source 20 , and at least one traction device 22 .
[0014] The linkage system 12 may include any structural unit that supports movement of the implement 14 . The linkage system 12 may include, for example, a stationary base frame 24 , a boom 26 , and a stick 28 . The boom 26 may be pivotally connected to the frame 24 , while the stick 28 may be pivotally connected to the boom 26 at a joint 30 . The implement 14 may pivotally connect to the stick 28 at a joint 32 . It is contemplated that the linkage system may alternatively include a different configuration and/or number of linkage members than the system depicted in FIG. 1 .
[0015] Numerous different implements 14 may be attachable to the stick 28 and controllable via the operator interface 18 . The implement 14 may include any device used to perform a particular task such as, for example, a bucket, a fork arrangement, a blade, a shovel, a ripper, a dump bed, a broom, a snow blower, a propelling device, a cutting device, a grasping device, or any other task-performing device known in the art. The implement 14 may be configured to pivot, rotate, slide, swing, lift, or move relative to machine 10 in any manner known in the art.
[0016] The operator interface 18 may be configured to receive input from an operator indicative of a desired movement of the machine 10 , including the implement 14 . More particularly, the operator interface 18 may include an operator interface device 34 such as, for example, a multi-axis joystick. The operator interface device 34 may be a proportional-type controller configured to position and/or orient the implement 14 and to produce an interface device position signal indicative of a desired movement of the implement 14 . It is contemplated that additional and/or different operator interface devices may be included within operator interface 18 such as, for example, wheels, knobs, push-pull devices, switches, pedals, and other operator interface devices known in the art.
[0017] The power source 20 may be an engine such as, for example, a diesel engine, a gasoline engine, a gaseous fuel-power engine such as a natural gas engine, or any other engine known in the art. It is contemplated that power source 20 may alternatively embody another source of power such as a fuel cell, a power storage device, an electric or hydraulic motor, or another source of power known in the art.
[0018] The traction device 22 may include tracks located on each side of the machine 10 . Alternatively, the traction device 22 may include wheels, belts, or other traction devices. Traction device 22 may or may not be steerable. It is contemplated that if the machine 10 embodies a stationary machine, the traction device 22 may be omitted.
[0019] As illustrated in FIG. 2 , the machine 10 may include a hydraulic system 40 having a plurality of fluid components that cooperate to move the implement 14 . Specifically, the hydraulic system 40 may include a tank 42 for holding a supply of fluid, and a source 44 configured to pressurize the fluid and to provide a flow of the pressurized fluid to the hydraulic actuators 16 a - c . While FIG. 1 depicts three actuators, identified as 16 a , 16 b , and 16 c , for the purposes of simplicity, the hydraulic schematic of FIG. 2 depicts only one hydraulic actuator identified as 16 . The hydraulic system 40 may include first and second valves 46 , 48 . The first valve 46 may be a directional valve 46 associated with each end of the hydraulic actuator 16 for directing the flow of pressurized fluid to the hydraulic actuator 16 . The second valve 48 may be a bypass valve located between the tank 42 and the source 44 .
[0020] The hydraulic system 40 also may include a head-end pressure sensor 50 and a rod-end pressure sensor 52 associated with the hydraulic actuator 16 . The hydraulic system 40 may further include a linkage sensor 54 and a controller 56 in communication with the fluid components of hydraulic system 40 and the operator interface device 34 . It is contemplated that hydraulic system 40 may include additional and/or different components such as, for example, accumulators, restrictive orifices, check valves, pressure relief valves, makeup valves, pressure-balancing passageways, temperature sensors, tool recognition devices, and other components known in the art.
[0021] The tank 42 may be a reservoir configured to hold a supply of fluid. The tank 42 may be in fluid communication with the source 44 , the directional valve 46 , and the bypass valve 48 . The fluid may include, for example, a dedicated hydraulic oil, an engine lubrication oil, a transmission lubrication oil, or any other fluid known in the art. The hydraulic system 40 within the machine 10 may draw fluid from and return fluid to the tank 42 . It is also contemplated that hydraulic system 40 may be connected to multiple separate fluid tanks.
[0022] The source 44 may be configured to produce a flow of pressurized fluid and may include a pump such as, for example, a load-sense variable displacement pump. The source 44 draws fluid from the tank 42 and provides fluid flow to the directional valve 46 , which then directs the fluid flow to the actuator 16 . The source 44 may be drivably connected to the power source 20 of the machine 10 by, for example, a countershaft 58 , a belt, an electrical circuit, or in any other suitable manner. Alternatively, source 44 may be indirectly connected to the power source 20 via a torque converter, a gear box, or in any other manner known in the art. It is contemplated that multiple sources of pressurized fluid may be interconnected to supply pressurized fluid flow to the hydraulic system 40 .
[0023] In operation, the source 44 may be a load-sense pump configured to maintain a constant pressure differential between the pressure indicated by a load sense line 59 and the pressure in a supply line 61 , which fluidly connects the source 44 to the directional valve 46 . For example, the load sense line 59 may extend between the directional valve 46 and the source 44 for transmitting, either electronically or hydro-mechanically, to the source 44 information regarding the magnitude of the load acting on the actuator 16 . It should be appreciated that the load sense line 59 may extend between the actuator 16 and the source 44 .
[0024] For example, in an embodiment, the load sense line 59 transmits a pressure value that represents the magnitude of the load acting on the actuator 16 . When a load having a large magnitude acts on the actuator 16 , the load sense line 59 transmits a correspondingly large pressure value to the source 44 . In response, the displacement of the source 44 increases, thereby increasing the pressure in the supply line 61 so as to maintain the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load-sense line 59 . Likewise, when a load having a small magnitude acts on the actuator 16 , the load-sense line 59 transmits a correspondingly small pressure value to the source 44 . In response to the small pressure value, the displacement of the source 44 decreases, thereby decreasing pressure in the supply line 61 so as to maintain the constant pressure differential.
[0025] The hydraulic actuator 16 may be a fluid cylinder that interconnects the implement 14 and linkage system 12 . It is contemplated that hydraulic actuators other than fluid cylinders may alternatively be implemented within hydraulic system 40 such as, for example, hydraulic motors or any other type of hydraulic actuator known in the art. As illustrated in FIG. 2 , the hydraulic actuator 16 may include a tube 60 and a piston assembly 62 disposed within tube 60 . One of the tube 60 and the piston assembly 62 may be pivotally connected between members of the linkage system 12 and/or implement 14 . The hydraulic actuator 16 may include a first chamber 64 and a second chamber 66 separated by a piston 68 . The first and second chambers 64 , 66 may be selectively supplied with pressurized fluid from the source 44 and selectively drained of the fluid to cause the piston assembly 62 to displace within tube 60 , thereby changing the effective length of the hydraulic actuator 16 . This expansion and retraction of hydraulic actuator 16 may function to move the implement 14 and linkage system 12 .
[0026] The piston assembly 62 , as shown, includes the piston 68 axially aligned with, and disposed within, the tube 60 , and a piston rod 70 connectable to the frame 24 , the boom 26 , the stick 28 , or the implement 14 . The piston 68 may include a first hydraulic surface 72 and a second hydraulic surface 74 opposite the first hydraulic surface 72 . An imbalance of force caused by fluid pressure on the first and second hydraulic surfaces 72 , 74 may result in movement of piston assembly 62 within tube 60 . For example, a force on the first hydraulic surface 72 greater than a force on the second hydraulic surface 74 may cause the piston assembly 62 to expand out of the tube 60 , thereby increasing the effective length of the hydraulic actuator 16 . Similarly, when a force on the second hydraulic surface 74 is greater than a force on the first hydraulic surface 72 , the piston assembly 62 may retract within tube 60 , thereby decreasing the effective length of the hydraulic actuator 16 . A flow rate of fluid into and out of the first and second chambers 64 , 66 may determine the velocity of the hydraulic actuator 16 , while a pressure of the fluid in contact with the first and second hydraulic surfaces 72 and 74 may determine an actuation force of the hydraulic actuator 16 . A sealing member, such as an o-ring, may be connected to the piston 68 to restrict a flow of fluid between an internal wall of the tube 60 and an outer cylindrical surface of the piston 68 .
[0027] The directional valve 46 may be disposed between the source 44 and the actuator 16 and between the tank 42 and the actuator 16 . The directional valve 46 may be configured to regulate the flow of pressurized fluid to and from the first and second chambers 64 , 66 of the actuator 16 in response to commands from the controller 56 , which receives commands from the operator interface device 34 . The directional valve 46 may move between a first-open position, a closed position, and a second-open position.
[0028] In the first-open position, the directional valve 46 directs fluid from the source 44 to first chamber 64 for expanding the hydraulic actuator 16 and moving the implement 14 in a first direction. When the actuator 16 is expanding, fluid exits the second chamber 66 and flows back to the directional valve 46 , which then directs the fluid back to the tank 42 . In the second-open position, the directional valve 46 directs fluid from the source 44 to the second chamber 66 , thereby retracting the piston assembly 62 into the tube 60 of the actuator 16 and moving the implement 14 in a second direction. The retracting piston assembly 62 forces fluid out of the first chamber 64 and back to the directional valve 46 , which then directs the fluid back to the tank 42 . When in the closed position, the directional valve 46 blocks fluid from flowing from the source 44 to the actuator 16 and from the actuator 16 to the tank 42 .
[0029] In the case where the source 44 is a load-sense pump and when the directional valve 46 is in either the first- or second-open position, more fluid flow is needed from the source 44 to maintain the pressure in the supply line 61 . Accordingly, to maintain the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load sense line 59 , the displacement/speed of the source 44 increases so as to provide more fluid flow in the supply line 61 when the directional valve 46 is in either the first- or second-open position.
[0030] The directional valve 46 may include a proportional spring biased mechanism that is solenoid actuated and configured to move the directional valve 46 between the first-open, closed, and second-open positions. The directional valve 46 may be movable to any position between these positions to vary the rate of flow to and from the first and second chambers 64 , 66 of the actuator 16 , thereby affecting the velocity of actuator 16 and the velocity of the moving implement 14 . It is contemplated that the directional valve 46 may alternatively be hydraulically actuated, mechanically actuated, pneumatically actuated, or actuated in any other suitable manner.
[0031] The bypass valve 48 may be fluidly connected to the supply line 61 for selectively permitting fluid to bypass the directional valve 46 and flow back to the tank 42 . The bypass valve 48 may include a proportional spring biased valve mechanism that is solenoid actuated and configured to move between an open position at which fluid is allowed to flow back to tank 42 , and a closed position at which fluid flow is blocked from flowing back to tank 42 . It is contemplated that bypass valve 48 may alternatively be hydraulically actuated, mechanically actuated, pneumatically actuated, or actuated in any other suitable manner.
[0032] The bypass valve 48 may be movable to any position between the open and closed positions to vary the rate of flow back to tank 42 , thereby affecting the displacement/speed of the source 44 . The rate of flow to tank 42 , which is controlled by the displacement of the bypass valve 48 , is directly proportional to the displacement of the source 44 . For example, in the case where the source 44 is a load-sense pump and when the bypass valve 48 is in the open position for allowing a rate of flow to tank 42 , increased displacement from the source 44 is needed to provide a corresponding increase in the rate of flow in the supply line 61 so as to maintain the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load sense line 59 .
[0033] The controller 56 may embody a single microprocessor or multiple microprocessors that include a means for controlling an operation of the hydraulic system 40 . Numerous commercially available microprocessors can be configured to perform the functions of the controller 56 . It should be appreciated that the controller 56 could readily be embodied in a general machine microprocessor capable of controlling numerous machine functions. The controller 56 may include a memory, a secondary storage device, a processor, and any other components for running and executing an application. Various other circuits may be associated with the controller 56 such as power supply circuitry, signal conditioning circuitry, solenoid driver circuitry, and other types of circuitry.
[0034] The controller 56 may be configured to command the bypass valve 48 to proportionally move between the first and second positions for increasing and decreasing the displacement of the source 44 . This may be useful, for example, when the source 44 is a load-sense pump. In such a case, when a load having a small magnitude acts on the implement 14 , the load sense line 59 indicates a correspondingly small pressure. Accordingly, to maintain the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load-sense line 59 , the load-sense pump 44 operates at a low displacement.
[0035] This characteristic of load-sense pumps 44 can be disadvantageous because oftentimes, after completing a task and when no load is acting on the implement 14 , an operator may want to rapidly shake the implement 14 , thereby dislodging mud, dirt, clay, or debris from the implement 14 . However, the load-sense pump 44 , which is operating at a low displacement, provides fluid having a low flow rate to the actuator 16 . Because the flow rate of the fluid entering and exiting the first and second chambers 64 , 66 of the actuator 16 determines the velocity at which actuator 16 expands and retracts, in conditions of low fluid flow rates to the actuator 16 , the actuator 16 may not expand and retract fast enough to rapidly shake the implement 14 . Accordingly, the movements of the implement 14 lag behind the operator's rapid commands.
[0036] To prevent this lag from occurring when a small-magnitude load acts on the implement 14 , the controller 56 , upon identifying a pattern of input commands that indicate a request for rapid shaking, is configured to automatically initiate a mode for controlling the displacement of the source 44 . For example, the controller 56 may initiate a destroke-reduction mode and/or a rapid-movement mode.
[0037] FIG. 3 provides a graphical illustration of the displacement of various components of the hydraulic system 40 when the controller 56 is operating in the destroke-reduction mode, which is a mode for reducing the destroke rate of the source 44 when an operator is attempting to rapidly shake the implement 14 . At time=0, the operator inputs a command, e.g., the operator moves the joystick, indicating a request for movement of the implement 14 . In response, the controller 56 instructs the directional valve 46 to move from the closed position to one of the first- and second-open positions, thereby increasing the displacement of the source 44 to 100% so as to provide fluid flow to the actuator 16 for moving the implement 14 in a manner consistent with the inputted command. At time=T 1 , the operator retracts the command, e.g., the operator moves the joystick back to a neutral position, thereby indicating a request to discontinue movement of the implement 14 . In response, the controller 56 instructs the direction valve 46 to move back to the closed position.
[0038] Accordingly, within the time elapsed between time=0 and time=T 1 , the operator inputted a pattern of commands indicating a request that the implement 14 move and then discontinue moving. The controller 56 is configured to recognize this pattern of commands as indicating an operator-request for rapid shaking of the implement and, in response, initiate the destroke-reduction mode. It is contemplated that T 1 can be defined according to user preferences. For example, T 1 can be one-quarter or one-half of a second. It is contemplated that that controller 56 can be configured to recognize other patterns of commands as indicating an operator-request for rapid shaking of the implement.
[0039] When operating in the destroke-reduction mode and when the operator inputs a command indicating a request to discontinue movement of the implement 14 , the controller 56 is configured close the directional valve 46 and open the bypass valve 48 . Opening the bypass valve 48 reduces the rate of decrease in the displacement of the source 44 because, in the case where the source 44 is a load-sense pump, the displacement of the source 44 must remain sufficiently high to maintain the pressure differential between the pressure in the supply line 61 and the pressure indicated by the load-sense line 59 . If the bypass valve 48 were not open when the directional valve 46 is closed, the source 44 would be forced to operate at a low displacement for maintaining the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load-sense line 59 . This concept is illustrated in FIG. 3 , where at time=T 1 , the operator inputs a command indicating a request for discontinuing movement of the implement 14 . In response to this command, the source displacement with the controller operated bypass valve 48 decreases to approximately 25%, whereas the source displacement without the controller operated bypass valve 48 decreases to approximately 0%.
[0040] As a result, when the operator inputs a subsequent command indicating a request for movement of the implement 14 , the source displacement with the controller operated bypass valve 48 will obtain 100% displacement in less time than the source displacement without the controller operated bypass valve 48 . This is also illustrated in FIG. 3 , where at time=T 2 , the operator inputs a command indicating a request for movement of the implement 14 and, in response to this command, the source displacement with the controller operated bypass valve 48 obtains 100% displacement at T 3 , whereas the source 44 displacement without the controller operated bypass valve 48 obtains 100% displacement later, at T 4 . As such, the directional valve 46 , when receiving fluid flow from the source 44 operating in combination with the controller operated bypass valve 48 , is capable of directing fluid flow at a high flow rate between the first and second chambers 64 , 66 of the actuator 16 , thereby providing rapid back-and-forth movement of the piston 68 and the implement 14 .
[0041] In an embodiment, the controller 56 is configured to operate in a rapid-movement mode which can increase the displacement of the source 44 . The controller 56 , when operating in the rapid-movement mode, is configured to proportionally open the bypass valve 48 to maintain the source 44 at about 50% of the maximum displacement when the operator inputs a command indicating a request that the implement 14 remain stationary, e.g., when the joystick is in the neutral position and when the directional valve 46 is in the closed position. Accordingly, when an operator inputs a pattern of commands indicating a request for rapid shaking of the implement 14 , the source 44 , operating at 50% displacement, can quickly increase to 100% displacement for providing an adequate flow rate of fluid flow in and out of first and second chambers 64 and 66 of the actuator 16 . It is contemplated that the bypass valve 48 may be proportionally opened or closed, e.g., the displacement of the bypass valve may be proportionally increased or decreased, for maintaining the source 44 at a standby displacement of less or more than 50%.
[0042] FIG. 4 provides a graphical illustration of the displacement of various components of the hydraulic system 40 when the controller 56 is operating in the rapid-movement mode. The controller 56 is configured to proportionally open the bypass valve 48 when the directional valve 46 moves to the closed position, e.g., when the implement 14 is stationary. Accordingly, at time=0, when the operator's command indicates a request that the implement 14 remain stationary, the controller 56 maintains the bypass valve 48 in an open position and the directional valve 46 in a closed position. As shown in FIG. 4 , at time=0, the open bypass valve 48 forces the source 44 to operate at a displacement of about 50% so as to maintain the constant pressure differential between the pressure in the supply line 61 and the pressure indicated by the load-sense line 59 . Also illustrated in FIG. 4 is the displacement of the source 44 without the controller 56 operated bypass valve 48 . As shown in FIG. 4 , without the bypass valve 48 , the displacement of the source 44 at time=0 is approximately 0%. The displacement of the source 44 operating without the bypass valve 48 is low because only a small amount of fluid flow is required to maintain the constant pressure differential when no load is acting on the implement 14 and when the directional valve 46 is in the closed position.
[0043] At time=T 1 , the operator inputs a command indicating a request for movement of the implement 14 . In response, controller 56 moves the directional valve 46 to either the first- or second-open position and moves the bypass valve 48 to the closed position. Closing the bypass valve 48 forces all of the flow in the supply line 61 to the directional valve 46 , which directs the flow to the actuator 16 . Because the source 44 is operating at 50% displacement when the directional valve 46 opens, the source 44 increases to 100% displacement in less time than the source 44 without the controller operated bypass valve 48 . Accordingly, as illustrated in FIG. 4 , the source 44 , and the actuator 16 which receives fluid flow from the source 44 , are more responsive to operator commands, e.g., commands requesting rapid movement of the implement, when the hydraulic system 40 includes the controller operated bypass valve 48 .
[0044] In operation, the controller 56 , when programmed to operate the bypass valve 48 pursuant to the destroke-reduction mode and/or the rapid-movement mode described herein, causes the source 44 to be capable of quickly providing sufficient rates of fluid flow to rapidly shale the implement 14 . Thus, for example, in the case of an excavator or backhoe having a load-sense pump and a bucket used for moving earth, the excavator or backhoe may, upon the command of an operator and without first having to manually open a binary bypass valve, rapidly shake the bucket at a time when the bucket is substantially empty to dislodge dirt, mud, clay, or debris from the bucket.
INDUSTRIAL APPLICABILITY
[0045] The industrial applicability of the system and method described herein will be readily appreciated from the foregoing discussion. A technique is described wherein the rate of flow to an actuator such as for rapid shaking of an implement is controlled to provide an adequate rate of flow to the actuator within a small amount of time.
[0046] The disclosed hydraulic system and method are applicable to any hydraulically actuated machine that includes a fluidly connected hydraulic actuator where it is desirable to provide fluid flow to the actuator for rapidly shaking an implement. The disclosed hydraulic system includes a controller that applies one or more modes to control a rate of flow to the actuator when an operator requests rapid movement of an implement. In this manner, an adequate rate of flow is available for rapid shaking, while minimizing unnecessary and wasteful displacement from a source, such as a pump.
[0047] During operation of the machine 10 , a machine operator manipulates the operator interface device 34 to create a desired rapid shaking of the implement 14 . Throughout this process, the operator interface device 34 generates signals indicative of desired flow rates of fluid supplied to hydraulic actuators 16 a - c to accomplish the desired shaking. The controller 56 , upon identifying signals indicative of a request for rapid shaking, executes the destroke-reduction mode and/or the rapid-movement mode, as described with reference to FIGS. 3 and 4 , to provide an adequate rate of flow to the hydraulic actuators 16 a - c for moving the implement 14 as requested by the operator.
[0048] It will be appreciated that the foregoing description provides examples of the disclosed system and technique. However, it is contemplated that other implementations of the disclosure may differ in detail from the foregoing examples. All references to the invention or examples thereof are intended to reference the particular example being discussed at that point and are not intended to imply any limitation as to the scope of the invention generally. All language of distinction and disparagement with respect to certain features is intended to indicate a lack of preference for those features, but not to exclude such from the scope of the invention entirely unless otherwise indicated.
[0049] Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
[0050] Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. | A fluid system for use with a machine that employs an actuator, that provides for rapid shaking of an implement. The fluid system includes a source for providing fluid flow to the actuator and an operator input device for enabling an operator to control the movement of the implement by inputting a plurality of commands that specify movement of the implement. A controller is provided for monitoring the commands received from the operator input device and entering a mode for controlling the displacement of the source when the controller detects a pattern of commands that indicates an operator-request for rapid movement of the implement. | 5 |
FIELD OF THE INVENTION
[0001] The invention relates to the general field of CPP GMR read heads with particular reference to the AP1-AP2 sub-structure.
BACKGROUND OF THE INVENTION
[0002] The principle governing the operation of most magnetic read heads is the change of resistivity of certain materials in the presence of a magnetic field (magneto-resistance or MR). Magneto-resistance can be significantly increased by means of a structure known as a spin valve where the resistance increase (known as Giant Magneto-Resistance or GMR) derives from the fact that electrons in a magnetized solid are subject to significantly less scattering by the lattice when their own magnetization vectors (due to spin) are parallel (as opposed to anti-parallel) to the direction of magnetization of their environment.
[0003] The key elements of a spin valve are illustrated in FIG. 1 . They are seed layer 11 on which is antiferromagnetic layer 12 whose purpose is to act as a pinning agent for a magnetically pinned layer. The latter is a synthetic antiferromagnet formed by sandwiching antiferromagnetic coupling layer 14 between two antiparallel ferromagnetic layers 13 (AP2) and 15 (AP1). In principle, any non-magnetic material could be used for layer 14 but some are more efficient than others, as will be discussed in greater detail below.
[0004] Next is a copper spacer layer 16 on which is low coercivity (free) ferromagnetic layer 17 . A contacting layer such as lead 18 lies atop free layer 17 . When free layer 17 is exposed to an external magnetic field, the direction of its magnetization is free to rotate according to the direction of the external field. After the external field is removed, the magnetization of the free layer will stay at a direction, which is dictated by the minimum energy state, determined by the crystalline and shape anisotropy, current field, coupling field and demagnetization field.
[0005] If the direction of the pinned field is parallel to the free layer, electrons passing between the free and pinned layers suffer less scattering. Thus, the resistance in this state is lower. If, however, the magnetization of the pinned layer is anti-parallel to that of the free layer, electrons moving from one layer into the other will suffer more scattering so the resistance of the structure will increase. The change in resistance of a spin valve is typically 8-20%.
[0006] Most GMR devices have been designed so as to measure the resistance of the free layer for current flowing parallel to its two surfaces. However, as the quest for ever greater densities has progressed, devices that measure current flowing perpendicular to the plane (CPP) have begun to emerge. For devices depending on in-plane current, the signal strength is diluted by parallel currents flowing through the other layers of the GMR stack, so these layers should have resistivities as high as possible. In contrast, in a CPP device, the total transverse resistance of all layers, other than the free layer, should be as low as possible so that resistance changes in the free layer can dominate.
[0007] A related device to the CPP GMR described above is the magnetic tunneling junction (MTJ) in which the layer that separates the free and pinned layers is a non-magnetic insulator, such as alumina or silica. Its thickness needs to be such that it will transmit a significant tunneling current. The principle governing the operation of the MTJ cell in magnetic RAMs is the change of resistivity of the tunnel junction between two ferromagnetic layers. When the magnetizations of the pinned and free layers are in opposite directions, the tunneling resistance increases due to a reduction in the tunneling probability. The change of resistance is typically 40%, which is much larger than for GMR devices.
[0008] Currently, all CIP devices use 8 Å of Ru as their choice of antiferromagnetic coupling material with an AP1/AP2 thickness in the range of 10-30 Å. In the CIP case, the AP1 and AP2 thickness cannot be increased since it will reduce the CIP GMR. Although Rh or Ru4 are known to increase the antiferromagnetic coupling strength 2-4 times relative to Ru8, a much higher annealing field (over 30 kOe) is needed. It is therefore not practical to use Rh or Ru4 for CIP structures.
[0009] Currently, all prior art CPP devices continue to use the same structure that was developed for CIP devices (Ru8 with AP1/AP2 in the range of 20-40 Å of CoFe) since it has been reasonable to assume that the same very high field during annealing would be needed.
[0010] The present invention discloses how Rh and Ru4 may be used, thereby increasing the CPP GMR, without the need of the afore-mentioned very high annealing fields
[0011] A routine search of the prior art was performed with the following references of interest being found:
[0012] In U.S. Pat. No. 6,493,195, Hayashi et al describe using Rh between pinned layers. In U.S. Pat. No. 6,462,541, Wang et al disclose Rh as an antiferromagnetic coupling layer. Grill (U.S. Pat. No. 6,456,469) teaches that any suitable non-magnetic material can be used between the pinned layers, but that Ru is preferred. Many other patents also teach that many materials are suitable. U.S. Pat. No. 6,430,015 (Ju et al)—a Headway patent—shows that Rh, Cr, and Ir can be substituted for Ru. Ueno et al. (U.S. Pat. No. 6,340,533) teaches using Cr, Rh, Ir, and alloys of Ru. Finally, in U.S. Pat. No. 6,338,899, Fukuzawa et al. show that Ru, Rh, Cr, and Ir, or the like, can be used between the pinned layers.
SUMMARY OF THE INVENTION
[0013] It has been an object of at least one embodiment of the present invention to provide a CPP GMR magnetic read head having improved stability and performance.
[0014] Another object of at least one embodiment of the present invention has been to provide a process for manufacturing said read head.
[0015] Still another object of at least one embodiment of the present invention has been that said process be compatible with existing processes for the manufacture of CPP GMR devices.
[0016] These objects have been achieved by using Rh as the AFM coupling layer in a synthetically pinned CPP GMR structure. This enables the AP1/AP2 thicknesses to be increased, which results in improved stability since the pinning field is increased, and for the free layer leading to an overall improvement in the device performance. Another key advantage of this structure is that the magnetic annealing requirements (to establish effective exchange coupling between AP1 and AP2) can be significantly relaxed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 shows a GMR stack of the prior art in which AFM coupling is achieved through Ru.
[0018] FIG. 2 shows a bottom spin valve manufactured according to the teachings of the present invention.
[0019] FIG. 3 shows a top spin valve manufactured according to the teachings of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] In a typical CPP spin valve structure with Ru, AP1/AP2 thickness is in the range of 20-30 Å. It is known that Rh(5-7 Å) has much higher exchange coupling strength than Ru (6-9 Å) when it is sandwiched between two CoFe layers. It is also known that in a CPP spin valve, a thicker AP1 yields a higher GMR and DRA.
[0021] Since AP1 and AP2, when coupled through Rh (as opposed to Ru), have a much stronger coupling field, AP1/AP2 thicknesses can be increased while still maintaining comparable performance to Ru and/or having better pinning strength than Ru. This implies that a more stable and/or better performing device can be obtained if Rh is substituted for Ru in a CPP GMR device. These considerations apply to both top and bottom spin valve designs as well as to top or bottom magnetic tunnel junction devices.
[0022] We will disclose the present invention through a description of the process for manufacturing a bottom spin valve. This description will also serve to make clear the structure of the present invention. It will be readily understood by those skilled in the art that manufacture of top spin valve designs and magnetic tunnel designs follow along similar lines.
[0023] Referring now to FIG. 2 , the process of the present invention begins with the deposition on a suitable substrate, such as a magnetic shield (not shown), of lower lead layer 10 . Seed layer 11 is then deposited onto layer 10 followed by the deposition of AFM layer 12 which will serve as the pinning layer. Although any antiferromagnetic material could, in principle, be used for layer 12 , our preferred choice has been MnPt deposited to a thickness between about 80 and 200 Angstroms.
[0024] Next, AP2 layer 13 is deposited to a thickness between 50 and 90 Angstroms and comprises CoFe or NiFeCo. This is followed by the deposition of layer 24 of rhodium, to a thickness between about 5 and 7 Angstroms after which AP1 layer 15 (of similar material to AP2) is deposited onto the rhodium layer to a thickness between 50 and 90 Angstroms. Together, layers 13 , 24 , and 15 constitute the pinned layer. It is important to note that the thicknesses just quoted for these layers are critical for the satisfactory performance of the device.
[0025] Then, follows the deposition of copper spacer layer 16 followed by the deposition thereon of free layer 17 to a thickness between 20 and 50 Angstroms. The latter thickness is important for keeping the total thickness of the device to a minimum. Although any low coercivity material could, in principle, have been used for the free layer, our preferred choice has been CoFe, NiFe, or CoFeNi.
[0026] In order for MnPt and AP2 to have exchange coupling, the usual annealing temperature is 250-300° C. The annealing field for CIP device with Ru8 is about 10 kOe but If Rh or Ru4 is used in a CIP device, an annealing field of about 30 kOe is needed.
[0027] If Rh and Ru4 are used in a CPP device together with prior art AP1/AP2 thicknesses, an over 20 kOe field is still needed during MnPt annealing. However, if Rh or Ru4 use is accompanied by a thicker AP1/Ap2, we have found that we can reduce the annealing field to less than 8 kOe. This is of great importance to us since it allows us to use our existing ovens, making it economical to manufacture CPP devices that use Rh or Ru4. The optimum conditions for the anneal have been determined to be 280° C. for 5 hours in a 10 kOe field.
[0028] The process of the present invention concludes with the deposition, on the free layer, of upper lead layer 18 .
[0029] It is readily seen from the structure illustrated in FIG. 3 that the process for manufacturing a CPP GMR device of the top spin valve type amounts to a reversal of the order in which the various layers are deposited.
[0030] We have not explicitly illustrated top and bottom magnetic junction devices since they may be readily visualized from FIGS. 2 and 3 by simply substituting a layer of insulating material for copper spacer layer 16 . Materials most commonly used for the tunneling insulation include Al 2 O 3 and ZrO 2 and they are generally deposited to a thickness between about 5 and 15 Angstroms.
[0031] If the various layer thicknesses disclosed above are used, the resulting structure (including the upper and lower leads) has a total thickness that is less than 400 Å. This is important because a small shield-to-shield spacing is required for achieving high linear density.
[heading-0032] Confirmatory Results
[0033] We have used a bottom spin valve design to demonstrate the effectiveness of the present invention but similar results would be obtained from any of the other designs disclosed above. A two-current-channel model was used to estimate the CPP GMR gain that results from the use of thicker AP1/AP2 with Rh:
Seed/MnPt/CoFe30/Ru8/CoFe30/Cu30/CoFe60/Cu10/Cap (this is the prior art) Performance: RA=64 mohmcm 2 , DRA=0.84 mohmum 2 , and GMR=1.31%
Seed/MnPt/CoFe60/Rh6/CoFe60/Cu30/CoFe60/Cu10/Cap (the present invention) Performance: RA=70 mohmcm2, DRA=1.3 mohmum 2 , and GMR=1.86%
[0034] As can be seen, over 40% GMR and DRA gain were obtained by using thicker AP1 and AP2 with Rh.
[0035] Besides using Rh, other nonmagnetic other spacers with strong antiferromagnetic coupling, such as Ru 3-4 Å, Ir, etc can also be used to replace Ru 8 Å, currently used by the prior art. Note, however, that 3-4 Å is barely a monolayer so problems with pin-holes make it a less than optimum choice.
[0036] We conclude by noting that the magnetic properties of thin films are known to be very sensitive to a number of factors in addition to their composition. Said factors include, but may not be limited to, thickness, deposition conditions, annealing treatments (particularly in the presence of a magnetic field), immediate underlayer, and immediate over-coating. Thus, as a general rule, the parameters that characterize the layers named in the claims to be recited below should be regarded as critical rather than merely optimal. | Replacing ruthenium with rhodium as the AFM coupling layer in a synthetically pinned CPP GMR structure enables the AP1/AP2 thicknesses to be increased. This results in improved stability and allows the free layer and AFM layer thicknesses to be decreased, leading to an overall improvement in the device performance. Another key advantage of this structure is that the magnetic annealing requirements (to establish antiparallelism between AP1 and AP2) can be significantly relaxed. | 8 |
FIELD OF THE INVENTION
This invention relates to a ball mill for continuous grinding and dispersion of material suspended in liquid. More particularly though not exclusively the invention relates to heavy duty agitator ball mills for the processing of viscous flowing masses in the foodstuffs industry, in the chemical industry and in paint manufacture, to finely grind solids material contained in those masses.
STATEMENT OF THE PRIOR ART
Agitator ball mills are known in which a rotor having outwardly radially extending agitator members is mounted for rotation within a stator having inwardly extending stator agitator members, to form a grinding chamber between the rotor and the stator holding a charge of usually spherical grinding elements of steel, glass, porcelain, ceramics or similar materials. Rotation of the rotor leads the agitator members to set the grinding elements into circulation, and at the same time grinding stock (i.e. material or product to be ground) is pumped into the grinding chamber where it is exposed to shearing and pressure stresses by the grinding elements resulting in an intensive comminution effect on the solids particles in suspension in the grinding masses. The heat resulting from friction is dissipated by cooling of the stator and the rotor.
At the outlet for the ground product from the grinding chamber separating devices are provided which allow the ground product to pass through but retain the grinding elements.
The size reduction forces obviously do not only act on the product to be ground but also subject the active parts of the mill, such as grinding elements, agitator members and walls, to strong wear. It has therefore already been proposed that the grinding elements should be made of high wear-resistant materials, such as tungsten carbide or similar hard metals, so that they have as long a working life as possible.
On the other hand, however, it must be accepted that the softer steels of which the stator, rotor and agitator members are generally made are subjected to increased wear and abrasion and continuous impact stress by the hard grinding elements present in the flowing medium.
For the desired grinding effect as regards degree of fineness, the dispersion and throughput aimed at, there are numerous parameters which apply, such as the selection of the size of mill, number and ball diameter of the charge of grinding elements, the rotation speed of the rotor, the shape and distance apart of the agitator members, the pressure and the time of dwell of the product to be ground in the grinding container.
In the mill constructions known hitherto there was a narrow limit set on the possibilities of improving the performance by any change in the above-mentioned relevant factors because of the wearing behaviour of walls, agitator members and grinding elements, so as not to risk an uneconomical operation as a result of the working life of the mill being too short.
In the case of agitator ball mills of the abovementioned type it is known, in order to achieve speed and pressure conditions which shall be as uniform as possible, to provide an annular grinding cross-section wherein the cylindrical agitator rotor has a diameter of at least one-third of the diameter of the stator. At the same time this also achieves a considerable increase in the cooling surface for the dissipation of heat via the cooled rotor. Reference may be had to German Auslegeschriften Nos. 1 214 516 and 1 233 237, German Offenlegungsschriften Nos. 2 443 799 and 2 633 225 and Swiss Pat. Nos. 459 724 and 400 734.
Agitator members which transmit the energy of motion of the rotor to the charge of grinding elements are generally finger-shaped, vane-shaped or tooth-shaped tools fitted on the rotor body in such a way that they can be easily replaced.
In order to improve the grinding and dispersing effect, the inner wall of the stator also carries similarly shaped tools which have the task of promoting movement of the charge of grinding elements relative to the agitator members.
It has now been found that when the relative movement in the grinding chamber increases, the size reduction effect is certainly enhanced, but also the wear of the agitator members and of the walls, as well as the heating of the product bring ground, increase enormously. In the result the process often becomes uneconomical and the maximum permissible temperature of the ground product is often exceeded.
The aim of the present invention is to provide an improved ball mill which by its construction, its components and especially the cooling means for dissipation of heat, and also by the advantageous selection of the materials for its active elements, such as stator, rotor and agitator members, is resistant to wear to an extent which has never before been achieved either as regards working life or as regards performance and economy.
BRIEF STATEMENT OF THE INVENTION
Accordingly the invention provides a ball mill for continuous grinding and dispersion of material suspended in a liquid, said mill comprising: a plurality of rotor ring elements, at least some of said rotor ring elements having rotor agitator members projecting outwardly therefrom, said rotor ring elements being aligned to constitute a rotor; a stator surrounding said rotor and having stator agitator members projecting inwardly therefrom; said rotor being mounted for rotation within said stator; said rotor and said stator forming a grinding chamber therebetween intended to hold a charge of grinding elements; stator cooling means for cooling said stator; rotor cooling means for cooling said rotor, said rotor cooling means comprising cooling ribs which at least in part form boundaries of rotor cooling channels and at least in part are bounded by a surface of said rotor ring elements; and said rotor ring elements being replaceable and being highly wear resistant on surfaces that are intended to come into contact with said grinding elements. Generally the rotor agitator members and the stator agitator members project radially.
In previous endeavours for achieving resistance to wear use was made mainly of structural steels for the rotor and stator. By their nature, however, such materials are of limited surface hardness, because according to known shaping technology they had to be capable of being machined by metal cutting and also had to be at least in some cases weldable, and had to withstand other forces than merely frictional and compression forces.
The modes of construction and shaping technology which can be adopted in mills embodying the invention can avoid these conditions regarding machinability and loading stresses and hence leads to far greater scope in the selection of materials. Furthermore, by use of the cooling ribs for increasing the surface areas for transmission of heat from the rotor to the coolant, it is possible to dissipate larger quantities of heat so that higher-grade materials can be stressed up to their permissible limits and the grinding output can be substantially increased. Moreover, the ring elements are replaceable so that even in the case of an overload of the rotor with consequent excessive wear the ball mill can be restored to readiness for operation by quite simple measures.
These features provided by the invention can be carried into practice in different ways, of which those regarded as the most important are listed below.
In a preferred embodiment the rotor ring elements which have rotor agitator members cast integrally with them arranged on a cylindrical rotor guide tube which bounds the rotor cooling channels on their inside. A central tensioning unit which also serves as a return pipe for coolant is under tensional stress and supplies the compressive force necessary for compressing the rotor ring elements. In another version the rotor ring elements are pressed together by tension bolts between two flanges fitted at the two ends of the rotor guide tube. The tension bolts are under high tensional force in order to take up the thermal expansions of the rotor rings with as little change as possible in the joint pressure. The end surfaces of the ring elements which adjoin one another are protected from the outlet of coolant by packings or packing compound. The surfaces can also be soldered or stuck together by adhesive.
The rotor cooling ribs provided for sub-dividing the annular space arranged between the rotor guide tube and the rotor ring elements through which the coolant flows can extend helically so that they form a continuous helical rotor cooling channel which is a favourable from the point of view of cooling. They can be cast together directly with the ring element or the guide tube or can be formed by welding a section rod of any desired cross-section on to the ring element or the guide tube, or by shaping by metal cutting.
The stator can be built up similarly from ring elements which are aligned in an outer guide tube and form with this and radial ribs a stator cooling channel running helically. Here again the ring elements advantageously hold shaped cast-on agitator members and can be held together by tensioning means.
The sub-division of the rotor and of the stator into ring elements can also be carried out by having a ring element carrying cast-on agitator members following a ring element devoid of agitator members. Accordingly, a smooth ring element of the stator can be arranged opposite a ring element of the rotor carrying agitator members and vice versa. When replacing the worn ring elements it is possible better in this way to take into account their different degree of wear.
A further advantage of this construction of the rotor resides in that it affords the possibility of spacing the rotor agitator members in different ways. Thus it is possible by simple rotary offset of the ring elements to arrange their agitator members for example so that they are staggered or so that they extend in alignment parallel to the rotor axis.
An agitator ball mill constructed in this way makes it possible to choose very hard materials for the production of the ring elements with agitator members which can only be shaped using the casting or grinding process.
The front edge of the agitator members seen in the direction of rotation is exposed to particularly high fatigue impact stresses as a result of the continuous impact and churning of the grinding elements. In known constructions such agitator members were designed as replaceable hardened steel pins screwed into the rotor and stator cylinders. Here again the choice of the hardness of the metal was limited by the machinability of the fixture and the stresses occurring.
A further subsidiary feature of the present invention therefore provides that the agitator members should be designed with supporting lugs cast on to the ring elements, on the front edges of which viewed in the direction of rotation there are fixed working elements, the material of which is harder than that of the supporting lugs.
The replaceable working element is advantageously placed on the supporting lug or fixed on to this in the form of a rod of hard metal of round or other cross-section.
In view of the known difficulty of shaping hard metals, the rod-shaped working elements are preferably brazed, adhered or riveted.
The supporting lug has the task of offering the hard metal working element a supporting surface which is suitable for pressure stresses and to release the hard brittle material to a large extent from bending stress.
Since tensional stresses are lacking, brazed and adhered joints are particularly suitable. As a result of this oxide-ceramic materials lend themselves for lining the supporting lug, such as aluminium oxide (Al 2 O 3 ) or zirconium dioxide (ZrO 2 ) which have hardnesses of up to 2,300 in the Vickers scale. Finally, sintered mixtures, for example aluminium oxide with tungsten carbide, can be considered for the working elements to be adhered to the lugs.
At the base of the supporting lug as a further subsidiary development of the invention, the hard metal tool is inserted in a recessed bore. This avoids a known disadvantage of earlier constructions, in which the joints between agitator pins and cylindrical rotor surfaces are increasingly undermined by the action of the grinding elements.
As regards maximising cooling of the grinding operation, an attendant disadvantage is that highly wear-resistant materials, especially oxide ceramic materials, have a coefficient of thermal conductivity which is many times worse than that of steel.
This circumstance is countered in that the heat transfer surfaces of ring element to cooling medium on the rotor and stator are increased by the provision of radial ribs. The heat transfer surfaces between the working element and the supporting lug on the one hand and between the supporting lug and the ring element on the other have also been considerably enlarged as compared with the known contact surfaces of simple radial pins.
The advantages of a preferred form of the invention as described, compared with already known agitator ball mills, can be summarised as follows:
(a) The possibility of using highly wear-resistant hard material for wall elements, agitator members and working elements.
(b) Great strength of the working element fixture. The fixing means are exposed mainly only to pressure stresses.
(c) No danger of undermining the working element fixture on account of the recessing of the joint surfaces.
(d) Simple easy replacement of the ring elements.
(e) Good heat transfer from working element to supporting lug, from supporting lug to ring element and from ring element to the cooling surface.
(f) The possibility of the mechanical cleaning of the cooling surface after the ring elements have been dismantled.
BRIEF DESCRIPTION OF THE DRAWINGS
Several preferred embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which:
FIG. 1 shows in longitudinal section one form of agitator ball mill;
FIG. 2 shows likewise in longitudinal section a second form of mill;
FIG. 3 is a cross-section through a rotor ring element and a stator ring element according to FIGS. 1 and 2 with integrally cast agitator members;
FIG. 4 illustrates a detail of a rotor agitator member with supporting lug and working element fixed thereto;
FIGS. 4a-d are similar to FIG. 4 and each illustrate a detail of a rotor agitator member with a supporting lug and working elements fixed thereto having different shaped ends;
FIG. 5 is a section of the rotor agitator member of FIG. 4 taken along the line V--V;
FIG. 6 is a section of the rotor agitator member of FIG. 4, on a larger scale, the working element being riveted to the supporting lug;
FIG. 7 shows in cross-section part of a rotor and a stator ring element according to FIGS. 1 and 2 with symmetrical agitator members;
FIG. 8 shows in longitudinal section a stator of a third form of mill and illustrates several ways of fixing the agitator rods;
FIG. 9 shows in longitudinal section a third form of mill; and
FIG. 10 is a transverse sectional view of the rotor illustrated in FIG. 9.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In the various figures corresponding parts have been designated by corresponding reference numerals.
The agitator ball mill according to FIG. 1 consists of a rotor 1 mounted for rotation about a vertical axis, with outwardly projecting rotor agitator members 2 and a stationary stator 3 surrounding the rotor 1 and having inwardly projecting stator agitator members 4. The rotor 1 has rotor ring elements 6 carrying the rotor agitator members 2. The ring elements 6 are aligned on a rotor guide tube 5, they are compressed between the rotor end piece 7 and the socket 8 and are pressed against the stub 9 of the drive shaft. The pressure force necessary for this purpose is supplied for example by the rotor guide tube 5 designed as a tensioning unit and firmly connected with the stub of the drive shaft 9 and whose end plate 10 is connected via a number of screws 11 with the rotor end piece 7. By tightening the screws 11 the rotor guide tube 5 is placed under tensional stress and the rotor ring elements 6 are compressed. The housing cover 12 is firmly connected with the stator 3 via the end ring 13 by means of screws shown in chain-dotted lines.
Between the rotor 1 and the stator 3 is a grinding chamber 16 with the charge of grinding elements 50. The lower cover 12 has an inlet aperture 17 for the grinding stock, i.e. the material of product to be ground. A separating gap 18, suitably formed between the rotor end piece 7 and a hole in a plate 19 firmly mounted between the lower cover 12 and the lower end ring 13, has the task of preventing the grinding balls from coming out of the grinding chamber 16, but allowing the grinding stock to pass through practically without hindrance.
At the top end of the grinding chamber 16 there is a separating device 20 through which the ground product, but no grinding balls, can pass into the separating chamber 21. The latter is connected with an outlet aperture 22 for the ground product provided in the upper bearing cover 14.
The stator 3 has replaceable stator ring elements 24 carrying stator agitator members 4. These are aligned in the stator guide tube 23 which fast with its ends has flanges projecting radially outwards, namely a lower flange 25 and an upper flange 26. The stator ring elements 24 are held in position between the lower end ring 13 and the upper end ring 15, the lower flange 25 being connected by screws (indicated by chain dotted lines) with the lower end ring 13 and the lower cover 12 and the upper flange 26 being connected by screws (likewise indicated by chain dotted lines) with the upper end ring 15 and the upper bearing cover 14. Alternatively, the rotor and the stator ring elements could be compressed in known manner, as shown in FIG. 2, by a plurality of parallel tension bolts 111 or 140.
The rotor cooling device provided for cooling the rotor 1 has a feed channel 27, a rotor cooling channel 28, a plurality of connecting channels 29 joining these and a discharge channel 30 connected to the rotor cooling channel 28. The rotor cooling channel 28 extends helically around the rotor guide tube 5 and is bounded on one side by rotor cooling ribs 31 extending helically and projecting radially inwards and cast together with the rotor ring elements 6, and on the other side by the interior surfaces of the rotor ring elements 6. The discharge channel 30 extends centrally in the axial direction of the rotor 1 and passes through the drive shaft stub 9, whereas the feed channel 27 in the drive shaft stub 9 is formed as an annular channel surrounding the discharge channel 30.
The stator cooling device provided for cooling the stator 3 has a feed bore 32 provided in the upper flange 26, a discharge bore 33 provided in the lower flange 25 and a stator cooling channel 34 connected with these and extending helically around the stator ring elements 24. The cooling channel is bounded on one side by the stator cooling ribs 35 cast together with the stator ring elements 24 and extending helically and projecting radially outwards, and on the other side by the outer surfaces of the stator ring elements 24 and the inner surface of the stator guide tube 23.
The grinding stock to be processed is fed under pump pressure through the product inlet aperture 17 and the separating gap 18 into the grinding chamber 16, flows through this in a vertical direction to the separating device 20 and leaves the mill via the separating chamber 21 and the outlet aperture 22.
During the passage of the grinding stock its suspended solid particles are subjected in the activated charge of grinding elements to strong frictional and shearing stresses between the mill balls which are moving at high differential speeds. The grinding balls are activated by the rotor agitator members 2 rotating with the rotor 1 and the corresponding stator agitating members 4 on the stator 3.
The ring elements 6 and 24 surrounding the annular grinding chamber 16 are made of highly wear-resistant material. By means of the cooling ribs 31 and 35 the heat transfer surfaces between the coolant and the rotor 1 and the stator 3 are enlarged so that the rotor and stator cooling is sufficiently intensive despite the increased amount of heat occurring as a result of the high grinding output and the poorer thermal conductivity of the highly wear-resistant materials. The ring elements 6 and 24 can easily be fitted and just as easily dismantled. A seal can be provided between neighbouring ring elements by the use of sealing compound on their end surfaces or by brazing, to prevent the escape of coolant liquid into the grinding chamber 16.
There is shown in FIG. 9 another manner of dividing a rotor 201 and a stator 203. Parts of the device shown in FIG. 9 which are similar to parts of the device shown in FIG. 1 will be indicated by like numerals in the 200 series. The ring elements 206, 224 of the rotor 201 and the stator 203 respectively are arranged so that a ring element 206, 224 which carries cast-on agitator members 202, 204 follows a ring element 206, 224 which is devoid of agitator members. Accordingly, a smooth ring element 224 of the stator 203 can be arranged opposite a ring element 206 of the rotor 201 carrying agitator members 202 and vice versa.
FIG. 2 shows a variant of the design of the ring elements 106 and 124 and shows the way they are mounted in the guide tubes 105 and 123. The rotor ring elements 106 have a smooth cylindrical internal surface and the helical rotor cooling ribs 131, e.g. of round cross-section, are set on the rotor guide tube 105, being brazed or welded to it, and form together with the adjoining surfaces of the rotor ring elements 106 the rotor cooling channel 128, which extends helically. In a similar manner the stator ring elements 124 have a smooth cylindrical outer surface and the helically designed stator cooling ribs 135, e.g. of rectangular cross-section, are inserted in the stator guide tube 123, being brazed or welded to it, and form together with the adjoining surfaces of the stator ring elements 124 the helical stator cooling channel 134.
Naturally it is also possible for the rotor cooling ribs 131 to be of rectangular cross-section and for the stator cooling ribs 135 to be of round or other desired cross-section, and they may if appropriate be formed integrally with the relevant guide tube. Furthermore, it is possible in both forms according to FIGS. 1 and 2 to provide several helical rotor and/or stator cooling channels extending in the manner of a multiple-thread screw.
The cross-section of FIG. 3 shows the rotor agitator members 2 and the stator agitator members 4 according to FIGS. 1 and 2. Here the direction of rotation of the rotor is indicated by the arrow P. The agitator members 2 and 4 are cast integrally with their respective ring elements from highly wear-resistant materials, their cross-sections and moments of inertia increasing in the direction of the bottom in such a way that, firstly they are easy to produce having regard to casting technology, and secondly the bending stresses occurring during operation do not exceed maximum permissible values, and thirdly good heat conducting capacity is provided in the transition from the agitator member to the ring element. By sub-division of the rotor, as of the stator, into ring elements carrying agitator members, the possibility is provided, during installation to alter the arrangement of the agitator members to best advantage by simply turning round the ring elements. In this way, for example, instead of arranging the agitator members in an axis-parallel line as shown in FIGS. 1 and 2, they can be arranged alternately in two successive planes interrupted by gaps. See FIG. 10. FIG. 10 is a transverse sectional view of the rotor 201. Agitator members 202A are attached to a first ring element 206A and agitator members 202B are attached to an adjacent ring element, not seen in FIG. 10. By simple rotary offset of the ring element 206A and an adjacent ring element, the agitator members 202A and 202B are arranged in a staggered relationship as seen in FIG. 10.
Now, since the leading edge of an agitator member viewed in the direction of rotation is subjected to particularly high wear, it is advantageous to make this edge as a replaceable working element of a still harder material. Such a rotor agitator member 2 is shown in FIG. 4 and consists of a supporting lug 36 and a replaceable working element 37, the latter extending in the radial direction of the rotor. The front edge of the supporting lug 36 has a concave recess 38 visible in FIGS. 5 and 6 to serve as a supporting or fixing surface for the working element 37, which possesses the shape of a straight rod of, for example, round cross-section with a rounded to flat point. FIGS. 4a and 4b each illustrate a working element 37 with a flat end. FIG. 4c illustrates a working element 37 with a beveled end and FIG. 4d illustrates a working element 37 with a rounded end. This working element 37, which naturally can also be provided for the stator agitator members 4, is made of materials that are particularly hard, to the point of brittleness such as tungsten carbide or molybdenum carbide hard metals, or oxide ceramic and sintered metal materials, which do not lend themselves to machining and are suitable to withstand stress only in compression.
The method of fixing assumed in FIGS. 4 and 5 by brazing or adhesion into the recess 38 of the supporting lug 16 ideally meets these conditions. In the rotor ring element a recessed hole 39 is provided for holding the working element 37, so that erosion by the grinding elements and by ground product on its supporting base will not undermine its anchorage.
Instead of brazing or adhesive it is possible for the working element 37 to be fixed to the supporting lug 36 by means of one or more rivets. In FIG. 6 such a releasable connection is shown, in which the rivet 40 brazed into the working element 37 passes through a hole in the supporting lug 36 and is riveted to the other end of the latter. Accordingly the working element 37 is already provided during its production in the sintering process with the blind hole for taking the rivet 40, and this is brazed into the blind hole.
The combination of working-element-with-rivet corresponds to the condition of supply as a spare part for re-fitting a mill. For the user of the mill it is therefore very simple, by drilling out the head of the rivet to remove the old worn working element, to introduce the new working element with its rivet and then to peen the heads of the rivets in the blind holes of the supporting lugs.
The cross-section according to FIG. 7 shows how it is also possible for symmetrically constructed agitator members to be provided with replaceable working elements. The working elements 37 are then no longer placed radially, but at an acute angle to the radial position. This is necessary if the agitator unit during its movement is intended to impart to the grinding stock and the grinding elements not only tangential but also a radial movement component, which can be advantageous for certain purposes.
In FIG. 8 there is shown a further variant of the stator which comprises a ring element 224 consisting of a body strong enough to provide anchorages, which is produced for example of stainless wear-resistant material by the sand casting process, possesses on its outer surface cast-in helical stator cooling ribs 235 and is surrounded by an outer cooling jacket 223. The ring element 224 surrounds with its cooling jacket 223 one or more helical stator cooling channels 234 which communicate with the inlet aperture 32 and the outlet aperture 33. The cooling jacket 223 is firmly brazed at both ends to the ring element 224 so as to prevent the coolant from running out.
The ring element 224 is equipped with a number of cylindrical agitator rods 236, 237, 238, projecting inwards in a radial direction, three of which are shown with different anchorages, and which can be arranged between the rotor agitator members (not shown) in various planes at right-angles to the axis of the stator. They can be made of machinable and hardenable highly wear-resistant types of steel. For holding the agitator rods recessed bores are provided in the form of counter-bores 239 in the stator ring element 224 in order to prevent any undermining by the erosion effect of grinding elements and ground product at the base surfaces of the agitator rods. The agitator rod 237 is shown screwed into the stator cylinder 224 for example with an external thread. The agitator rod 236 is shown with a different anchorage namely a brazed-in threaded pin 240, which in turn is screwed into the stator cylinder. Finally the connection shown for the agitator rod 238 is also releasable in that the threaded pin 241 is welded into the stator cylinder and the agitator rod 238 has an internally threaded bore to receive the pin 241.
If desired the ring element 224 can have a smooth outer surface and the cooling ribs 235 of round or rectangular cross-section can be brazed or welded to the cooling jacket 223 or to the ring element 224, as has already been shown in relation to FIG. 2. Furthermore, instead of the agitator rods 236, 237, 238 it is possible to provide agitator members cast integrally with the ring elements such as those according to FIG. 3 or agitator members with supporting lugs and working elements like those according to FIGS. 4 to 7, as regards their construction and materials. | A heavy duty agitator ball mill for continuous grinding and dispersion of material suspended in a liquid has an upright rotor made of aligned rotor ring elements, mounted for rotation within a stator which preferably is also made up of aligned stator ring elements. Rotor and stator form a grinding chamber between them which holds a charge of grinding balls. Agitator members extend into the grinding chamber both from the rotor and from the stator. Both rotor and stator have cooling channels for flow of coolant, bounded in part by ribs formed on rotor and stator and hence promoting heat conduction. Working surfaces are of hard wearing materials as is made possible by the construction. The ring elements are readily replaceable, as are hard inserts of the agitator members. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to the protection of switches. More specifically, the present invention relates to the protection of a bidirectional switch upon occurrence of an overcurrent, resulting for example from a short-circuit in a load controlled in A.C. mode by the switch.
[0003] 2. Discussion of the Related Art
[0004] [0004]FIGS. 1A and 1B illustrate a known method for protecting a bidirectional switch for controlling an A.C. load against overcurrents.
[0005] [0005]FIG. 1A schematically and partially illustrates a load 1 series-connected with a bidirectional switch 2 across an A.C. voltage source 3 . Bidirectional switch 2 is formed by the anti-series connection, between two terminals A and C, of two insulated-gate bipolar transistors (IGBT) 4 and 5 . “Anti-series” means that IGBT transistors 4 and 5 are in series and that their junction point is a common emitter point. Each terminal A and C is then connected to the collector of one of transistors 4 and 5 . For clarity, the collector of transistor 4 is designated in the following description of FIG. 1 as “A” and the collector of transistor 5 is designated as “C”. The emitter of each of transistors 4 and 5 is connected to its respective collector A, C by a respective diode D 1 , D 2 . Each diode D 1 , D 2 is in antiparallel with the junction of its associated transistor 4 , 5 . Collector A of transistor 4 is connected to a supply terminal of load 1 . Collector C of transistor 5 is connected to a terminal of source 3 , non-connected to load 1 . A circuit 6 for controlling and protecting transistor 4 is connected between its gate G 1 and its collector A. Similarly, for transistor 5 , another control and protection circuit 7 is connected between its gate G 2 and its collector C. The two protection circuits 6 and 7 are identical.
[0006] [0006]FIG. 1B schematically and partially illustrates a protection circuit ( 6 or 7 , FIG. 1A) connected between a collector A or C and a gate G 1 or G 2 . A control block 10 (CTRL) comprises two supply terminals respectively connected to a high supply rail Vcc and a low supply or ground rail GND connected to the emitter of protected transistor 4 or 5 . An output terminal of block 10 is connected to an end of a resistor 11 having another end forming the output terminal of protection circuit 6 , respectively 7 , connected to gate G 1 , respectively, G 2 , of transistor 4 , respectively 5 . An input terminal of block 10 is connected to an output terminal OUT of a comparator 12 . Two supply terminals of comparator 12 are respectively connected to high supply rail Vcc and low supply rail GND. An inverting input IN 1 of comparator 12 is connected to a reference D.C. voltage source (V) 13 . A non-inverting input IN 2 of comparator 12 is connected to high supply rail Vcc, via a biasing resistor 14 . Non-inverting input IN 2 is also connected to the anode of a diode 15 having its cathode connected to collector A, respectively C, of protected unidirectional switch 4 , respectively 5 . Circuits 6 , respectively 7 , ensure their protection function by controlling gate G 1 , respectively G 2 , of transistor 4 , respectively 5 , according to the result of the comparison, by comparator 12 , of the current value of the collector-emitter voltage with voltage reference V provided by source 13 .
[0007] The protection circuit of FIG. 1B enables controlling collector-emitter voltage Vce across protected transistor 4 or 5 by means of comparator 12 . Given the current-vs.-voltage characteristic of a transistor, a voltage Vce unusually high as compared to the reference set by source 13 corresponds to the occurrence of an overcurrent, linked to a malfunction of load 1 or of source 3 . Diode 15 is a protection diode intended to protect non-inverting (+) input IN 2 of comparator 12 , especially when protected transistor 4 or 5 is off.
[0008] A disadvantage of the structure previously described in relation with FIGS. 1A and 1B is the need to repeat twice a protection circuit of a one-way switch to obtain a bidirectional switch protection circuit.
[0009] Another disadvantage of the previous structure is that protection diodes 15 of circuits 6 , 7 must be able to hold a high voltage, especially when switch 2 is off. High-voltage diodes are relatively complex and bulky to make in integrated form.
[0010] It has previously been considered that bidirectional switch 2 is formed of the anti-series connection of two IGBT transistors, each being associated with a free wheel diode in anti-parallel. However, the same disadvantages are encountered if the transistors are of MOS type.
[0011] [0011]FIG. 2 schematically and partially illustrates another known embodiment in which bidirectional switch 2 is formed of the antiparallel connection of two IGBT or MOS transistors of same conduction type T 1 and T 2 , each transistor T 1 , T 2 being in series with a respective rectifying diode D 3 , D 4 . For clarity, the connection of switch 2 in series with load 1 across A.C. source 3 described in relation with FIG. 1A is indicated only by the mentioning of terminals A and C in FIG. 2. Terminal A is connected to the anode of diode D 3 , the cathode of which is connected to the collector of transistor T 1 . Terminal A is also connected to the cathode of diode D 4 , the anode of which is connected to the emitter of transistor T 2 . Terminal C is connected to the emitter of transistor T 1 and to the collector of transistor T 2 .
[0012] Protection circuit 17 of switch 2 here is comprised of two separate comparators 121 and 122 . Non-inverting (+) input IN 21 of comparator 121 is connected to the anode of a diode 151 having its cathode connected to the collector of transistor T 1 (cathode of diode D 3 ). The inverting (−) input IN 11 of comparator 121 receives a reference voltage Vref+, positive with respect to the ground defined by one of the two terminals of switch 2 , for example, terminal C, and provided by a voltage source 131 .
[0013] Non-inverting (+) input IN 22 of comparator 122 is connected to the cathode of a diode 152 having its anode connected to the emitter of transistor T 2 (anode of diode D 4 ). Inverting (−) input IN 12 of comparator 121 receives a reference voltage Vref−, negative with respect to ground GND and provided by a second voltage source 132 .
[0014] The respective outputs OUT 1 and OUT 2 of comparators 121 , 122 are connected to input terminals of a control circuit (not shown) driving, generally via resistors (not shown), gates G 1 and G 2 of transistors T 1 and T 2 .
[0015] The supply of comparator 121 is ensured by a source 133 of a positive supply voltage +Vcc connected between a supply terminal of comparator 121 and ground GND. Similarly, a source 134 of a negative supply voltage −Vcc is connected between a supply terminal of comparator 122 and ground GND.
[0016] The operating principle of protection circuit 17 of FIG. 2 is similar to that of a protection circuit 6 , 7 of FIGS. 1A and 1B, voltage Vce of each transistor being compared with a respective reference Vref+, Vref− set by respective source 131 or 132 . Diode 151 , 152 of each portion of circuit 17 dedicated to the protection of one of the two switches unidirectional in current T 1 , D 3 and T 2 , D 4 is homologous to diode 15 of each circuit 6 , 7 of FIG. 1.
[0017] A disadvantage of such a structure is the need to provide two voltage reference supply sources 133 and 134 .
[0018] Another disadvantage of such a structure is the presence of high-voltage diodes 151 and 152 .
[0019] According to another known method, a read resistor is introduced in series with the load and the bidirectional switch and the occurrence of overcurrents across this resistor is detected. As compared to the diagram of FIG. 2, the two non-inverting inputs of comparators 121 and 122 are then connected to the junction point of the switch and the detection resistor, the other terminal of this resistor being connected to ground, which corresponds to one of the terminals of application of the A.C. supply voltage. Diodes 151 and 152 are then no longer necessary.
SUMMARY OF THE INVENTION
[0020] An object of the present invention is to provide a circuit for protecting a bidirectional switch which overcomes the disadvantages of conventional circuits and which, especially, is more easily integrable.
[0021] The present invention also aims at providing a circuit such that it does not use a negative independent power supply.
[0022] The present invention also aims at providing such a circuit that is common to the two one-way switches forming it.
[0023] To achieve these and other objects, the present invention provides a circuit for detecting an overcurrent in an element run through by an A.C. supply current, comprising detecting a variation in the voltage across the element beyond two predetermined thresholds, said circuit comprising:
[0024] a first comparator, assigned to the halfwaves of a first sign of the A.C. power supply, receiving on a reference input a first reference voltage setting a first one of said thresholds;
[0025] a second comparator, assigned to the halfwaves of a second sign of the A.C. power supply, receiving on a reference input a second reference voltage setting a second one of said thresholds; and
[0026] an input stage providing, to respective interconnected read inputs of the comparators, a voltage proportional to said voltage across said element, said stage comprising at least one first resistive element introducing a voltage drop between a first one of the terminals of the element and said read inputs.
[0027] According to an embodiment of the present invention, the circuit is supplied between a high supply rail and a ground to which is connected one of said terminals of the element not connected to said first resistive element.
[0028] According to an embodiment of the present invention, the input stage comprises:
[0029] a first series connection of two low-voltage diodes, between said high rail and the ground, the anode of a first diode being grounded while the cathode of a second diode is connected to the high rail; and
[0030] a second series connection, between said high rail and said ground, of at least two resistive elements, the midpoints of said first and second series connection being interconnected to said read inputs of said first and second comparators.
[0031] According to an embodiment of the present invention, said first and second reference voltages are set by at least one resistive dividing bridge formed between said high rail and the ground.
[0032] According to an embodiment of the present invention, said first and second reference voltages are set by a single resistive dividing bridge formed of a series connection, between said high rail and said ground, of three resistive elements, said predetermined thresholds being respectively sampled across the intermediary resistor of the bridge.
[0033] According to an embodiment of the present invention, outputs of the first and second comparators are combined.
[0034] According to an embodiment of the present invention, the outputs are combined by a logic two-input OR gate.
[0035] According to an embodiment of the present invention, the that conducts an A.C. supply current is a bidirectional switch.
[0036] According to an embodiment of the present invention, the element conducting an A.C. supply current is a resistor.
[0037] The present invention also provides a circuit of protection against an overcurrent of a bidirectional switch in the on state, run through by an A.C. supply current.
[0038] According to an embodiment of the present invention, said resistor is in series with said switch.
[0039] The foregoing objects, features, and advantages of the present invention will be discussed in detail in the following non-limiting description of specific embodiments in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] [0040]FIGS. 1A and 1B, previously described, illustrate a first conventional mode of switch protection against overcurrents;
[0041] [0041]FIG. 2, previously described, illustrates another conventional mode of switch protection against overcurrents;
[0042] [0042]FIG. 3 schematically and partially illustrates an embodiment of the protection of a bidirectional A.C. load control switch against overcurrents according to the present invention; and
[0043] [0043]FIG. 4 schematically and partially illustrates another embodiment of the of a bidirectional A.C. load control switch against overcurrents according to the present invention.
DETAILED DESCRIPTION
[0044] [0044]FIG. 3 schematically and partially illustrates an embodiment of the present invention. A load 21 is connected in series with a bidirectional switch 22 across an A.C. voltage source 23 . Bidirectional switch 22 is a switch with two input/output terminals A and C and two control terminals G 1 and G 2 . For example, terminal A is connected to a supply terminal of load 21 , terminal C is connected to a terminal of source 23 , another terminal of which is connected to another supply terminal of load 21 . Hereafter, terminal C forms the low voltage reference or ground point. The structure of switch 22 may be identical to that of switch 2 of FIG. 1A.
[0045] According to the embodiment illustrated in FIG. 3, switch 22 is formed of the anti-parallel connection of two switches unidirectional in current. Each unidirectional switch is formed of the series connection, between terminals A and C, of a diode D 3 , D 4 and of a transistor T 1 , T 2 .
[0046] The series connection in each branch of switch 22 of a transistor T 1 , T 2 with a respective diode D 3 , D 4 may be similar to that of FIG. 2.
[0047] According to a preferred embodiment illustrated in FIG. 3, each collector of a transistor T 1 , T 2 is connected to the cathode of its respective rectifying diode D 3 , D 4 .
[0048] Transistors T 1 , T 2 of the two one-way switches are MOS transistors of the same conduction type or, for example, insulated-gate bipolar transistors (IGBT).
[0049] According to the present invention, switch 22 is protected against overcurrents by a single protection circuit 24 with two inputs, respectively connected to terminals A and C, and two output terminals, respectively connected, preferably via a respective protection resistor 46 , 47 , to control terminals G 1 and G 2 of switch 22 . More specifically, circuit 24 comprises a detection circuit 25 and a control circuit (CTRL) 26 .
[0050] According to the present invention, detection circuit 25 comprises a resistor 30 having one end forming the input of protection circuit 24 connected to terminal A. Another end of resistor 30 is connected to the midpoint 31 of a series connection, between a high supply rail Vdd and the ground, of two low-voltage diodes 32 and 33 . The anode of diode 33 is grounded while the cathode of diode 32 is connected to rail Vdd.
[0051] Midpoint 31 is connected to the midpoint of a series connection, also between high rail Vdd and the ground, of two resistors 34 and 35 . Midpoint 31 is also connected, on the one hand, to an inverting (−) read input 36 of a first comparator 37 and, on the other hand, to a non-inverting (+) read input 38 of a second comparator 39 .
[0052] A non-inverting (+) input 40 of comparator 37 forms a reference input connected, via a resistor 41 , to high rail Vdd. Output COMP 1 of comparator 37 is connected to a first one of two inputs of an OR gate 42 . An inverting (−) input 43 of comparator 39 forms a reference input connected, via a resistor 44 , to ground. Output COMP 2 of second comparator 39 is connected to a second input of gate 42 .
[0053] Preferably, an intermediary resistor 45 is connected between the non-inverting (+) input 40 of first comparator 37 and the inverting (−) input 43 of second comparator 39 . The values of resistors 41 , 44 , and 45 of reference inputs 40 , 43 are adjusted so that the high threshold of first comparator 37 is greater than the low threshold of second comparator 39 . As an alternative, series resistors 41 , 44 , and 45 may be replaced with resistive voltage dividers respectively assigned to inputs 40 and 43 of comparators 37 and 39 . An advantage of the embodiment of FIG. 3 however is to link together the operating range thresholds so that they undergo the same possible drifts, resistor 45 guaranteeing the separation between thresholds.
[0054] The output of gate 42 forms the output of detection circuit 25 and is connected to an input of control circuit 26 .
[0055] For simplification and clarity, as will be understood by those skilled in the art, it has been omitted to show the supplies Vcc of comparators 37 and 39 and of control circuit 26 in FIG. 3.
[0056] In normal operation, load 21 conducts an A.C. current predetermined by its nature and/or its operating mode, the A.C. voltage between terminals A and C of on switch 22 is very small (due to the series resistance of switch 22 in the on state) as compared to the A.C. voltage provided by source 23 . The values of the different input resistances 30 , 34 , and 35 are set so that the voltage signal applied on inverting 36 and non-inverting 38 input of the first 37 and second 39 comparators, respectively remains within a voltage range between the thresholds set by resistors 41 , 44 , and 45 . Then, the voltage signal transmitted by input resistor 30 is such that, for both comparators 37 and 39 , the low-voltage signal on their non-inverting input is always (in normal operation) greater than the low-voltage signal on their inverting input. Outputs COMP 1 and COMP 2 then take a same logic state. Detection circuit 25 thus provides control circuit 26 with a signal of a first logic value. Control circuit 26 is designed to ensure, as a response to this first logic value, the holding of switch 22 in the on state.
[0057] Upon occurrence of an overcurrent, generally linked to a malfunction of load 21 or of source 23 , as soon as the image of the voltage between terminals A and C of switch 22 comes out of the acceptable voltage range set by the thresholds of comparators 37 and 39 and an attenuation coefficient linked to the presence of resistors 30 , 34 , and 35 , one of comparators 37 and 39 switches states. This low-voltage image is obtained due to the arrangement of the input stage formed of resistors 30 , 34 , and 35 and of diodes 32 and 33 which are used to limit the voltage at midpoint 31 within a range from Vdd+VD 32 to GND−VD 33 , when switch 22 is off, VD 32 and VD 33 begin the voltage drop introduced by the respective diode 32 and 33 . In the case of a positive halfwave, the detection is performed in the case where the high threshold of reference input (+) 40 is exceeded. In the case of a negative halfwave, the detection is performed in the case where it is fallen below the low threshold of the reference input 43 (−). The corresponding switching of a single input of gate 42 causes a switching of the output of this gate. Control circuit 26 then receives a second logic value complementary to the first one. Control circuit 26 is designed to modify, as a response to this second logic value, the control of gates G 1 and G 2 to turn off switch 22 .
[0058] An advantage of the present invention is to provide a circuit of protection against overcurrents of a bidirectional switch controlling an A.C. load easier to integrate than known circuits. Indeed, the detection circuit according to the present invention, conversely to known circuits, requires no additional negative power supply.
[0059] Further, one and the same circuit connected across a bidirectional switch advantageously enables protecting two controllable one-way switches forming it.
[0060] Another advantage of the present invention is that the detection and protection circuits according to the present invention are advantageously usable with anti-parallel type switches as well as with anti-series type switches. For an anti-series assembly, a shunt should however be used (for example, a resistor) between the two switches.
[0061] Further, the detection circuit according to the present invention may advantageously be used with a so-called MBS-type bidirectional switch which exhibits the antiparallel structure of the drawing, in which the cathode of diode D 3 , D 4 is connected to the collector of the associated transistor T 1 , T 2 . On the contrary, the known detection and protection circuit of FIG. 2 could not be used with such an MBS bidirectional switch. Indeed, for protection circuit 17 of FIG. 2, input terminal IN 22 of comparator 122 must be connected to the emitter of transistor T 2 . In the case of a bidirectional MBS switch, such a connection results in directly connecting terminal A and the anode of diode 152 . As illustrated in FIG. 2, input IN 22 must be protected by interposing diode D 4 between terminal A and the anode of diode 152 . This has a double advantage, on the one hand, that the circuit according to the present invention may be used with more switches than in the state of the art. On the other hand, MBS-type switches are easier to form in terms of integration.
[0062] The values of the different resistances 30 , 34 , 35 , 41 , 44 , and 45 are set, on the one hand, to enable detection of an overcurrent according to the previously-discussed principles. On the other hand, the values of resistances 30 , 34 , and 35 are also set to limit, when switch 22 is off, the parallel leakage current of switch 22 as well as the power dissipated in resistors 30 , 34 , 35 , 41 , 44 , and 45 .
[0063] As a specific example of implementation, the following values will be set for the resistors:
[0064] resistor 30: 1. 10 6 Ω;
[0065] resistor 34: 1.3. 10 6 Ω;
[0066] resistor 35: 360. 10 3 Ω;
[0067] resistor 41: 47. 10 3 Ω;
[0068] resistor 44: 4.3. 10 3 Ω; and
[0069] resistor 45: 13. 10 3 Ω.
[0070] In this case, for an A.C. voltage supplied by source 23 of 220 V, the thresholds of comparators 37 and 39 are on the order of 4 volts and 1 volt, respectively, which enables detecting the occurrence of an overcurrent as soon as the collector-emitter voltage Vce across a transistor T 1 or T 2 exceeds, in absolute value, 7 volts.
[0071] Further, diodes 32 and 33 are low-voltage diodes. They are thus easier to form and less bulky in integrated form than homologous high-voltage diodes ( 15 , FIG. 1B) of known circuits. Indeed, the diodes according to the present invention are connected to low voltage power supply Vdd. Conversely to protection diodes of known circuits, they are not intended to protect the protection circuits when the switch is off, that is, when the voltage thereacross is high. Further, upon occurrence of an overcurrent, diodes 32 and 33 are protected in current by input resistor 30 .
[0072] As will be understood by those skilled in the art, the detection circuit of according to the present invention is not limited to a detection of an overcurrent across a bidirectional switch.
[0073] Thus, FIG. 4 schematically and partially illustrates another embodiment of the protection of a bidirectional switch 22 for controlling an A.C. load 21 supplied by an A.C. source 23 . This embodiment differs from that of FIG. 3 in that protection circuit 24 according to the present invention now is connected across a resistor 70 series-connected with switch 22 and load 21 across source 23 . The ground indicated in FIG. 4 as corresponding to terminal C may however, as an alternative, correspond to terminal A.
[0074] Of course, the present invention is likely to have various alterations, modifications, and improvements which will readily occur to those skilled in the art. In particular, the present invention has been described hereabove as applied to a specific bidirectional switch. However, the present invention also applies to a bidirectional switch formed of the anti-series connection of two controllable switches unidirectional in current connected in anti-parallel to respective free wheel diodes. Further, it has been considered in the foregoing description that the one-way switches are IGBT transistors. The one-way switches may however be N- or P-channel MOS transistors, conmected in series or in antiparallel. Further, specific circuit elements may be replaced with functionally equivalent elements. In particular, it will be within the abilities of skilled in the art to select a control circuit 26 capable of appropriately driving of the control terminals of switch 22 . Similarly, the comparison function described in relation with comparators 37 and 39 may be carried out by any appropriate circuit.
[0075] Further, it has been considered in the description of the present invention that the switch controls the supply of a load placed in series with the switch. However, the switch could be placed in parallel with the load and control its supply according to a predetermined cycle, for example, according to the voltage thereacross.
[0076] Moreover, load 21 may be any A.C.-supplied bidirectional load. In particular, the load may especially be a resistive element, for example, in lighting or heating devices.
[0077] Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and the scope of the present invention. Accordingly, the foregoing description is by way of example only and is not intended to be limiting. The present invention is limited only as defined in the following claims and the equivalents thereto. | A circuit for detecting an overcurrent in an element in which an A.C. supply current flows, including a first comparator, assigned to the halfwaves of a first sign of the A.C. power supply, receiving on a reference input a first reference voltage setting a first one of the thresholds, a second comparator, assigned to the halfwaves of a second sign of the A.C. power supply, receiving on a reference input a second reference voltage setting a second one of said thresholds, and an input stage providing, to respective interconnected read inputs of the comparators, a voltage proportional to said voltage across the element, the stage including at least one first resistive element introducing a voltage drop between a first one of the terminals of the element and the read inputs. | 7 |
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Application No. 61/443,794, filed Feb. 17, 2011, the entirety of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates generally to fluid flow control and, in particular, to an improved flow control valve assembly.
BACKGROUND
[0003] Control valves of the type to which this invention pertains are used to control or throttle high pressure fluid flows such as applications that involve steam flow.
SUMMARY OF THE INVENTION
[0004] The present invention provides a new and improved control valve assembly for controlling or throttling the flow of fluid such as steam.
[0005] According to one preferred embodiment of the invention, a flow control valve is provided that includes a valve housing that defines a valving chamber. A port member mounted within the valving chamber receives a reciprocally movable piston/spool assembly. The relative position of the piston/spool assembly within the port member determines the flow rate of fluid through the valving chamber. An actuator is used to move the piston/spool assembly within the port member. The piston/spool assembly is engageable with a valve seat which, when engaged, blocks fluid flow through the valving chamber. An actuating member is operatively connected to the piston/spool assembly and can move the assembly in opening and closing directions within the port member.
[0006] According to the invention, the piston/spool assembly includes a piston body that defines a seal recess for receiving an annular seal. The seal sealingly engages an inside surface of the port member and inhibits fluid flow between the piston/spool assembly and the inside surface of the port member. The assembly also includes a bonnet that is received by the piston body and is engageable with the annular seal. The seal, the bonnet and the actuating member are arranged such that when the actuating member moves the piston/spool assembly into sealing contact with the valve seat, forces are exerted on the annular seal by the bonnet which cause increased sealing engagement between the inside surface of the port member and the annular seal.
[0007] In the exemplary embodiment, the bonnet applies compression forces to the seal which, in turn, causes the seal to expand in the radial direction, thus increasing its sealing engagement with the inside surface of the port member.
[0008] According to a further feature of this embodiment, the actuating member abutably engages the bonnet and is attached to the associated piston body with a connection that allows relative movement between the actuating member and the piston body. With this preferred embodiment, when the actuating member moves the piston/spool assembly into sealing contact with the valve seat, the bonnet, by virtue of the lost motion connection (between the actuating member and the piston body) moves relative to the piston body a slight amount, thus applying forces to the seal that is captured between the bonnet and the piston body. These forces cause at least a portion of the annular seal to expand in the radial direction, thus increasing the sealing contact between the annular seal and the inside surface of the port member.
[0009] With the disclosed embodiment, the annular seal engages the inside surface of the port member with increased engagement force only when the piston/spool assembly is moved to a position where it sealingly engages the associated valve seat. When the actuating member moves the piston/spool assembly away from the valve seat, the compression forces applied by the bonnet are released, thereby relaxing the seal and reducing the friction between the seal and the inside surface of the port member. As a result, reciprocal movement of the piston/spool assembly within the port member is not resisted by a substantial frictional force that would be present if the seal were permanently preloaded to exert the substantial sealing engagement that is present when the piston/spool assembly is moved to its valve seat engaging position.
[0010] According to a further feature of the invention, a gap is preferably maintained between the bonnet and the piston body. The gap, in cooperation with pressure balancing passages equalizes fluid pressures on the piston/spool assembly.
[0011] The preferred method of controlling the flow rate of high pressure fluid in a control valve, includes the steps of providing a valve housing that defines a valving chamber, providing a port member within the valving chamber that receives a reciprocally movable piston/spool assembly. In addition, the method provides a valve seat engageable by the piston/spool assembly for blocking flow through the valving chamber. Enhanced sealing between the piston/spool assembly and an inside surface of the port member is provided by moving the overall assembly within the port member with an actuating member. The actuating member is allowed to move relative to a portion of the piston/spool assembly in order to allow another portion of the piston/spool assembly to move relative to the first portion thereby applying forces to the seal. This causes the seal to expand radially and to increase its sealing engagement with the inside surface of the port member.
[0012] With the disclosed invention, sealing between a piston/spool assembly and its associated port member are substantially increased when the piston/spool assembly engages its associated valve seat. When the piston/spool assembly is in a position other than its valve seat engaging position, the seal is relaxed. With the seal relaxed, friction between the seal and port member is reduced. Consequently, the relative movement between the piston/spool assembly and the port member is not substantially resisted by the engagement of the seal with the port member. Thus, the control of the fluid flow rate through the valving chamber is substantially improved.
[0013] Additional features of the invention will become apparent and a fuller understanding obtained by reading the following detailed description made in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a fragmentary sectional view of a prior art valve assembly;
[0015] FIG. 1A illustrates an overall view of the type of valve to which this invention pertains;
[0016] FIG. 2 is a fragmentary sectional view of a valve assembly constructed in accordance with a preferred embodiment of the invention;
[0017] FIG. 3 is a side devotional view of a piston assembly and associated sleeve constructed in accordance with a preferred embodiment of the invention;
[0018] FIG. 4 is a sectional view of the assembly shown in FIG. 3 , as seen from the plane indicated by the line 4 - 4 in FIG. 3 ; and
[0019] FIG. 5 is an exploded view of the assembly shown in FIG. 3 .
DETAILED DESCRIPTION
[0020] FIG. 1 illustrates, in sectional view, a portion of a prior art valve assembly 10 . The valve assembly is termed a balance seal or flow control valve which is used, for example, in the steam industry to control or throttle steam flow. FIG. 1A illustrates an overall view of the type of valve shown in FIG. 1 and that this invention pertains to.
[0021] The valve assembly 10 includes a valve housing 12 , which includes a flow passage 20 having an inlet end 20 a and an outlet end 20 b. In the illustrated construction, the inlet and outlet ends 20 , 20 b define respective bolt flanges 22 a, 22 b to which suitable piping (not shown) is fastened in a known way.
[0022] The flow of fluid (i.e., steam) from the inlet 20 a to the outlet 20 b is controlled by a valving assembly indicated generally by the reference character 30 . The valving assembly 30 includes a ported sleeve 32 that is fixed within a valve chamber 20 c also defined by the valve housing 12 . In the illustrated construction, the sleeve 32 may be captured within the valve body between a step 40 and a cylindrical spacer 42 . A valve cap 50 exerts a clamping force on the sleeve 32 . The valve cap 50 is secured by a plurality of studs 54 that extend upwardly from the valve housing 12 , extend through bores 56 in the cap 50 and receive suitable nuts 58 which retain the cap in position and apply a clamping force to the cylindrical spacer 42 .
[0023] A flow control piston or spool 60 is reciprocally movable within the sleeve 32 and when it is moved upwardly, (as viewed in FIG. 1 ), it uncovers one or more ports 32 a defined by the sleeve 32 . The more ports 32 a that are uncovered, the greater the fluid flow between the inlet 20 a and the outlet 20 b. The piston/spool 60 is reciprocally movable by an operating stem 66 is which operatively attached to an actuator, one of which is shown in Appendix 1. The actuator is conventional and does not form part of the present invention.
[0024] FIG. 2 illustrates a valve assembly 10 ′ constructed in accordance with a preferred embodiment of the invention. The valve assembly 10 ′ constitutes a substantial improvement over the valve assembly 10 shown in FIG. 1 . To facilitate the explanation, components in FIG. 2 that are the same or perform similar functions as components in FIG. 1 will be given the same reference character followed by an apostrophe.
[0025] The valve assembly 10 ′ includes a valve housing 12 ′ that defines a flow passage 20 ′ having an inlet end 20 a ′, an outlet end 20 b ′ and a valve chamber 20 c ′. A valving assembly 30 ′ constructed in accordance with a preferred embodiment of the invention in located in the valve chamber 20 c ′ and controls the flow of fluid i.e. steam, from the inlet 20 a ′ to the outlet 20 b ′. The valving assembly 30 ′ includes a ported sleeve 32 ′ that is clamped between the seat or step 40 ′ and the annular spacer 42 ′.
[0026] The valving assembly 30 ′ includes a piston/spool assembly 60 ′ constructed according to a preferred embodiment of the invention. The piston/spool assembly 60 ′ is reciprocally movable within the port sleeve 32 ′ and controls or throttles fluid flow between the inlet 20 a ′ and outlet 20 b ′. It should be apparent that the more ports 32 a ′ that are exposed as the piston/spool assembly 60 ′ is raised (as viewed in FIG. 2 ), the greater the flow of fluid, i.e., steam through the valve housing 12 ′. Referring also to FIGS. 4 and 5 , when the piston/spool assembly 60 ′ is moved to its lowermost position (as viewed in FIG. 2 ), the lower annular edge 61 of the piston/spool assembly 60 ′ contacts and sealingly engages an angled seat surface 40 a defined by the seat 40 ′ (shown best in FIG. 5 ). In this position, the piston/spool assembly 60 ′ blocks flow through the passage 20 .
[0027] The piston assembly 60 ′ includes a piston body 76 having an upper, reduced diameter section 76 a which defines an open-ended groove for receiving an annular seal 78 . A compression bonnet 80 is at least partially received by the reduced diameter section 76 a of the piston body 76 and includes a downwardly depending (as viewed in FIG. 4 ) axial flange 80 a. The lower edge of the axial flange 80 a abuts the upper (as viewed in FIG. 4 ) radial face of the annular seal 78 and can exert compression forces on the seal when the bottom edge 61 of the piston body 76 is moved into sealing contact with the sealing surface 40 a of the seat 40 ″.
[0028] Referring to FIGS. 3-5 , the piston/spool assembly 60 ′ includes a central bore 70 which slidably receives a reduced diameter portion 66 a ′ of the operating stem 66 ′. The reduced diameter portion 66 a ′ defines a step 72 , the function of which will be described
[0029] When the piston body 76 is in contact with seat 40 ′ and the stem 66 ′ continues to be urged downwardly by its associated actuator, the step 72 applies a downward directed force to the top of the compression bonnet 80 and urges it downwardly. This downward force causes the axial rim 80 a of the bonnet 80 to exert a compression force on the annular seal 78 and may reduce its axial dimension (depending on the material composition of the seal 78 ). The compression of the seal 78 in the axial direction causes the seal to expand radially and thus create a tight sealing engagement between the upper part 80 a of the piston body 76 and the inside surface of the sleeve 32 ′, thus inhibiting leakage between the piston body 76 and the sleeve 32 .
[0030] In the preferred embodiment, the piston body 76 includes pressure-balancing bores 88 and the compression bonnet 80 includes arcuate slots 80 b for equalizing fluid pressure above and below the piston assembly 60 ′ when the piston body 76 is in sealing contact with the associated seat 40 ′. In this position, fluid flow from the inlet 20 a ′ to the outlet 20 b ′ is blocked. Absent the balancing bores 88 and openings 80 b in the bonnet 80 , full inlet pressure would urge the piston body 76 upwardly, which would tend to move the piston assembly 60 ′ toward an open position. The communication of inlet fluid pressure to the top surface of the bonnet/ 80 (as viewed in FIG. 4 ) balances the force on the piston assembly 60 ′.
[0031] With the disclosed construction, sealing engagement of the piston body 76 to the sleeve 32 ′ is substantially enhanced without detrimentally affecting the ability of the piston assembly 60 ′ to be reciprocally moved within the sleeve 32 ′ by the associated actuator. Downward movement of the stem 66 ′ (by an associated actuator) causes compression of the annular seal 78 once the bottom edge or skirt 61 of the piston body sealingly contacts the associated seat 40 ′. As discussed above, compression of the annular seal 78 causes radial expansion, thus causing a tight engagement between the seal 78 and the inside surface of the ported sleeve 32 ′. However, when the piston body 76 moves off the seat 40 ′, as the stem 66 ′ is raised upwardly, the upward movement of the bonnet 80 ′ (which depending on the material from which the seal 78 is made may be very slight) relaxes the seal 78 , thus decreasing the force necessary to reciprocally slide the piston assembly 60 ′ within the sleeve 32 ′ to achieve a desired flow rate. With the disclosed invention, when the piston body 76 is off its seat 40 ′, the piston assembly 60 ′ can be moved by the actuator relatively easily in order to control the flow rate through the valve. In normal operation, the actuator may continually move or dither the piston assembly 60 ′ within the sleeve in order to achieve a desired flow rate. In the prior art, the piston seal was fully loaded at all times, thus requiring significant actuator force to reciprocally move the piston within the sleeve even when the piston disengaged the associated seat.
[0032] It should be noted here, that the connection of the stem 66 ′ with the compression bonnet 80 ′ and piston body 76 ′ resembles a lost motion connection. In particular, the narrow diameter portion 66 a ′ of the stem 66 ′ can move relative to the piston body 76 a predetermined amount in order to relax and compress the seal 78 . The distal end 66 b of the stem 66 ′ is threaded and receives a nut 90 by which an initial pre-load is preferably applied to the seal 78 by the compression bonnet 80 , to initially compress the seal 78 a minimal amount. When the stem moves downwardly from its relaxed position to its full force applying position shown in FIG. 4 , the compression bonnet 80 preferably moves downwardly a slight amount thus slightly reducing the gap “G” between the underside of the bonnet 80 and the top of the piston body 76 to compress the seal 78 and effect the substantial sealing engagement between the seal 78 , the inside surface of the ported sleeve 32 ′ and the upper portion 76 a of the piston body 76 . It is should be noted here that the compressibility of the seal will determine the extent of movement of the compression bonnet 80 with respect to the piston body 76 . Accordingly, the amount that the gap “G” is reduced when the compression bonnet 80 is in the force applying position shown in FIG. 4 , will be dependent on the compressibility of the seal material. In the preferred embodiment, however, it is preferred that the material for the seal and the gap “G” is chosen such that there is always some gap between the compression bonnet 80 and the piston body 70 when the seal 78 is fully compressed.
[0033] As seen best in FIG. 5 , a cotter pin 92 is used to lock the relative rotated position of the preload adjustment nut 90 on the threaded end 66 b of the stem 66 ′.
[0034] In the preferred embodiment, a gap G was maintained between the underside of the compression bonnet 80 and the top of the piston body 76 . Depending on the material composition of the seal 78 , the gap may change slightly or substantially. In any event, in the preferred embodiment, a gap G preferably always exists even when the piston body 76 is in tight sealing engagement with the seat 40 a. By maintaining a gap G throughout valve operation, the full downward force applied by the stem 66 ′ is always applied to the seal, rather than directly to the piston body 76 . With this preferred construction, fluid communication between the pressure balancing bores 88 and the arcuate slots 80 a is maintained even if the slots are not aligned with the bores 80 a. In addition, any wear that occurs in the seal 78 is taken up by slight reductions in the gap G without reducing the forces applied to the seal when the piston body 76 is seated against the seat 40 ′.
[0035] Although the invention has been described with a certain degree of particularity, it should be understood that those skilled in the art can make various changes to it without departing from the spirit or scope of the invention as hereinafter claimed. | A flow control valve and method for controlling fluid flow includes a valve housing defining a valve chamber. A port member mounted within the valve chamber receives a reciprocally movable piston/spool assembly. The assembly is engageable with a valve seat for blocking fluid flow through the chamber. The assembly includes a piston body defining an annular recess for receiving an annular seal and a compression bonnet received by the piston body which is operatively engageable with the annular seal. When the assembly is not engaging its associated valve seat, the seal is relaxed and thus reciprocal movement between the assembly and the port member is not substantially hindered or resisted. | 5 |
This is a divisional of co-pending application Ser. No. 848,675 filed on Apr. 4, 1986, now U.S. Pat. No. 4,673,025.
BACKGROUND OF THE INVENTION
This invention relates to metal casting apparatus and methods which employ gas permeable shell molds.
Gas permeable shell mold casting for casting of metal in an evacuated/inert gas atmoshere is known and is disclosed in U.S. Pat. Nos. 3,863,706; 3,900,064; 4,112,997; and 4,340,108. Gas permeable shell mold casting was developed to permit precision casting, on a high production basis, of metals which must be cast in an evacuated or inert gas atmosphere. Prior to the development of gas permeable shell mold casting, precision casting of metals in an evacuated or inert gas atmosphere presented a number of problems. In part, those problems were due to the time necessary to establish the required seals and to evacuate the casting apparatus, especially insofar as the relatively large melting and pouring chamber was concerned. There were also problems caused by the inclusion in the cast parts of dross or other impurities present on the surface of the molten metal.
Although gas permeable shell mold casting solved many of the problems of casting metals in an evacuated or inert gas atmoshere, problems still remain. The most critical problem is in providing a constant level of molten metal to the mold. Until the present invention, this problem has remained largely unsolved.
It is therefore an object of the invention to provide an apparatus and method for providing a constant level of molten metal to a mold in gas permeable shell mold casting which is simple, effective and reliable. Other objectives and advantages of the invention will become apparent hereinbelow.
SUMMARY OF THE INVENTION
The present invention is an apparatus for providing a constant level of molten metal to a mold in gas permeable shell mold casting. The apparatus comprises furnace means for melting and holding metal to be cast, means for locating a mold to be filled in casting relationship with the molten metal in the furnace means, and means for causing molten metal to be drawn from the furnace means into the mold. Sensor means are provided for sensing the change in the level of the molten metal in the furnace means relative to the mold as molten metal is drawn into the mold. Means responsive to the sensor means are provided for tilting the furnace means relative to the mold for causing the level of the molten metal to remain constant relative to the mold as the mold is being filled.
The present invention includes a method of providing a constant level of molten metal to a mold in gas permeable shell mold casting, and comprises the steps of melting and holding metal to be cast in a furnace means, locating a mold to be filled in casting relationship with the molten metal in the furnace means, causing molten metal to be drawn from the furnace means into the mold, sensing the change in the level of the molten metal in the furnace means relative to the mold as molten metal is drawn into the mold, and tilting the furnace means relative to the mold in response to change in the level of the molten metal relative to the mold to cause the level of the molten metal to remain constant relative to the mold as the mold is being filled.
DESCRIPTION OF THE DRAWINGS
For the purpose of illustrating the invention, there is shown in the drawings a form which is presently preferred; it being understood, however, that this invention is not limited to the precise arrangement and instrumentalities shown.
FIG. 1 is a simplified elevational view of apparatus in accordance with the present invention.
FIG. 2 is a simplified block diagram of the present invention.
FIG. 3 is a partial sectional view of the apparatus of FIG. 1, showing the furnace means in a tilted position relative to the mold.
FIG. 4 is a top plan view of a portion of the apparatus shown in FIG. 1, taken along the lines 4--4.
FIG. 5 is a partial sectional view of a novel furnace construction especially useful in connection with the present invention.
DESCRIPTION OF THE INVENTION
Referring now to the drawings, wherein like numerals indicate like elements, there is shown in FIG. 1 a casting machine 10 equipped with the apparatus of the present invention. The casting machine 10 includes a furnace 12 for melting and holding metal to be cast. As will be understood by those skilled in the art, furnace 12 comprises a housing or shell 14 and a crucible 16 constructed of a suitable refractory material, such as a high temperature ceramic, within the shell 14. Furnace 12 is provided with a plurality of induction coils 18 surrounding crucible 16 and through which high frequency electric current is passed to inductively heat and melt the metal to be cast. Induction coils 18 are connected to a suitable source of electrical power (not shown in FIG. 1) in known manner.
As best seen in FIGS. 1 and 4, furnace 12 includes a pair of arms 20 and 22 on opposite side of the furnace by means of which furnace 12 may be mounted to a support structure or frame 24. Frame 24 comprises a pair of upright standards 26 and 28 which are mounted on horizontal support members 30 and 32. Arms 20 and 22, which are fixed to furnace 12, are pivotably mounted to standards 26 and 28 as shown at locations 34 and 36. Pivot locations 34 and 36 may have any suitable structure for providing a pivotable connection between arms 20 and 22 and standards 26 and 28. A pivot axis 38 about which furnace 12 may tilt, as will be described in greater detail below, is defined through pivot locations 34 and 36, as best seen in FIG. 4. The ends of arms 20 and 22 opposite pivot locations 34 and 36 are connected to cylinders 40 and 42, respectively. Cylinders 40 and 42 may be pneumatic or hydraulic, and include extensible/retractable cylinder rods 44 and 46, respectively. Rods 44 and 46 are extensible and retractable by cylinders 40 and 42 in known manner, and have their free ends pivotably connected to arms 20 and 22 at pivot locations 48 and 50, respectively. The opposite end of cylinders 40 and 42 are pivotably connected to base 30, as at location 52 in FIG. 1. Cylinders 40 and 42 may be connected to a source of pneumatic or hyraulic fluid by suitable valving and connections, in known manner.
Horizontal support members 30 and 32 may be provided with wheels 54 and mounted on track members 56 and 58 so that furnace 12 can be moved left to right with respect to casting machine 10 in FIG. 1. Movement of furnace 12 can be accomplished by cylinder 60, as will be understood by those skilled in the art. A stop member 62 may be provided on casting machine 10 to limit movement of furnace 12 to the left (as viewed in FIG. 1) and to properly position furnace 12 with respect to casting machine 10.
As best seen in FIG. 1, casting machine also includes a head 64 in which may be located a gas permeable shell mold 66. Gas permeable shell molds are well known in the art, and need not be described in detail here. Head 64 is connected by a vacuum line (not shown) to a vacuum pump (not shown), by means of which a vacuum may be drawn on mold 66 so that molten metal may be drawn into the mold, in known manner. Head 64 and mold 66 may be moved vertically toward and away from furnace 12 by means of cylinder 70 and rod 72, in known manner. Guide rods 74 and 76 are provided in tubular guides 78 and 80 so that head 64 and mold 66 can be moved straight up and down and will not be skewed when head 64 and mold 66 are raised or lowered.
Next to head 64 is mounted a remote level sensor 100. Level sensor 100 may be mounted on a standard 102 which is fixed with respect to casting machine 10. Level sensor 100 may be any suitable remote level sensor, such as a laser level sensor, familiar to those skilled in the art. Standard 102 and level sensor 100 are located so that the level sensor has a clear line of sight to the level of molten metal in the furnace, unobstructed either by head 64 or the edge of the furnace when the furnace is tilted.
Casting machine 10 may also be supplied with a suitable charge system for adding metal to be melted to furnace 12. Alternatively, liquid metal may be added directly. Any suitable charge system, such as a conveyor system, may be employed. Charge for furnace 12 is directed into crucible 16 via a chute 104. Chute 104 may be pivoted as at location 106, so that chute 104 may pivot out of the way to allow for tilting of furnace 12.
The apparatus of the invention is shown schematically in FIG. 2. The central controller for the invention is computer 108, which may be a mini-computer or dedicated microprocessor suitably programmed to carry out the operations of the invention. As inputs, computer 108 receives the output signal from level detector 100 and the output of a shaft position encoder 110, which is not shown in FIGS. 1 or 4, but which may be mounted on furnace 12 along pivot axis 38 to sense the angle through which furnace 12 is tilted. Shaft encoders for sensing angular position are well known, and need not be described in detail here.
An additional input to computer 108 is a signal from a temperature sensor which senses the temperature of the metal in the furnace. Temperature of the molten metal may be sensed by any suitable means, such as a contact probe or infrared pyrometer. This measurement may be made separately and the results inputted to computer 108 by a conventional keyboard (not shown).
In response to the inputs, computer 108 generates a number of control outputs for the apparatus. One output is a control signal to the furnace power supply 112 to control the power being supplied to induction coils 18 of furnace 12. Computer 108 controls power supply 112 so that a predetermined temperature of the molten metal in the furnace may be maintained, and so that additional power may be supplied to furnace 12 for melting when furnace 12 is charged with cold metal. The way in which computer 108 may control power supply 112 for these functions will be well understood by those skilled in the art, and need not be described here in detail.
Computer 108 also processes the signals from level sensor 100 and shaft encoder 110 and generates a tilt control output, which is used to control the operation of cylinder 40.
The mode of operation of the invention is now described.
After furnace 12 has been charged with and melted the metal to be cast, or has been charged with liquid metal, head 64 and mold 66 are lowered into furnace 12 so that mold 66 is partially immersed in the molten metal 114. A vacuum is then drawn on mold 66 to draw molten metal into the mold.
Level sensor 100 continuously monitors the level 116 of molten metal 114 relative to mold 66. It will be appreciated that, as molten metal is drawn up into mold 66, level 116 will drop. The change in level 116 is sensed by level sensor 100, and a signal representative of the change in level 116 is sent to computer 108. Computer 108 processes this signal and generates a tilt control signal which, through appropriate hyraulic or pneumatic lines and valving causes cylinder 40 to extend shaft 44. As shaft 44 is extended, furnace 12 tilts about pivot axis 38. See FIG. 3. Tilting furnace 12 in effect raises the level 116 of molten metal 114 with respect to mold 66. Computer 108 may be programmed to continuously tilt furnace 12 as molten metal is drawn up into mold 66, with the effect that the level 116 of molten metal 114 remains constant with respect to mold 66.
When the mold 66 is full, it is withdrawn from furnace 12, and casting machine 10 sends a signal to computer 108 that the casting operation is complete. When the casting operation is complete, head 64 and mold 66 are raised out of furnace 12, a new mold is placed in head 64, and the process repeated.
Computer 108 may be programmed to control the operation of the charge system so that additional charge may be added to furnace 12 to continually replenish the metal being drawn into mold 66. The shaft position encoder signal is processed by computer 108 to determine whether the angle of tilt of furnace 12 is sufficiently large that more metal should be added. If so, computer 108 activates the charge system, charging additional metal into the furnace. The computer 108 will maintain level 116 constant as metal is charged into the furnace by reducing the angle of tilt of the furnace. The change in angle of tilt of the furnace is continuously sensed by shaft position encoder 110. When the shaft position encoder senses that furnace 12 has returned to its original horizontal position, computer 108 terminates the charging operation. The computer 108 calculates the total charge being placed in the furnace by the change in angle of tilt, and signals power supply 112 to maintain an average power level in furnace 12 so that cold metal can be melted and temperature stability is maintained.
Computer 108 may be prorammed to stop the tilting of furnace 12 after furnace 12 has been tilted for a preselected number of degrees. When furnace 12 has been tilted to the preselected number of degrees, as indicated by shaft position encoder 110, computer 108 will stop the tilting of furnace 12, and reverse the drive to cylinder 40. Cylinder 40 will then retract rod 44, allowing furnace 12 to be tilted back to its original horizontal position.
Alternatively, the change in level 116 sensed by level sensor 100 may be processed to generate a signal representative of the change in level 116. This signal is sent to computer 108, which processes this signal and generates a lift control signal that controls the vertical position of mold 66 relative to level 116 of liquid metal 114. In this alternate form of the invention, furnace 12 remains in a horizontal position and no tilting takes place. Instead, as level 116 falls as metal is drawn into mold 66, the mold is lowered to keep level 116 constant relative to mold 66. When the level 116 falls below a predetermined value, level control 100 sends a signal to computer 108 and either solid or liquid metal is added to the furnace.
The furnace 12 needs to have a very large surface area to accomodate mold 66. However, for holding of metal, especially ductile iron, for example, it is important to have the minimum quantity of metal on hand at the casting station. This is because changes in metallurgy of the molten metal can occur over time which affect the quality of the end casting. The longer the "dwell time" of the molten metal in furnace 12, the greater the changes in metallurgy will be. To minimize "dwell time", a very small depth of metal is preferred in this casting process.
A furnace construction which makes possible the efficient melting and/or holding of small depths of metal is shown in FIG. 5. For ease of correlating the various parts of the furnace of FIG. 5 to the other drawings, primed reference numerals are used. Furnace 12' in FIG. 5 comprises a furnace shell 14' within which is a crucible 16'. As shown in FIG. 5, the interior of crucible 16' is very shallow. Surrounding crucible 16' within shell 14' are induction coils 18'.
Normally in a coreless furness, the load length and coil length are equal. However, it is well known that a coreless furnace is inefficient when the load and coil length are short in comparison to the load and coil diameter, as is required here to maintain a very small depth of molten metal. Accordingly, in the novel furnace according to the present invention, the coil length is made much longer than the load. So as not to allow stray flux to heat the mold surroundings, the minimum metal level is held to the top of the induction coil. Thus, the induction coil 18' extends far below the metal. The bottom turns of the coil 18' couple magnetically to the bottom of the molten metal and, thus, act as if both the load and coil were very much longer than the load depth. Thus, small load depths can be made to act as if they were equal to the much larger depth shown by the induction coil with similar electrical characteristics and efficiencies. Coil to load depth ratios of 1 to 1 or more can be achieved, with higher ratios yielding higher efficiencies. Preliminary calculations show that extension of the coils 18' of three times the load depth produce optimum efficiencies. Thus, it is believed that optimum results are achieved at a ratio of 4 to 1.
The furnace of FIG. 5 thus enables very small depths of metal to be melted and/or held at very high efficiencies, which in turn allows "dwell time" and changes in metallurgy to be minimized.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention. | Apparatus and method for providing a constant level of molten metal to a mold in gas permeable shell mold casting. The apparatus includes a furnace for melting and Holding metal to be cast. Structure is provided for locating a mold to be filled in casting relationship with the molten metal in the furnace and for causing molten metal to be drawn from the furnace into the mold. Structure responsive to the sensor is provided for tilting the furnace relative to the mold causing the level of the molten metal to remain constant relative to the mold as the mold is being filled. | 1 |
FIELD OF THE INVENTION
The present invention concerns self adjusting lift tables.
BACKGROUND OF THE INVENTION
Self adjusting lift tables or elevators consist of a load platform which is supported on a base by an air pressure actuator comprised of a heavy duty bellows containing compressed air. The bellows is reduced in height as weight is added to the platform by each successive part loaded onto the platform, causing the platform to be lowered. As a worker removes each part, the platform rises tending to keep the remaining parts at an easy accessible height during the entire unloading process.
The spring characteristic of the bellows can be adjusted to a limited degree by adjusting the air pressure in the bellows, so as to adapt the table to a variety of load weights.
Replaceable mechanical springs have also been employed to adapt to varying part weights, but this requires significant time and effort in changing the springs.
The air pressurized bellows spring characteristic is essentially nonlinear, as the pressure rises non linearly as weight is added.
In an effort to improve linearity, the effective volume of the bellows has been increased by connecting a fixed volume air reservoir. See U.S. Pat. No. 5,299,906 issued on Apr. 5, 1994, for a "Self Adjusting Pneumatic Load Elevator" for a description of such a lift table, in which the air in the reservoir augments the total volume of air in the system which is compressed by the load.
The fixed volume reservoir has the disadvantage that it is sometimes regarded as a pressure vessel, requiring testing and certification, increasing the cost of the equipment.
A problem has been encountered in adapting the adjustment feature to loaded parts of substantially differing densities. If a relatively dense part is being supported, the extent of deflection is desirably less than for a more bulky part so that the uppermost loaded parts remain at substantially the same height. Adjustment of the air pressure allows a change in stacking height of the table, but does not appreciably change the effective spring rate such that heavier loaded parts deflect the table the same as bulky parts, creating a mismatch in the degree of table deflection for one or both of the loaded parts.
While adding a fixed volume reservoir improves the load deflection linearity to some degree, there has still not been provided a satisfactory ability to tailor the load-deflection characteristic to various part densities to achieve a load-deflection curve matching a part weight and height.
Accordingly, it is an object of the present invention to provide a lift table of the type described in which the load deflection characteristic is improved, and is easily matched to various part densities.
SUMMARY OF THE INVENTION
This object, and other which will be appreciated upon a reading of the following specification and claims are achieved by the present invention, comprised of a lift table which is supported by an air actuator bellows as in conventional lift tables, but which has an auxiliary bellows in fluid communication with the load platform supporting bellows. The auxiliary bellows is adjustably compressed between a pair of spring loaded plates to variably increase the effective volume of the main actuator bellows to improve the load-deflection characteristic. The auxiliary reservoir provides a variable volume reservoir since the clamping plates are spring loaded to allow some expansion of the auxiliary volume, when the pressure in the main bellows is increased by an added loading.
The degree of spring loading is itself adjustable as the springs are each disposed on a respective one of a plurality of guide shafts passing through the clamping plates to allow adjusting movement towards or away from the sandwiched auxiliary bellows. This enables the effective spring rate of the system to be adjusted for a given air pressure and thus enables the deflection rate to be matched to a given part density.
In the described embodiment, the guide shafts are threaded at each end to allow the spring precompressing to be varied by threaded advance of nuts engaging each spring.
Thus, the combined effects of the main bellows, the auxiliary bellows and the spring preloading of the auxiliary bellows provides improved load-deflection characteristics as well as an improved adjustment capability.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the improved lift table according to the invention.
FIG. 2 is a side elevational view of the lift table shown in FIG. 1.
FIG. 3 is an enlarged fragmentary view of the auxiliary reservoir included in the lift table shown in FIGS. 1 and 2.
FIG. 4 is a simplified schematic diagram of the air circuit of the lift able according to the present invention.
DETAILED DESCRIPTION
In the following detailed description, certain specific terminology will be employed for the sake of clarity and a particular embodiment described in accordance with the requirements of 35 USC 112, but it is to be understood that the same is not intended to be limiting and should not be so construed inasmuch as the invention is capable of taking many forms and variations within the scope of the appended claims.
Referring to FIGS. 1 and 2, the lift table 10 includes a planar load platform 12 adapted to receive parts 14 placed thereon.
The load platform 12 is supported on a base 16 by means of a pair of scissors linkages 18 so as to be able to be moved up and down. The scissors linkages 18 each includes pairs of elongated members 20, 22, provided on either side of the platform 12 and base 16, pinned together at their midpoint and are pivoted at 11, 13 at one of their ends 11, 13 to the platform 12 and base 16 respectively in conventional fashion.
The other end of each member 20, 22 is free to move on support rollers 15, 17 so that operation of the scissors linkages 18 can raise or lower the platform 12, in the manner described in U.S. Pat. No. 5,299,906.
The scissors linkages 18 are supported by air spring means defined by a compressible enclosure filled with a gas under pressure, here comprised of an air bellows actuator 24 precharged with air at a selected pressure. Such actuators are commercially available from Firestone under the "Airstroke" trademark. The bellows 24 is compressed between upper and lower bellows support pans 26, 28 supported on shafts 30 and 34 telescoped into tubes 32, 36, both fixed to respective upper and lower cross members 38, 40 in turn pivoted at either end to respective scissors members 20, 22 so as to be able to rotate. Extension of the shafts 20, 34 in the tubes 32, 36 and pivoting of cross members 38, 40 maintains the support pans 26, 28 level as the scissors action occurs during raising and lowering of the load platform 12.
Thus, as weight is added or removed from the load platform 12, the bellows is compressed or relaxed causing lowering or raising of the platform 12. Additional bellows may be added for heavier weight capacities.
According to the concept of the present invention, an auxiliary adjustable rate air spring is provided, comprised of a smaller auxiliary bellows 42 supported beneath one of the upper cross members 40 compressed between a pair of clamping plates 44, as best seen in FIG. 3. The clamping plates 44 sandwich the auxiliary bellows 42 and exert a compressive force thereon generated by a series of helically wound mechanical compression springs 46 received over each end of threaded studs 50.
Studs 50 are located at each corner of the square clamping plates 44, passing through holes therein which allow free sliding movement of the clamping plates 44 towards and away from each other.
Lock nuts 52 are threaded on each end of each stud 50 and allow the compression of each spring 46 to be selectively varied to enable adjustment of the force exerted by the clamping plates 44 on the bellows 42.
The main bellows 21 can be precharged with air (or air bled therefrom) via a valve 54 (FIG. 4), connected to a shop air source 56 and to a vent 58. This enables the unloaded height of the lift table to be varied by changing the starting air pressure.
The auxiliary bellows 42 does not generate any lifting force on the load platform 12, but is connected via line 58 to the air pressure in the main bellows 24 so as to act as an auxiliary, variable volume reservoir. As the main bellows 24 is compressed, the air volume subject to this force includes the air in the auxiliary bellows 42. Thus, a slight increase in its volume will occur with a slight decrease in the enclosed volume of the main bellows 24.
By changing system air pressure, the unloaded height of the load platform 12 is varied. Changes in the level of spring force exerted by the springs 46 causes a variation in the effective spring rate of the bellows system. Thus, by loosening the nuts 52, the spring rate of the air system is lowered. Removal of less dense parts can thus be caused to create a relatively great deflection. By tightening the nuts 52, a greater spring rate results, so that denser parts will cause less deflection.
This arrangement thus allows convenient adjustment for different loading applications to achieve the objects of the invention. | A lift table of the type having an air actuator bellows raising and lowering a load platform with a scissors linkage has an auxiliary expansible reservoir in fluid communication with the air bellows to improve the load-deflection characteristic. The auxiliary reservoir consists of an auxiliary bellows clamped between plates with an adjustable spring force. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to radio-frequency (RF) power amplifiers. More particularly, the invention relates to an RF power amplifier circuit that includes a bias adjustment circuit that causes the output signal of the amplifier to contain an amount of intermodulation distortion that increases linearly (on a log scale) as the output power increases.
BACKGROUND OF THE INVENTION
[0002] An RF power amplifier is a circuit that is capable of receiving an RF input signal and amplifying it to produce an RF output signal. RF power amplifiers are frequently used in communications systems, such as cable-television systems (CATV). They normally include bipolar junction transistors or field-effect transistors as amplifying elements, and, if so, they also invariably include a bias circuit that sets the quiescent operating point of the transistor. (The quiescent operating point of a transistor is the “point on the family of characteristic curves . . . that corresponds to the average electrode voltages or currents in the absence of a signal.” JOHN MARKUS, ELECTRONICS DICTIONARY 445 (4th ed. 1979). The quiescent operating point of a bipolar junction transistor includes such parameters as quiescent base-emitter current, quiescent base-emitter voltage, quiescent collector-emitter current, and quiescent collector-emitter voltage.)
[0003] In such transistor-based power amplifiers, there are tradeoffs between maximizing efficiency and ensuring that the desired amplification characteristics are maintained. The efficiency of an amplifier, or output circuit efficiency, is the amplifier's signal output power divided by the power supplied to the amplifier by the power supply. The former quantity—the signal output power—is determined by the gain of the amplifier and the input drive level (or signal input power). The latter quantity—the power supplied to the amplifier by the power supply—is largely determined by the quiescent operating point of the amplifier. An amplifier with a high quiescent operating point will draw a large amount of power from the power supply, and the amplifier will have a low efficiency. Conversely, an amplifier with a low quiescent operating point will draw a small amount of power from the power supply, and the amplifier will have a high efficiency. In summary, the relationship among efficiency, signal output power, and quiescent operating point is this: the lower the quiescent operating point and the higher the signal output power, the higher the efficiency of the amplifier.
[0004] But an amplifier with a low quiescent operating point and a high signal output power will produce (in addition to an amplified RF signal) large intermodulation and harmonic distortion signals. Harmonics, or noise signals having frequencies that are integer multiples of the signal frequency f (i.e., 2f, 3f, etc.) are generated when a pure sinusoidal waveform is clipped. If clipping occurs when more than one signal is simultaneously applied to an amplifier, then intermodulation distortion (hereinafter, “IMD”) occurs in addition to harmonic generation.
[0005] For amplifiers with less than a one-octave bandwidth, the dominant IMD term is the third-order component. The theoretical power of such third-order IMD products resulting from waveform clipping increases by about three decibels for every one-decibel increase in signal input power, provided that the highest-order term in the nonlinearity of the amplifier is cubic. In other words, if the theoretical power (in decibels) of the third-order IMD is graphed against the signal input power (in decibels), the result is a straight line having a slope of about 3:1. This graph of the third-order IMD versus input power level is referred to hereinafter as the theoretical 3:1 curve.
[0006] In practice, however, real amplifiers contain nonlinear processes that cause the third-order IMD produced to deviate from the theoretically-calculated amount. The power of the IMD caused by these nonlinear processes is determined by the vector addition of the components generated by each nonlinear process. Such terms may partially cancel or add, depending on the frequency and phase of the components. As a consequence, the actual third-order IMD does not follow the theoretical 3:1 curve. As the output power increases, rather, the third-order IMD tends to deviate more and more from the theoretically-predicted 3:1 curve, and the rate of increase of IMD with input power may become 4:1, 5:1 or even worse.
[0007] The inventor of the present invention has recognized that this unpredictable variation in IMD from the theoretically-predicted 3:1 curve causes problems to designers of CATV systems, who must be able to calculate signal power and distortion power at each point in a cascaded CATV system. The calculations are normally performed using large spreadsheet programs making use of the assumption that the IMD produced by each amplifier follows the theoretical 3:1 curve. But the calculations are inaccurate if the third-order IMD produced is greater or less than the amount that is theoretically predicted. Thus, it would be desirable to have an RF amplifier that produces a predictable amount of IMD, in accordance with the theoretical 3:1 curve.
[0008] Existing techniques for compensating for excessive IMD are not adequate to this task. A first known technique is to decrease or attenuate the power level of the amplifier input signal. A decrease in input power causes a corresponding decrease in the output power of the amplifier, so that the third-order intermodulation and harmonic distortion is reduced to acceptable levels. The useful output power range over which the amplifier can be used is therefore limited, in order to avoid excessive IMD. This limitation in output power range is highly undesirable.
[0009] A second technique that has been used to compensate for excessive distortion is described in U.S. Pat. No. 5,712,593 (hereinafter, the '593 patent). According to this technique, there is selected a power level of total distortion (including both harmonic and intermodulation distortion) that is acceptable in the output of the amplifier. An adjustable bias circuit is then employed to continually adjust the operating point of the amplifier, depending on the power of the distortion in the output of the amplifier, so that the power level of distortion that is acceptable is maintained. If the power of the distortion is too high, the operating point of the amplifier is raised to a point at which the amplifier operates more linearly and produces less distortion. Conversely, if the power of the distortion is lower than the acceptable amount, the operating point of the amplifier is lowered, thereby improving the efficiency of the amplifier but increasing the distortion produced by the amplifier.
[0010] Although the system of the '593 patent successfully maintains the total distortion in the output of an amplifier at a predetermined power level, however, it does not accomplish the desired objective of causing the third-order IMD to increase at the 3:1 rate. Rather, in the system of the '593 patent, the power level of the third-order IMD in the output of the amplifier remains at approximately the same level as the power of the input signal increases, because the amplifier bias voltage is continually adjusted to maintain the level of distortion constant. Thus, the technique of the '593 patent does not fulfill the need for predictability in amplifier performance.
OBJECT OF THE INVENTION
[0011] It is accordingly an object of the invention to provide an amplifier bias adjustment that maintains the theoretically-expected 3:1 third-order IMD slope for output power.
SUMMARY OF THE INVENTION
[0012] The invention is directed to a circuit for amplifying an input RF signal. The circuit comprises the following elements: (1) an RF amplifier circuit that amplifies the input RF signal and produces an output RF signal that comprises a third-order IMD product signal; (2) a power divider circuit that divides a signal output from the RF amplifier circuit into the output RF signal and a feedback signal; (3) a feedback circuit comprising an RF detector that detects the feedback signal and produces a DC voltage proportional to the power of the feedback signal that is used to bias the RF amplifier circuit. With this circuit, the third-order IMD product signal responds, over a predetermined range of power of the output RF signal, by increasing substantially three decibels in response to each one-decibel increase in the level of the input RF signal. Preferably, the feedback circuit further comprises a DC level shifter and a DC amplifier to amplify and shift the level of the DC voltage before it is used to bias the RF amplifier circuit.
[0013] In one embodiment, the power divider circuit produces the RF output signal and the feedback signal with equal strength. Preferably, though, the power divider circuit produces the RF output signal and the feedback signal with unequal strength. In a preferred embodiment, the feedback signal has a strength at least ten decibels less than the RF output signal. The power divider circuit may comprise a coupler with a ferrite core. Alternatively, it may comprise a resistor or any other circuitry that divides power. The RF amplifier circuit preferably comprises a monolithic gallium arsenide (GaAs) metal-semiconductor field-effect transistor (MESFET). The detector circuit preferably comprises a DC blocking capacitor, a detector diode, a DC bias inductor, a DC bias resistor, and an RF bypass capacitor.
[0014] The invention is also directed to a method for amplifying an input RF signal to produce an output RF signal that comprises a third-order IMD product signal, where the third-order IMD product signal responds over a predetermined range of power of the output RF signal by increasing substantially three decibels in response to each one-decibel increase in the level of the input RF signal. The method comprises the following steps: (1) amplifying the input RF signal in an amplifier to produce an amplified signal; (2) dividing the amplified signal into an output RF signal and a feedback signal; (3) generating a DC signal with a DC voltage proportional to the power of the feedback signal; and (4) biasing the amplifier based on the DC signal. Preferably, the method further comprises the steps of amplifying the DC signal and level-shifting the DC voltage before using it to bias the amplifier.
[0015] In one embodiment, the step of dividing produces the RF output signal and the feedback signal with equal strength. Preferably, though, this step produces the RF output signal and the feedback signal with unequal strength. In a preferred embodiment, the feedback signal has a strength at least ten decibels less than the RF output signal. The step of dividing may be performed with a circuit that comprises a coupler with a ferrite core. Alternatively, it may be performed with a circuit that comprises a resistor or any other circuitry that divides power. The amplifier preferably comprises a monolithic GaAs MESFET. The step of generating a DC signal is preferably performed with a circuit that comprises a DC blocking capacitor, a detector diode, a DC bias inductor, a DC bias resistor, and an RF bypass capacitor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a block diagram illustrating the feedback circuit of the invention used to maintain the theoretically-expected 3:1 third-order IMD slope for output power.
[0017] [0017]FIG. 2 is a schematic circuit diagram for the RF detector, DC amplifier, and level shifter blocks shown in FIG. 1.
[0018] [0018]FIG. 3 is a flowchart of the method of the invention for maintaining the theoretically-expected 3:1 third-order distortion slope for output power.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The invention relates to an amplifier device wherein the theoretical 3:1 third-order IMD power slope is maintained. This is achieved by using a feedback mechanism that adjusts the bias current, increasing it as a function of output power, to keep the third-order IMD on this theoretical slope.
[0020] The feedback circuit is illustrated in FIG. 1. RF input signal 10 is amplified by the circuit, producting RF output signal 40 . RF input signal 10 is first amplified by RF amplifier 20 . The amplified signal is then fed into a power divider 30 . In one embodiment, the RF amplifier 20 is a monolithic GaAs metal-semiconductor field-effect transistor (“MESFET”) circuit, although alternative amplifiers are also within the scope of the invention. Such alternative amplifiers include, but are not limited- to, amplifiers formed from different types of transistors, including other field-effect transistors as well as bipolar junction transistors.
[0021] Power divider 30 samples the power of the amplified signal and feeds it into RF detector 50 . In one embodiment, power divider 30 is a simple power divider with an equal power split. In a preferred embodiment, however, power divider 30 provides an unequal split, with the signal fed to RF detector 50 having a strength less than that for RF output signal 40 . This is to minimize the through loss of the RF signal. Preferably, the strength of the signal fed to RF detector 50 is at least 10 dB less than the strength of RF output signal 40 . In one embodiment, the power divider 30 is a coupler fabricated using a ferrite core. In an alternative embodiment, the power divider 30 comprises a resistor or other circuitry that divides power.
[0022] RF detector 50 produces a DC voltage that is proportional to the RF signal power input from RF power divider 30 . This DC signal is fed back to RF amplifier 20 , preferably through a DC amplifier 60 and a level shifter 70 . The function of DC amplifier 60 and level shifter 70 are to ensure that the DC signal that is fed back into RF amplifier 20 increases the DC bias in the RF amplifier 20 as a function of the RF output power such that the third-order IMD remains on the 3:1 slope.
[0023] [0023]FIG. 2 is a schematic circuit diagram illustrating an embodiment of RF detector 50 , DC amplifier 60 , and level shifter 70 . In FIG. 2, the RF output from power divider 30 passes through DC blocking capacitor C 1 . Detector diode D 1 , given a small forward-bias current (about 20 microamperes for a typical Schottky diode detector) by resistor R 1 and inductor L 1 , rectifies the RF signal by conducting current only when the voltage at node 200 is less than the voltage at node 210 minus the diode cut-in voltage (normally 0.6 V for a silicon diode). Diode D 1 does not conduct when the voltage at node 200 is greater than the voltage at node 210 minus the diode cut-in voltage. The current through diode D 1 accordingly follows the negative peaks of the input signal waveform with an inversely proportional linear relationship between the diode current and the input voltage.
[0024] The voltage at node 210 behaves as follows. When diode D 1 is forward biased by a negative voltage at node 200 , the voltage at node 210 tracks the voltage at node 200 (plus the voltage developed across diode D 1 , which is approximately 0.7 V for a silicon diode or 1.3 V for a GaAs diode. When diode D 1 is reverse biased, however, the voltage at node 210 is held fixed by bypass capacitor C 2 . This capacitor should be sufficiently large that the voltage at node 210 tracks slow changes in the average output power of the RF amplifier rather than instantaneous changes in output power or in the modulation of the carrier. In the preferred embodiment, the size of bypass capacitor is selected to cause the video bandwidth of the detector to be about 1 Hz.
[0025] Thus, the output of the detector (the voltage at node 210 ) is a DC signal that is inversely proportional to the RF power output from power divider 30 . When the RF power is small, the DC signal is large (more positive or less negative); when the RF power is large, the DC signal is small (less positive or more negative).
[0026] This DC signal then passes to DC amplifier 60 , formed by resistors R 2 , R 3 , R 4 , and R 5 and transistors Q 1 and Q 2 . The transistors may be field-effect or bipolar-type transistors. Resistors R 4 and R 5 , connected in series between positive voltage supply +V and ground, create a reference voltage at node 220 through voltage division. This voltage at node 220 (V 220 ) is determined by the ratio of the values of R 4 and R 5 :
V 220 = + V * R5 R4 + R5
[0027] Transistors Q 1 and Q 2 and resistors R 3 and R 2 form a conventional differential amplifier. Resistor R 2 sets the gain of the differential amplifier, while resistor R 3 sets the current through transistors Q 1 and Q 2 . In a preferred embodiment, resistor R 3 is quite large in relation to resistor R 2 .
[0028] The output of DC amplifier 60 is the voltage at node 230 (V 230 ), which is proportional to the difference between the voltage V 210 at the gate of transistor Q 1 and the reference voltage V 220 . V 230 is thus proportional to, and inverted to, V 210 . For example, an increase in the RF detector 50 output voltage at node 210 would cause a decrease in the voltage at node 230 , and vice versa. The magnitude of V 230 is, of course, determined by the gain of the differential amplifier.
[0029] The voltage at node 230 (V 230 ) is then input to level shifter 70 , which in one embodiment comprises a buffering transistor Q 3 and resistors R 6 and R 7 , which provide the DC voltage level-shifting. Resistors R 6 and R 7 are selected to provide an appropriate range for the bias control voltage V CONTROL . The magnitude of this voltage is dependent on the RF amplifier design and, in a preferred embodiment, varies about 100 mV over the full range of RF output power.
[0030] To summarize, when an input signal is present at the input of capacitor C 1 , detector 50 causes a proportional inverted signal to appear at node 210 . The DC amplifier 60 then inverts the inverted signal to a non-inverted, amplified signal, and level shifter 70 shifts the amplified signal to a range appropriate for biasing RF amplifier 20 . When the input signal power is small, the RF amplifier bias voltage will be small, and when the input signal is large, the RF amplifier bias voltage will be large. Thus, the quiescent operating point of RF amplifier 20 is continuously adjusted so that RF amplifier 20 operates in a more linear range on its I-V curve, and the third order IMD is maintained on the theoretically-expected curve even at high RF output power.
[0031] [0031]FIG. 3 is a flowchart illustrating the method of the invention for maintaining third-order IMD products on the theoretical 3:1 slope. While it is preferred that the steps be performed by a circuit configuration similar to the one shown in FIG. 1 and described above, alternative configurations may also be used.
[0032] In step 110 , the RF signal to be amplified is input. This signal is amplified in step 120 . The amplified signal is then divided at step 130 . Preferably, division of the amplified signal is unequal, with the signal fed along path 132 having a strength less than that fed along path 134 . This is to minimize the through loss of the RF signal. It is preferred that the strength of the signal fed along path 132 be at least 10 dB less than the strength of the signal fed along path 134 . The portion of the divided signal fed along path 132 is then used at step 150 to generate a DC signal with a voltage proportional to the RF signal input along path 132 . This DC signal is preferably amplified at step 160 and level-shifted at step 170 so that it can be fed back to step 120 .
[0033] The portion of the divided signal fed along path 134 is output as the amplified RF signal at step 140 . The steps of amplifying 160 and level-shifting 170 the DC signal have the effect of increasing the DC bias used at the RF amplification step 120 at such a rate that the third-order IMD remains on the theoretical 3:1 slope.
[0034] While the invention has been described with reference to a specific embodiment, it will be appreciated by those of ordinary skill in the art that modifications can be made to the structure and form of the invention without departing from its spirit and scope, which is defined in the following claims. | An circuit and method are provided for amplifying RF input signal to produce RF output signals with third-order intermodulation distortion products. The circuit and method use a feedback signal to control the bias voltage of the amplifier, such that the output third-order intermodulation distortion product increases monotonically with the RF input signal power. Specifically, the third-order intermodulation distortion product responds over a predetermined output power range by increasing three decibels in response to each one-decibel increase in input power. | 7 |
BACKGROUND OF THE INVENTION
This invention relates in general to pressure vessels and more particularly to a layered head for a pressure vessel and to a method of producing such a head.
The typical pressure vessel has a cylindrical shell and heads that close the two ends of the shell. The shell and heads are manufactured as separate components and are thereafter joined together by welding to produce a unitary structure. The heads are somewhat dome-shaped to enable them to better withstand elevated pressures.
It is generally recognized that vessel walls composed of multiple layers are superior to thick single walls in many respects. For example, the individual plates of a layered wall, generally speaking, have better metallurgical properties than thick solid walls, since they are subjected to greater rolling at the mill. As a consequence, a layered vessel is usually safer than a solid wall vessel of equivalent wall thickness. Whereas thick solid walls exhibit a tendency to laminate, layered walls rarely display this tendency because of their better metallurgical properties. Also, in layered vessels it is possible to vary the metal alloy from layer to layer, thus enabling an expensive corrosion resistant liner to be used with less expensive surrounding layers. While thick steel plates clad with various corrosion resistant alloys are available from steel mills, they are more expensive. Moreover, thin layers are relatively easier to shape than the heavy steel plate used in solid wall vessels. Thus, layered walls can be manufactured in greater thickness than solid walls. Aside from that, the individual layers that comprise the wall of a layered vessel, upon being welded together, tend to shrink as the welds which join them solidify and cool, and this places the inner layers in a state of precompression. This is desirable since the elevated pressures within the vessel create tensile forces in the vessel walls. In contrast, solid wall vessels are normally heat treated to relieve them of the stress concentrations resulting primarily from the welds that are made during fabrication.
Heretofore different procedures have been developed for fabricating cylindrical shells from multiple layers, one highly successful procedure being set forth in U.S. Pat. No. 4,478,784. Heads, by reason of their compound curvatures are not easily fabricated in multiple layers, and as a consequence most heads are still of the solid wall construction. Thus, to a large measure, the limitations of present pressure vessels are set by the heads at their ends.
SUMMARY OF THE INVENTION
The present invention is embodied in a layered head for a pressure vessel with the head being comprised of a frame and curved plates arranged in layers on the frame. Another object is to provide a head of the type stated which is relatively easy and simple to construct. A further object is to provide a head of the type stated which may without difficulty be fabricated in large sizes. An additional object is to provide a head in which the inner layers of head are initially in a state of precompression. Still another object is to provide a head in which the welds for the overlying layers are offset from each other. Yet another object is to provide a process for producing a head of the type stated. These and other objects and advantages will become apparent hereinafter.
The present invention is embodied in a pressure vessel head including a frame formed from a plurality of stiffeners arranged in a grid and overlying plates occupying the openings in the grid. The plates are welded to the stiffeners along their peripheral edges. The invention also resides in the combination of the head and a shell and the process for producing the head. The invention also consists in the parts and in the arrangements and combinations of parts hereinafter described and claimed.
DESCRIPTION OF THE DRAWINGS
In the accompanying drawings which form part of the specification and wherein like numerals and letters refer to like parts wherever they occur
FIG. 1 is a perspective view of a pressure vessel provided with heads constructed in accordance with and embodying the present invention;
FIG. 2 is a perspective view of the frame for a head and a series of plates that fit into grid openings of the frame;
FIG. 3 is a sectional view taken along line 3--3 of FIG. 2 and showing one of the frame stiffeners in cross section;
FIG. 4 is a fragmentary sectional view taken along line 4--4 of FIG. 1; and
FIG. 5 is an elevational view, partially broken away and in section, of a modified head.
DETAILED DESCRIPTION
Referring now to the drawings (FIG. 1), A designates a pressure vessel including a shell B and heads C which extend across and close the ends of the shell B. The shell B is cylindrical in configuration and may be a single wall structure or a layered structure. A separate head C is welded to each end of the shell B, and each head C curves outwardly away from the end of the shell B so that the end of the pressure vessel A is convex or dome-shaped. While the specific curvature of the head C may be critical from the standpoint of a particular application, it is not critical insofar as the general principles of construction are concerned. Those principles apply to hemispherical heads as well as heads of other contour such as ellipsoidal heads. They likewise apply to curved heads, irrespective of whether they have auxiliary shapes and appendages, such as inspection ports, flues, and extensions. Also, it should be recognized that a suitable pressure vessel may be produced without the shell B, that is with the heads C joined directly together.
In its simplest form, each head C includes a frame 2 (FIG. 2) formed from a circumferential base stiffener 4 and a plurality of meridional stiffeners 6 which curve away from the circumferential stiffener 4 and meet at an apex 8 along the centerline or axis X of the head C. The circumferential base stiffener 4 is circular and corresponds in diameter to the diameter of the shell B. The curvature of the meridional stiffeners 6 depends on the type of head that is desired. Also, the frame 2 preferably has at least one circumferential intermediate stiffener 10 which connects the meridional stiffeners 6 intermediate the base stiffener 4 and the apex 8 and is truly circular in configuration so as to completely encircle the frame 2. The stiffeners 4, 6 and 10 are all joined together by welding such that the inwardly presented surfaces of any two intersecting stiffeners 4, 6, 10 are flush at the welded joint, and the same holds true as to the outwardly presented surfaces.
Each stiffener 4, 6, 10 is formed from a bar of high strength metal such as steel. The bar is machined or otherwise shaped to provide the stiffener 4, 6, or 10 with a stepped cross-sectional configuration. Then it is deformed into a curvature suitable for the particular stiffener 4, 6, or 10. More specifically, each stiffener 4, 6, 10 has a relatively wide inwardly presented surface 16 (FIG. 3), a relatively narrow outwardly presented surface 18, and a series of alternate shoulders 20 and lands 22 between the two surfaces 16 and 18. The shoulders 20 face laterally insofar as the stiffener 4, 6, or 10 is concerned, whereas the lands 22 face outwardly. Each shoulder 20 has a height m, while each land 22 has a width n. The total height o of the stiffener 4, 6, or 10 equals the sum of the heights m for the various shoulders 20. The width P of the inwardly presented surface 16 equals the sum of the widths n of the several lands 22 plus the width of the outwardly presented surface 18. In the case of the circumferential base stiffener 4, the shoulders 20 and lands 22 are only along one side of it. However, each meridional and intermediate stiffener 6 and 10 has shoulders 20 and lands 22 along both of its sides. Any stiffener 4, 6, 10 that is used in the head C of a vessel A that is to contain a corrosive substance, should be machined from a bar, the metal of which is resistant to attack by the substance, since the inwardly presented surfaces 16 of the stiffeners 4, 6, 10 are exposed to the interior of the vessel A. In the alternative, the stiffeners 4, 6, 10 may be a clad along their inwardly presented surfaces 16 with a metal that withstands attack by the corrosive substance. Likewise special metals or claddings are required where the contents of the vessel A produces other deleterious effects such as hydrogen embrittlement.
The frame 2, being in the shape of a grid, has openings of both somewhat trapezoidal and somewhat triangular configuration. These openings are occupied by trapezoidal and triangular plates 26, 26a, 26b, and 26c (FIGS. 2 and 4) which are dished or curved outwardly to match the contour of the frame 2 itself. In other words, the plates 26, 26a, 26b, and 26c are outwardly convex, meaning their outwardly presented surfaces are convex in configuration. The plates 26, 26a, 26b, 26c have their side edges 28 located directly opposite the shoulders 20 on the stiffeners 4, 6, 10 and are arranged in layers which correspond in thickness to the shoulders 20.
More specifically, the innermost plates 26 are installed first, and each has its side edges 28 located opposite to the innermost shoulders 20 on the several stiffeners 4, 6, 10 that surround it (FIG. 4). Indeed, the thickness of the plate 26 should equal the thickness of the innermost shoulder 20. The plate 26 should further be dished outwardly so that its curvature corresponds with that of the particular location on the frame 2 at which it is located. Since the plate 26 is attached to the surrounding stiffeners 4, 6, 10 by welding, its surface area should be slightly smaller than the grid opening into which the plate 26 fits. This provides a narrow space or groove between the side edges 28 of the plate 26 and the adjacent shoulders 20 on the surrounding stiffeners 4, 6, 10, and that space of course is capable of accommodating a weld for securing the plate 26 to the stiffeners 4, 6, 10. Since the plate 26 is relatively thin, it is not necessary to bevel its side edges to accommodate a weld.
The curved plate 26 is easily fabricated from a flat steel plate by a simple dishing procedure. This procedure is old and need not be considered in detail.
To install the plate 26 in the frame 2, the plate 26 is first manually held in the position that it is to assume within the frame 2, that is, with its inwardly presented surface flush with the inwardly presented surfaces 16 of the stiffeners 4, 6, 10 that surround it. Its outwardly presented surface will then be flush with the first or innermost lands 22 on those stiffeners 4, 6, 10. Its side edges 28, on the other hand, will be located opposite the innermost shoulders 20 on the stiffeners 4, 6, 10, although a slight space or groove will exist between the two. With the plate 28 in that position, several tack welds are made in the groove to temporarily secure the plate 26 to the frame 2. Then a complete butt weld 30 (FIG. 4) is made in the groove along the entire side edge 28 of the plate 26. After this weld cools, it is ground off flush with the first lands 22 on the surrounding stiffeners 4, 6, 10 and with the outwardly presented surface of plate 26.
The remaining plates 26 of the innermost layer are attached to the frame 2 in a similar manner.
As in the case of the stiffeners 4, 6, 10, if the vessel A is to contain a corrosive substance, then the plates 26 of the innermost layer should be formed from an alloy which resists attack by the corrosive substance. Of course that alloy should be compatible with the alloy of the stiffeners 46, 6, 10 in the sense that the two alloys can be welded together. In the alternative, the plates 26 of the innermost layer may be clad with a corrosion resistant alloy.
Once the plates 26 of the innermost layer have been welded to the frame 2 and the welds 20 have been ground flush, the plates 26a (FIGS. 2 and 4) of the second layer are attached to the frame 2 in a similar manner. These plates overlie the plates 26 of the first layer, yet are in face-to-face contact with the plates 26 of the first layer. They further overlie the welds 30 and the first lands 22 of the stiffeners 4, 6, 10. Consequently, the plates 26a of the second layer have slightly less curvature than the corresponding plates 26 of the first layer and slightly larger surface area as well. The thickness of each plate 26a for the second layer equals the height m of the second shoulders 20 on the stiffeners 4, 6, 10, so that the second lands 22 of the stiffeners 4, 6 and 10 and the outwardly presented surfaces of the plates 26a are flush. The primary consideration for the selection of the metal from which the plates 26a of the second layer are produced is its ability to withstand the stresses produced by elevated pressures within the vessel A. Of course, the metal should also be compatible with the metal of the stiffeners 4, 6, 10 in the sense that the two metals can be welded together. The plates 26a are formed in the same manner as the plates 26, only different contour templates and patterns are utilized.
After a plate 26a is cut to the proper size and deformed to the proper contour, it is laid into the frame 2 directly over the corresponding plate 26 of the first layer (FIG. 2). Its peripheral edge is spaced slightly inwardly from the second shoulder 20 on the surrounding stiffeners 4, 6, and 10 to form an outwardly opening groove in which another butt weld 30a (FIG. 4) is made. As the weld 30a solidifies and cools still further, it contracts, and this contraction draws the plate 26a of the second layer down tightly onto the underlying plate 26 of the first layer. In effect, the plates 26 of the first layer and the stiffeners 4, 6, 10 as well are placed in a state of precompression which enables them to better withstand the forces exerted on them by the highly pressurized contents in the vessel A.
After the plates 26a of the second layer are welded in place and the welds 30a ground flush, more plates 26b (FIGS. 2 and 4) are placed over the plates 26a of the second layer and they are also welded in place. Successive layers are built up in this manner until all of the lands 22 on the stiffeners 4, 6 and 10 are covered. The outermost layer of plates 26c overlies the outermost lands 22 on the stiffeners 4, 6, 10, and its outwardly presented surface lies flush with the outwardly presented surfaces 18 on the stiffeners 4, 6, 10. Moreover, the welds of each succeeding layer tend to draw the plates of that layer down tightly onto the plates of the underlying layer and increase the precompression of the underlying layers. Thus, by the time the outermost layer is in place, the plates 26 of the innermost layer are in substantial compression. No need exists for heat treatments, and indeed such treatments would relieve the precompression.
Once the head C is completed, it is welded to the end of the shell B along the circumferential base stiffener 4.
The plate 26 of the innermost layer as well as the stiffeners 4, 6, 10 and welds 30 which hold the plates 26 to the stiffeners 4, 6, 10 are completely impervious, and this of course enables the vessel A to hold elevated pressures. However, the plates 26a, 26b, 26c of the other layers are provided with weep holes 32 (FIGS. 2 and 4) which need not be aligned. The weep holes 32 permit entrapped air to escape during fabrication of the head C, and this insures that each plate 26a, 26b, 26c fits snugly over the plate immediately beneath it. Moreover, should one of the plates 26 or welds 30 of the innermost layer develop a leak, the vessel contents that escape from that leak will pass through the succession of weep holes 32 in the overlying plates 26a, 26b, 26c and will in short duration appear at the weep hole 32 in that plate 26c of the outermost layer which lies directly over the leak. Thus, the weep-holes 32 permit a source of pending failure to be detected well in advance--long before a major rupture occurs.
Heads may be formed in shapes other than hermispherical and with different frame configurations. For example, a modified head D (FIG. 5), which is also suitable for closing the end of the shell B, has an ellipsoidal configuration, that is in cross section it resembles one-half of an ellipse, and at its base it is provided with an extension 50 which facilitates attachment to the shell B. In effect, the extension 50, once the head D is welded to the shell B, serves as a short axial projection of the shell B, thereby making welding easier.
The head D includes a frame 52 which has base and end circumferential stiffeners 54 and 56, and meridional stiffeners 58 as well, but the meridional stiffeners 58 do not extend all the way to an apex. Instead, they terminate at the end circumferential stiffener 56. The stiffeners 54, 56 and 58 have the same stepped configuration as their counterparts in the frame 2 of the head C.
The generally trapezoidal spaces formed by the base, end, and meridional stiffeners 54, 56 and 58 are occupied by side plates 60 with each space containing a plurality of side plates 60 which are curved to match the contour of the side of the frame 52 and are attached to the frame 52 in the same manner as the corresponding plates 26 of the head C.
The circular space that is surrounded by the end circumferential stiffener 56 is occupied by a series of dished cap plates 62 which likewise are stacked upon each other and are welded to the circumferential stiffener 56 in the manner previously disclosed. The circular cap plates 62 may be fitted with an entry port that is closed by a removable cover or they may be provided with some other end configuration such as a flue.
While perhaps the stepped configuration is best suited for the stiffeners, other cross-sectional configurations are possible. For example, the stiffeners may be triangular in cross section.
The heads C and D are relatively easy to fabricate and provide all the advantages of layered construction. No limits exist on the thickness of the walls, as is true of solid wall constructions, for the thickness is merely dependent on the number of plates which are placed over one another in the grid openings of the frames 2 or 52.
This invention is intended to cover all changes and modifications of the example of the invention herein chosen for purposes of the disclosure which do not constitute departures from the spirit and scope of the invention. | A layered head for a pressure vessel includes a frame which has the general contour of the head and is formed from a plurality of stiffeners, some of which extend circumferentially and others of which extend meridionally. The stiffeners create a grid and each opening of the grid is occupied by a plurality of plates which are curved to match the contour of the frame and are stacked upon one another in face-to-face contact. Moreover, the several plates in each grid opening are progressively larger in surface area, with the innermost plate having the smallest surface area and the outermost plate having the largest. The peripheral edges of the plates are located directly opposite the sides of the stiffeners, and to accommodate the variance in the surface areas of the plates, the sides of the stiffeners are stepped. The individual plates are welded along their peripheral edges to the stiffeners, and because of the stepped configuration of the stiffeners and the variances in the surface areas of the plates, the welds of successive plates are offset from each other. | 4 |
REFERENCE TO PRIOR APPLICATION
This application is based on and claims priority from U.S. Provisional Patent Application Ser. No. 60/562,439, filed Apr. 15, 2004, which is hereby incorporated by reference.
FIELD OF THE INVENTION
This invention relates to a compact device for use in a work area to organize professional tools and to display personal items such as photographs.
BACKGROUND OF THE INVENTION
It is fairly ubiquitous that workers not only like to keep a variety of useful tools and supplies within reach, but also like to personalize their work space by displaying personal items such as mementos and photographs of family and friends. For example, professional service providers have frequent need of such things as writing utensils and supplies, e.g., pens, pencils, note cards and pads, along with a readily available supply of business cards, fee schedules, and advertisements or brochures to market auxiliary products. No less profound is the need of those working long hours, often in impersonal, institutional environments, to surround themselves with pictures, photographs, and memorabilia that give the work space a more individual character.
It is no surprise, then, that the work stations of workers such as professional service providers commonly become cluttered with an eclectic mixture of professional tools, informational notes and reminders, certificates such as diplomas and licenses, and personal memorabilia such as photographs and drawings. In the case of a beautician, cosmetologist, or hair stylist, for example, such items become intermingled on work stations with an assortment of various types of scissors and shears for cutting hair. This then leads to inefficient use of the work space, and the surfaces of such work stations are difficult to keep clean and can make a bad impression on clients and customers.
Although prior devices for organizing professional specialty tools are known to the art, none have met the fairly ubiquitous desire of most professional service providers to co-organize professional tools along with personal memorabilia, especially flat media such as photographs. Thus, workers are in need of a compact device that not only organizes and stores professional tools in an accessible manner, but also provides a tidy and efficient vehicle for the display of personal items such as photographs.
SUMMARY OF THE INVENTION
The invention features a display organizer that includes a frame having a substantially rigid shape, the frame including a top portion having a substantially horizontal surface, two side portions having side surfaces and supported structurally by the top portion, and an interior space at least partially confined by the top portion and two side portions. The frame also includes at least one opening in a limited area of the top portion, that is configured to receive and retrievably hold an object within the space (i.e., “interior space”) that is defined dimensionally by the top portion and side portions of the frame. By “limited area” is meant that enough of the plane of the top portion remains to maintain the structural shape of and support for the side portions. The opening is configured so that a user has access to the object and can thereby retrieve the object from the display organizer. In addition, the display organizer of the invention features, on at least one of the side portions, an externally accessible media storage sleeve designed to provide viewable display of flat items such as paper or card items, or printed or photographic media.
Preferably, the display organizer of the invention rests stably on a flat surface, such as the surface of a workstation. This can be achieved by proper geometric alignment of the top and side portions, so that substantially planar alignment of the edges of the side portions allow the display organizer to rest stably on a flat surface. It is not essential, therefore, that the display organizer include an actual base element or bottom portion.
In other embodiments, the display organizer can further include an optional bottom portion, in which case the portion of the frame that includes the top and side portions is referred to herein as a ‘top frame’ and the portion of the frame that includes a base element is referred to as a ‘bottom frame.’ The base is preferably substantially planar, so as to allow the display organizer to rest stably on a flat surface. In yet another embodiment, the bottom frame can further include a substantially planar bottom portion attached to one or two end portions, each end portion attached to one of the two opposite ends of the bottom portion. One or both of the end portions can serve to support an upwardly open container mounted on at least one of the end portions.
As used herein, the terms “side,” “end”, “front”, and “rear” are relative terms and are not intended to limit the invention. Features ascribed to ‘side portions’ can be easily applied to end portions and vice versa. The relative nature of such terms will be further understood to be consistent with the ability of a user to alter, e.g., rotate, the orientation and placement of the display organizer.
In one embodiment, the opening can be a receptacle opening, in which case the display organizer further includes a receptacle within the interior space in object receiving communication with the receptacle opening. The receptacle serves as a cup or container for holding objects, e.g., one or more writing instruments.
Alternatively, or in addition to, the opening can be an aperture configured to receive and hold an object within the interior space, the aperture further configured to support the object so as to maintain at least a portion of the object without the interior space, thereby enabling a user to easily grab the object and remove it from the display organizer. Preferably the object is held in a substantially upright position by the aperture, but it will be understood that an object resting against a side of the aperture can be in a tilted position. In cases in which the object has a handle portion, e.g., the handle of a pair of scissors or the handle of a letter opener, the opening can be configured to support the object so that the handle portion is accessible to the user from the outside of, e.g., from above, the display organizer.
In another embodiment, the display organizer of the invention can include at least one end portion attached to the top portion and two side portions. The end portion can be molded as part of the frame, e.g., as part of the top frame or as part of the bottom frame, or can be attached to the frame, e.g., attached by an adhesive, in which case the end portion can be attached to the top and side portions of the devise or, alternatively, can be attached to an optional bottom portion of the devise to form a “bottom frame”, the end and bottom portions subsequently attached to the top frame.
The end portion of the device can serve as a template to support one or more containers, cups, or compartments for holding additional items in the organizer. For example, the upwardly open the container can be configured to receive and hold business cards.
The display organizer of the invention features, on at least one of the side portions, an externally accessible media storage sleeve designed to provide viewable display of flat items such as paper or card items, or printed or photographic media. The side portion can include a display surface portion and a back surface portion, the back surface portion extending from the display surface portion and turned back toward the interior space to define the storage sleeve between the display surface portion and the back surface portion. The storage sleeve can include at least one slot sized to accept the sliding entry or exit of a flat media display item. To facilitate view of the item within the sleeve, the storage sleeve can have an outer surface that is translucent or, preferably transparent, to the eye. The display item can be, e.g., a professional license or professional certificate, or can be a photograph or a postcard. The display item can also be an item for communicating professional services, e.g., a professional announcement of a professional schedule.
One embodiment of the present invention is shown in the accompanying drawings which, together with the description thereof, will serve to exemplify the invention. The particular structure illustrated can be modified by those skilled in the art without departing from the broad scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is top front perspective view of an organizer device of the invention.
FIG. 2 is a top rear perspective view of an organizer device of the invention.
FIG. 3 is a plan view of an organizer device of the invention.
FIG. 4 is a view of section 4 – 4 , as indicated in FIG. 3 .
FIG. 5 is a view of section 5 – 5 , as indicated in FIG. 3 .
FIG. 6 is a view of section 6 – 6 , as indicated in FIG. 3 .
FIG. 7 is a perspective view, illustrating insertion by a user of a flat article into an organizer device of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The display organizer of the invention provides a system for assembling frequently used tools within immediate reach, parking equipment that is sensitive or expensive in a safe perch, while also providing a medium that is attractive and tidy for displaying personal memorabilia. The system thereby provides an efficient organizational system in a manner that balances the functional needs of the user with the esthetic and subjective need to personalize work space. A display organizer of the invention is useful in the work space of most types of workers, but is especially appropriate for use in the work areas of professional service providers, such as, without limitation, beauticians, hair stylists, draftsmen, and opticians.
By way of example, the embodiment shown in FIGS. 1–7 is directed to an organizing device that meets the needs of a hair stylist for organizing and displaying such items as, e.g., one or more pairs of scissors, a stack of business cards, plenty of pens and pencils, Post-Its® and/or a pad of paper, a protective sleeve for a display of a cosmetology license, and one or more favorite photographs.
FIGS. 1 and 2 are top perspective views of an organizer 1 , showing the front and rear ends of the device respectively, it being understood that the terms ‘front’ and ‘rear’ are assigned arbitrarily to refer to opposite ends of the device. Organizer 1 can be, e.g., a unit that is sized to fit easily on the surface of the work station of a hair stylist, e.g., approximately six inches long by four inches wide by four and a half inches tall. Organizer 1 can be, or can be assembled from, a frame or partial housing that includes top portion 5 . Attached to and/or extending from the side edges of top portion 5 are two side portions. One or both of the sides can be constructed so that the side portion turns back on itself to form a U-shape structure 7 . U-shape structure 7 forms sleeve 12 between an outer side surface, display surface portion 8 , and an inner side surface, back surface portion 9 . Preferably, display surface portion 8 is made from a material that is transparent, or at least translucent, to the eye.
The display organizer is provided with means for removably storing various instruments used by the operator. For this purpose, the horizontal top portion 5 serves as a shelf or deck that is provided with holes for receiving the instruments referred to, such as, without limitation, scissors. The instruments are put in position by merely inserting an end of each into one of the holes, and the instrument remains in position by gravity, although it may be in a tilted or canted position. The holes can be either apertures for receiving and storing objects in a ‘standing up’ position, e.g., aperture 14 , or the holes can be openings such as receptacle opening 18 into containers or cups that are attached to the top portion 5 . Various arrangements of apertures and container openings can be designed to fit the particular assortment of types of objects intended to be placed in the organizer.
Sleeve 12 is of a shape and size for receiving and holding a substantially flat item, display item 19 , e.g., an item of paper, cardboard, or stiff cloth. In a preferred embodiment, display item 19 is a photograph, certificate, postcard, or the like, that can be viewed through display surface portion 8 . The overall size and dimensions of organizer 1 can vary, and should be selected to accommodate a flat media of a predetermined size. As an example, the frame can be dimensioned to hold popular postcards or photographs, e.g., 3″×5″ photographs, or 4″×6″ photographs. For example, where an organizer is approximately six inches long by four inches wide by four inches tall, sleeve 12 can accommodate a display item 19 that is, e.g., a four inch by six inch photograph. The perspective view shown in FIG. 7 illustrates insertion by a user of a flat article into an organizer device of the invention.
Optionally, a recess can be cut in the wall of display surface portion 8 to form thumb indent 21 , which facilitates inserting and removing display item 19 into and out of sleeve 12 .
As shown in the plan view in FIG. 3 , top portion 5 can further include one or more aperture(s) 14 , having shapes and sizes chosen to fit a particular professional tool. For example, where the preferred tool is a pair of scissors, aperture 14 can have the shape shown in FIGS. 1 , 2 , and 3 , which is designed to fit an inverted pair of hairstylist shears, the aperture 14 having ‘ears’ that allow scissors to be held snugly when slightly opened. In this case, aperture 14 is a hole of, e.g., ¾ inch, or preferably ⅝ inch.
The top surface of top portion 5 can further include one or more receptacle opening(s) 18 to serve as openings into receptacle 20 . Receptacle 20 is a cup-like vessel for storing items such as writing implements, e.g., pens, pencils, markers, or other necessary implements. Although receptacle corners 22 are shown in FIGS. 1 and 2 with a round or curved shape, those skilled in the art will appreciate that the sides of receptacle 20 alternatively can join in an angled, e.g., a perpendicular, alignment to form a receptacle having squared off edges. Receptacle 20 can be formed as an integrally molded part of the frame of the organizer, such as that shown in FIG. 4 , in which case receptacle opening 18 is formed by the downward recess of receptacle 20 from the top portion 5 . Alternatively, receptacle opening 18 is a pre-cut opening in top portion 5 , to which receptacle 20 can be attached at receptacle opening 18 by an adhesive to form a permanently adhered vessel. In yet another alternative embodiment (not shown), the top open edge of receptacle 20 can have a lip portion which is sufficiently wide to support receptacle 20 when receptacle 20 is set down into receptacle opening 18 , the lip portion resting above and against opening 18 .
The frame of organizer 1 can further include end portions, arbitrarily referred to herein as front end portion 30 and rear end portion 40 . One or both of the end portions can be formed as solid end caps to the frame, within back surface portion 9 of U-shaped structure 7 . FIG. 4 is a view of section 4 — 4 , as indicated in FIG. 3 , showing front end portion 30 and rear end portion 40 attached to top portion 5 by, e.g., an adhesive.
Alternatively, end portions can be formed as the sides of another open box-like structure. The second open box-like structure, or “bottom frame,” includes a front end portion 30 , a rear end portion 40 , and a bottom 50 (not shown). The bottom frame can be fit into a frame that includes top portion 5 and the two side portions (“top frame”) to form housing for a display organizer of the invention.
The front and rear end portions can serve as panels to support various sizes and shapes of containers, e.g., one or more upwardly open container, cup, or trough. Containers are mounted in various numbers and locations, and different kinds and shapes of containers can be used. For example, compartment 15 can be of a size and shape suitable for holding business cards ( FIGS. 1 , 5 , and 7 ), e.g., a rectangular cup-like business card holder. Holder 17 can be of a size and shape suitable for holding a pad of note paper, note book, address book, a personal data organizer (PDA), or other desired item ( FIGS. 2 , 7 , and 9 ), e.g., a rectangular cup-like memo pad holder. Optionally, the open edges of compartment 15 or holder 17 can be given a decorative shape such as curves or fluting.
Preferably, the device of the invention is prepared from materials that result in products having a substantially firm, stiff, or rigid shape, such as acrylic or plastic, e.g., thermoplastic or thermoset plastic. Additional materials known to those skilled in the art can include glass, polycarbonate, polyethylene tetraphtalate glycol (PETG), Lexan® (General Electric Company Corporation, NY, N.Y.), or a form of polymethyl methacrylate (PMMA) such as, e.g., Plexiglass® (Rohm & Haas Company, Philadelphia, Pa.) or Lucite® (E. I. DuPont De Nemours And Company, Wilmington, Del.). Materials used in the invention can be clear or tinted.
Depending on the types of materials used for the housing, frame, receptacles or compartments, respectively, receptacles and compartments can be attached to the housing or frame by a heat weld, a solvent weld, a glue joint, an epoxy joint, a silicon joint or other types of heat, chemical or adhesive connection such as is well known by persons skilled in the art.
Preferably, the device, or at least that portion used to store a display item for viewing, is made from a material that is clear and transparent; or the device is clear and tinted with a color, e.g., black or grey tint, or other colors as known to those skilled in the art.
The device can be prepared by methods known by those skilled in the art, e.g., by injection molding, blow molding, or by a combination of machine processes and manual assembly. In another embodiment, a portion of the device is made by injection molding, and one or more additional portions of the device, e.g., a receptacle or pocket compartment, are then attached by a bonding technique. Suitable bonding techniques can include ultrasonic welding, hot air welding, or application with an adhesive, e.g., epoxy, glue, or solvent adhesive. For example, an injection molded piece can be formed having a shape that includes top portion 5 and the side portions, e.g., side portions having a U-shaped structure 7 to form display structures for holding photographs. To this piece is glued receptacle 20 , e.g., an acrylic box shaped to hold pencils or other instruments. End caps are also glued to the frame. Holder 17 can be glued to end portion 40 , e.g., as a container for cards or licenses. In other embodiments, one portion of the device can be prepared from, e.g., a translucent or opaque material, to which are adhered additional portions of the device, e.g., a compartment or receptacle intended for display of a photograph or other informational piece, that is prepared from a clear or transparent material.
In another optional embodiment, the interior space of a display organizer of the invention can be further enclosed by a bottom portion. For example, the organizer can be assembled from two pre-molded frames, a top frame and a bottom frame, one or both being a U-shaped structure. The top frame can encompass a storage sleeve on one or both side portions for a flat media to be displayed, such as a picture, a top portion having predetermined cut outs or openings for, e.g., attachment of a holder or receptacle to hold, e.g., pencils, and/or a slot for holding, e.g., scissors and/or other items that are deemed useful in a work setting (paper clip holder, stapler holder, letter opener, etc), and then the back picture sleeve. The bottom frame can encompass a flat base portion and front and rear ends. The top and bottom frames can be joined together by, e.g., thermal joining, or by using a solvent adhesive to join the two frames, forming a box shape apparatus. Any number and size of cup or container storage options can be affixed to the front or rear ends of the device, or, in the event that a flat media display sleeve is on only one of the side surfaces, to that side surface lacking a flat media display sleeve.
Another option is to embellish the device by adding a brand or label. The brand can be applied by thermal transfer, or ‘hot stamp’. Alternative methods of applying a brand or label include etching, applying a colored material, e.g., silver or gold colored etching, or by laser etching. Without limitation, the brand or label can be a trademark or can be a UPC code by which the device can be scanned for inventory or retail purposes. (See, e.g., U.S. Pat. No. 6,531,208 B2, issued Mar. 11, 2003, hereby incorporated by reference.
EXAMPLE 1
One embodiment of the invention is directed to a device that serves as both an organizer and a display of professional tools and personal items for a beautician or hairstylist. Such a display organizer must be able to store a diverse assortment of hair styling, cosmetic, and related professional and personal accessories in a convenient but unobtrusive fashion. Preferably, the display organizer includes apertures, receptacles, and containers that are suitable for those items known to those skilled in the art to be desired by a professional during the work day, and permissibly displayed and stored in a display organizer of the invention according to any applicable local regulatory requirements. Clientele have a wide range of needs, so modern hair styling and cosmetology professionals are challenged to maintain equipment and other essentials in an efficient manner and a convenient, accessible location as they work. For example, during the course of an ordinary working day a beautician may desire to have available on his/her work station an assortment of varied hair styling accessories such as one or more of scissors, hair driers, razors, trimmers, clippers with variable sized blade attachments, tweezers, roller sets, and curling irons. The beautician would also desire to have available a stack of business cards, plenty of pens and pencils, a pad of paper or the like, a protective sleeve for a cosmetology license, and one or more favorite photographs. The display organizer of the invention can provide an organizational system for storing and displaying such items that is compact and attractive.
EXAMPLE 2
Another embodiment of the invention is directed to a device that serves as both an organizer and a display of professional tools and personal items for a draftsman. It can contain sleeve frames for storing photographs or other flat media, along with, e.g., a container for business cards, a container for a scientific calculator, and, from the top portion, could hold, e.g., a standard 7½ inch compass, a small shape triangle (landscape templates), a knife, e.g., an X-Acto® knife, and/or various rulers and pens, e.g., micron pens.
EXAMPLE 3
Yet another example of an embodiment of the invention is directed to a device that serves as both an organizer and a display of professional tools and personal items for an optician. It can contain sleeve frames for storing photographs or other flat media, along with, e.g., various sized compartments to hold various instrument used to adjust eyeglasses, e.g., slots for the basic types of pliers necessary to make adjustments, e.g., adjustment and nose pad pliers, cutting pliers, gripping and forming pliers, lens pliers, and semi rimless pliers, as well as containers for one or more optical screwdrivers and tweezers, calipers, cleaning fluids, and wipers or wipes. | The invention addresses the needs of a professional service provider to organize and display items at or on his or her work stations that are of both a personal and professional nature, in a manner that is compact, efficient, and tidy. The apparatus includes a substantially rigid frame having a plurality of openings and/or receptacles which are adapted to receive objects, for example, scissors or shears, pens, pencils, or a pad of note paper, as well as an assortment of optional holders adapted to receive and display, for example, business cards, a professional license, professional announcements and fee schedules. The device further includes an externally accessible media storage sleeve configured for viewable display of a flat media display item, for example a photograph. | 1 |
TECHNICAL FIELD
The present disclosure relates generally to a machine navigation system and, more particularly, to a machine navigation system utilizing scale factor adjustment.
BACKGROUND
Machines such as, for example, dozers, motor graders, wheel loaders, wheel tractor scrapers, and other types of heavy equipment are used to perform a variety of tasks. Autonomously and semi-autonomously controlled machines are capable of operating with little or no human input by relying on information received from various machine systems. For example, based on machine movement input, terrain input, and/or machine operational input, a machine can be controlled to remotely and/or automatically complete a programmed task. By receiving appropriate feedback from each of the different machine systems during performance of the task, continuous adjustments to machine operation can be made that help to ensure precision and safety in completion of the task. In order to do so, however, the information provided by the different machine systems should be accurate and reliable. The velocity and distance traveled by the machine are parameters whose accuracy may be important for control and positioning of the machine.
Conventional machines typically utilize a navigation or positioning system to determine various operating parameters such as velocity, pitch rate, yaw rate, roll rate, etc. for the machine. Some conventional machines utilize a Distance Measurement Indicator (DMI) or odometer measurement to determine the velocity and distance traveled by the machine. For example, the machine controller may receive a measurement of the number of rotations of a wheel of the machine from the odometer and may calculate a distance traveled by the machine by using the number of rotations and a predetermined size of the wheel. The distance traveled may be utilized to determine the velocity of the machine. However, the distance calculated using the above method may have an error associated with it because the wheel size may change due to heat, tire pressure, road conditions, etc and the predetermined wheel size used to calculate the distance may not capture this wheel size change. Further, the rotations of the wheel may not accurately reflect the distance traveled if the wheels are subject to slipping. To compensate for such errors, some conventional machines utilize a scale factor for the distance calculation. In order to estimate the scale factor, an independent measurement for the distance traveled may be obtained by utilizing a Global Navigation Satellite System (GNSS). The distance calculated using GNSS data may be compared with the distance calculated using the odometer measurements and the scale factor may accordingly be adjusted to compensate for changes in wheel size due to the factors mentioned above.
An exemplary system that may be used to compensate for odometer measurement errors is disclosed in U.S. Pat. No. 6,360,165 (“the '165 patent”) to Chowdhary that issued on Mar. 19, 2002. The system of the '165 patent is capable of calculating the distance traveled by a vehicle. Specifically, the system of the '165 patent multiplies an odometer signal proportionate to the number of rotations of a drive train member (such as a wheel) with an odometer conversion parameter to convert the odometer signal into an estimated distance (D r ) traveled. When a Global Positing System (GPS) signal is available, a distance (D g ) traveled by the vehicle is calculated using the GPS signal and the odometer conversion parameter is calibrated to bring D r into closer proximity to D g . However, if the GPS signal is not reliable or the slip of the vehicle is higher than a certain threshold, the odometer conversion parameter is not updated to avoid introduction of slip related errors into the odometer conversion parameter.
Although the system of the '165 patent may be useful in determining the distance traveled by a machine, the system may not provide accurate estimates for distance traveled and velocity of the machine while dead-reckoning (i.e., during periods of time when GPS signals are unavailable) because the odometer conversion parameter is not updated during loss of GPS signals. For example, the system of the '165 patent may not compensate for any changes in the wheel size due to road conditions or weather conditions when the GPS signal is lost. In another scenario where the machine is loading or dumping materials carried by it while operating in an area where GPS signals are unavailable, a change in the wheel size is likely to occur but the system of the '165 patent may not compensate for this wheel size change because it does not update the odometer conversion parameter when GPS signals are unavailable.
The navigation system of the present disclosure is directed toward solving one or more of the problems set forth above and/or other problems of the prior art.
SUMMARY
In one aspect, the present disclosure is directed to a system for estimating velocity of a machine. The system may include an odometer configured to generate a first signal indicative of a distance traveled by the machine, and a locating device configured to receive a second signal indicative of a location of the machine. The system may further include a sensor configured to provide parametric values associated with performance of the machine, and a controller in communication with the odometer, the locating device, and the sensor. The controller may be configured to calculate a scale factor to compensate for an error associated with the first signal and determine whether the second signal is received by the locating device. The controller may be further configured to selectively adjust the scale factor using the parametric values to generate an adjusted scale factor where selectively adjusting may be performed based on whether the second signal is received by the locating device. The controller may be further configured to estimate the velocity of the machine based on the first signal and the adjusted scale factor.
In another aspect, the present disclosure is directed to a method of estimating velocity of a machine. The method may include receiving, from an odometer, a first signal indicative of a distance traveled by the machine and calculating a scale factor to compensate for an error associated with the first signal. The method may further include determining whether a second signal indicative of a location of the machine is received by the machine and selectively adjusting the scale factor using machine parameters to generate an adjusted scale factor, where selectively adjusting may be performed based on whether the second signal is received by the machine. The method may further include estimating the velocity of the machine based on the first signal and the adjusted scale factor.
In yet another aspect, the present disclosure is directed to a non-transitory computer-readable storage device storing instruction for enabling a process to execute a method of estimating velocity of a machine. The method may include receiving, from an odometer, a first signal indicative of a distance traveled by the machine and calculating a scale factor to compensate for an error associated with the first signal. The method may further include determining whether a second signal indicative of a location of the machine is received by the machine and selectively adjusting the scale factor using machine parameters to generate an adjusted scale factor, where selectively adjusting may be performed based on whether the second signal is received by the machine. The method may further include estimating the velocity of the machine based on the first signal and the adjusted scale factor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a pictorial illustration of an exemplary disclosed machine;
FIG. 2 is a diagrammatic illustration of an exemplary disclosed navigation system that may be used in conjunction with the machine of FIG. 1 ; and
FIG. 3 is a flowchart depicting an exemplary disclosed method performed by the navigation system of FIG. 2 .
DETAILED DESCRIPTION
FIG. 1 illustrates a machine 100 having an exemplary disclosed navigation system 110 . The machine 100 may be configured to perform some type of operation associated with an industry such as mining, construction, farming, transportation, power generation, or any other industry known in the art. For example, machine 100 may be an earth moving machine such as a haul truck, a dozer, a loader, a backhoe, an excavator, a motor grader, a wheel tractor scraper or any other earth moving machine. Machine 100 may generally include a frame 12 that at least partially defines or supports an operator station, one or more engines mounted to the frame, a plurality of traction devices 14 driven by the engine to propel machine 100 . The traction devices 14 , in the disclosed exemplary embodiments, are wheels located at opposing sides of machine 100 . Each traction device 14 may be independently driven to turn machine 100 or simultaneously and dependently driven to propel machine 100 in a straight direction. It is contemplated that one or all of traction devices 14 may be replaced with another type of traction device, if desired, such as belts or tracks.
FIG. 2 illustrates an exemplary embodiment of the navigation system 110 . The navigation system 110 may include an odometer 210 , a sensor 220 , a locating device 230 , and a controller 250 . The above sensors and the controller 250 may be connected to each other via a bus 290 . While a bus architecture is shown in FIG. 2 , any suitable architecture may be used, including any combination of wired and/or wireless networks. Additionally, such networks may be integrated into any local area network, wide area network, and/or the Internet.
The odometer 210 may provide a signal indicative of a distance traveled by the machine. The odometer 210 may provide as the signal, a measurement of number of rotations of the traction device 14 (such as a wheel 14 ). The odometer 210 may also provide, as the signal indicative of a distance traveled by the machine, a measurement of number of rotations of a member of the machine 100 's drive train. For example, the odometer 210 may provide a measurement of number of rotations of an axle of the machine 100 .
The sensor 220 may include any device capable of providing parametric values or machine parameters associated with performance of the machine 100 . For example, the sensor 220 may include a payload sensor that provides a signal indicative of a payload of the machine 100 . The sensor 220 may further include a slip detector that provides a signal indicative of a slip of the machine 100 . The sensor 220 may further include devices capable of providing signals indicative of a slope of the ground on which the machine 100 is operating, an outside temperature, tire pressure if the traction device 14 is a wheel, etc. It will be understood that the sensor 220 may have one or more of the above-mentioned devices that provide the different parametric values or machine parameters such as payload, temperature, tire pressure, slip, slope, etc.
The locating device 230 may include any device capable of providing a signal that indicates the machine's location. For example, the locating device 230 could embody, a global satellite system device (e.g., a GPS or GNSS device), a laser range finding device, or any other known locating device that receives or determines positional information associated with machine 100 and can provide an independent measurement of the machine's position. The locating device 230 may be configured to convey a signal indicative of the received or determined positional information to one or more of interface devices for display of machine location, if desired. The signal may also be directed to a controller 250 for further processing. In the exemplary embodiments discussed herein, the locating device 230 receives a GPS signal as the location signal indicative of the location of the machine 100 and provides the received location signal to the controller 250 for further processing. However, it will be understood by one of ordinary skill in the art that the disclosed exemplary embodiments could be modified to utilize other indicators of the location of the machine 100 , if desired.
Controller 250 may include processor 251 , storage 252 , and memory 253 , included together in a single device and/or provided separately. Processor 251 may include one or more known processing devices, such as a microprocessor from the Pentium™ or Xeon™ family manufactured by Intel™, the Turion™ family manufactured by AMD™, any of various processors manufactured by Sun Microsystems, or any other type of processor. Memory 253 may include one or more storage devices configured to store information used by controller 250 to perform certain functions related to disclosed embodiments. Storage 252 may include a volatile or non-volatile, magnetic, semiconductor, tape, optical, removable, nonremovable, or other type of storage device or computer-readable medium. Storage 252 may store programs and/or other information, such as information related to processing data received from one or more sensors, as discussed in greater detail below.
In one embodiment, memory 253 may include one or more velocity estimation programs or subprograms loaded from storage 252 or elsewhere that, when executed by processor 251 , perform various procedures, operations, or processes consistent with the disclosed embodiments. For example, memory 253 may include one or more programs that enable controller 250 to, among other things, collect data from the odometer 210 , the sensor 220 , and the locating device 230 , process the data according to disclosed embodiments such as those embodiments discussed with regard to FIG. 3 , and estimate the velocity of the machine 100 based on the processed data.
In certain exemplary embodiments, the velocity estimation programs may enable the controller 250 (more particularly enable the processor 251 ) to process the received signals using a Kalman filter to estimate the velocity of the machine 100 . A Kalman filter is a mathematical method that may be used to determine accurate values of measurements observed over time, such as measurements taken in a time series. The Kalman filter's general operation involves two phases, a propagation or “predict” phase and a measurement or “update” phase. In the predict phase, the value estimate from the previous timestep in the time series is used to generate an a priori value estimate. In the update phase, the a priori estimate calculated in the predict phase is combined with an estimate of the accuracy of the a priori estimate (e.g., the variance or the uncertainty), and a current measurement value to produce a refined a posteriori estimate.
In certain exemplary embodiments, the controller 250 may be enabled to implement a “predict” and “update” phase of a Kalman filter. In the “predict” phase, the controller 250 may receive, from the odometer 210 , a signal indicative of the distance traveled by the machine 100 . For example, the controller 250 may receive, from the odometer 210 , a measurement of number of rotations of a traction device 14 (for example, wheel 14 ). The controller 250 may also receive a scale factor, which when multiplied by the number of rotations of traction device 14 , provides the distance traveled by the machine 100 in a given time period. The scale factor received by the controller 250 may be calculated in a previous “update” phase of the Kalman filter implemented by the controller 250 .
The controller 250 may calculate, during the “predict” phase, the distance traveled by the machine 100 by multiplying the received scale factor with the number of rotations of traction device 14 . During the “predict” phase, the controller 250 may also estimate a velocity of the machine 100 by dividing the calculated distance by a time period corresponding to the calculated distance. In the “predict” phase, the controller 250 may also calculate an estimated uncertainty for the scale factor. Exemplarily, an uncertainty measure from an error covariance matrix of the Kalman filter may be utilized as the estimated uncertainty for the scale factor.
Having completed the “predict” phase, the controller 250 may execute the “update” phase of the Kalman filter. In the “update” phase, the controller 250 may utilize an independent measurement of the distance traveled or the velocity of the machine 100 to adjust the scale factor. Exemplarily, the controller 250 may utilize the location signals (for example, GPS signals) received from the locating device 230 to calculate a distance traveled by the machine 100 . The controller 250 may then utilize the calculated distance to calculate a velocity of the machine 100 . The controller 250 may next compare the distance/velocity from the “predict” phase and the distance/velocity from the “update” phase and adjust the scale factor to bring the “predict” phase distance/velocity closer to the “update” phase distance/velocity. The adjusted scale factor may be utilized by the controller 250 in the next iteration of the “predict” phase. In the “update” phase, the controller 250 may also calculate an estimated uncertainty for the scale factor. Exemplarily, an uncertainty measure from an error covariance matrix of the Kalman filter may be utilized as the estimated uncertainty for the scale factor.
Under certain conditions, the controller 250 may not execute the “update” phase of the Kalman filter after the “predict” phase. For example, if a location signal is not received by the locating device 230 , the controller 250 may not execute the “update” phase of the Kalman filter because an independent measurement of the distance traveled or velocity of the machine 100 is not available. Exemplarily, the controller 250 may determine that a location signal is not received by the location device 230 if no location signal is received by the locating device 230 or an unreliable (for example, very weak) location signal is received by the locating device 230 . Such a situation may occur, for example, when the machine 100 is operating in an area where GPS signals are not available or only very weak GPS signals are available.
In such conditions, where the controller 250 determines that a location signal is not received by the locating device 230 or that an unreliable location signal is received by the locating device 230 , the controller 250 may utilize machine parameters or parametric values from the sensor 220 to adjust or update the scale factor used in the “predict” phase. For example, the controller 250 may receive one or more machine parameters or parametric values such as payload, slip, slope, temperature, and tire pressure from the sensor 220 . The controller 250 may also retrieve corresponding lookup tables from storage 252 or memory 253 for the received machine parameters. For example, the memory 253 or storage 252 may store a lookup table for each of payload, slip, slope, temperature, and tire pressure, and the controller 250 may retrieve one or more of these lookup tables based on the machine parameters received from the sensor 220 . The lookup tables may specify a measure of adjustment for the scale factor and scale factor uncertainty for a value of the received machine parameter. For example, a lookup table for slip may specify that if the slip increases by a certain amount, the scale factor and the scale factor uncertainty should be adjusted by a certain amount. In another example, a lookup table for slip may specify particular values or ranges for the scale factor and scale factor uncertainty corresponding to specific values or ranges for the slip of the machine 100 . Similar lookup tables may be stored in the storage 252 or memory 253 for the other machine parameters such as payload, outside temperature, tire pressure etc.
The controller 250 may utilize the above lookup tables to adjust the current scale factor and scale factor uncertainty to generate an adjusted scale factor. In an exemplary embodiment, the controller 250 may add the different scale factor changes for the different machine parameters to adjust the scale factor. The adjusted scale factor may be utilized by the controller 250 in the next cycle or iteration of the “predict” phase to calculate the distance traveled and velocity of the machine 100 .
FIG. 3 is an exemplary process implemented by the controller 250 to estimate the velocity of the machine 100 . A detailed description of FIG. 3 is provided in the next section.
Industrial Applicability
The disclosed navigation system 110 may be applicable to any machine where accurate detection of the machine's velocity and/or distance traveled is desired. The disclosed navigation system may provide for improved estimation of the machine's velocity and/or distance traveled by utilizing machine parameters to adjust the scale factor when the machine is operating under conditions where a location signal is unavailable. Operation of the navigation system 110 will now be described in connection with the flowchart of FIG. 3 .
In step 301 , the controller 250 may receive, from the odometer 210 , a signal indicative of the distance traveled by the machine 100 . For example, the controller 250 may receive, from the odometer 210 , a measurement of number of rotations of a traction device 14 (for example, wheel 14 ).
In step 302 , the controller 250 may calculate or “predict” the distance traveled and/or velocity of the machine 100 by utilizing a scale factor and the signal received from the odometer 210 . For example, the controller 250 may multiply the scale factor the with the number of rotations of traction device 14 indicated by the signal received from the odometer 210 . Further, the controller 250 may also estimate a velocity of the machine 100 by dividing the calculated distance by a time period corresponding to the calculated distance. Also, the controller 250 may calculate an estimated uncertainty for the scale factor. Exemplarily, an uncertainty measure from an error covariance matrix of the Kalman filter may be utilized as the estimated uncertainty for the scale factor. It will be noted that steps 301 and 302 discussed above may correspond to the “predict” phase of the Kalman filter.
In step 303 , the controller 250 may determine whether a location signal is received by the locating device 230 . Exemplarily, the controller 250 may determine that a location signal is not received by the location device 230 if no location signal is received by the locating device 230 or an unreliable (for example, very weak) location signal is received by the locating device 230 . Such a situation may occur, for example, when the machine 100 is operating in an area where GPS signals are not available or only very weak GPS signals are available.
If the controller 250 determines in step 303 that a reliable location signal (a strong enough location signal) is received by the locating device 230 , the controller 250 may proceed to executing the “update” phase of the Kalman filter in step 304 . Exemplarily, the controller 250 may utilize the location signals (for example, GPS signals) received from the locating device 230 to calculate an updated distance traveled by the machine 100 . The controller 250 may then utilize the updated distance to calculate an updated velocity of the machine 100 .
Having calculated the distance and/or velocity in step 304 , the controller 250 may adjust the scale factor in step 305 . For example, the controller 250 may compare the distance/velocity from the “predict” phase and the distance/velocity from the “update” phase and adjust the scale factor to bring the “predict” phase distance/velocity closer to the “update” phase distance/velocity. The adjusted scale factor may be utilized by the controller 250 in the next iteration of the “predict” phase. In step 305 , the controller 250 may also calculate an estimated uncertainty for the scale factor. Exemplarily, an uncertainty measure from an error covariance matrix of the Kalman filter may be utilized as the estimated uncertainty for the scale factor.
If the controller 250 determines in step 303 that a location signal is not received by the locating device 230 or that an unreliable locating signal is received by the locating device 230 , the controller 250 may proceed to step 306 . In step 306 , the controller 250 may utilize machine parameters or parametric values from the sensor 220 to adjust or update the scale factor previously used in the “predict” phase. For example, the controller 250 may receive one or more machine parameters or parametric values such as payload, slip, slope, temperature, and tire pressure from the sensor 220 . The controller 250 may also retrieve corresponding lookup tables from storage 252 or memory 253 for the received machine parameters, as discussed previously. The controller 250 may utilize the lookup tables to adjust the current scale factor and scale factor uncertainty to generate an adjusted scale factor. The adjusted scale factor may be utilized by the controller 250 in the next cycle or iteration of the “predict” phase to calculate the distance traveled and velocity of the machine 100 . The process may continue to repeat in this manner until receiving instructions to stop or until new data ceases to be collected from the machine 100 .
The disclosed exemplary embodiments may allow for accurate estimation of the distance traveled and/or velocity of the machine 100 . For example, by adjusting the scale factor by using machine parameters when the location signals are not available, an accurate estimation of the velocity of the machine 100 may be possible.
It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed navigation system. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the disclosed navigation system. It is intended that the specification and examples be considered as exemplary only, with a true scope being indicated by the following claims and their equivalents. | A machine navigation system and method for estimating velocity of a machine is disclosed. The method may include receiving, from an odometer, a first signal indicative of a distance traveled by the machine and calculating a scale factor to compensate for an error associated with the first signal. The method may further include determining whether a second signal indicative of a location of the machine is received by the machine and selectively adjusting the scale factor using machine parameters to generate an adjusted scale factor, where selectively adjusting may be performed based on whether the second signal is received by the machine. The method may further include estimating the velocity of the machine based on the first signal and the adjusted scale factor. | 6 |
FIELD OF THE INVENTION
[0001] The present invention belongs to the field of light sources and more particularly relates to a novel arrangement of light cells into a multi-dimensional light source arranged in a continuous manner, connected to a single power source and capable of unlimited configuration.
BACKGROUND OF THE INVENTION
[0002] Light sources such as light emitting diodes (LEDs), Electroluminescence (EL), and organic light-emitting diodes (OLEDs) have paved the way for energy efficient lighting means. Oleg Vladimirovich Losev independently reported on the creation of an LED in 1927. Rubin Braunstein of the Radio Corporation of America reported on infrared emission from gallium arsenide (GaAs) and other semiconductor alloys in 1955. Braunstein observed infrared emission generated by simple diode structures using gallium antimonide (GaSb), GaAs, indium phosphide (InP), and silicon-germanium (SiGe) alloys at room temperature and at 77 kelvin.
[0003] In 1961, American experimenters Robert Biard and Gary Pittman working at Texas Instruments, found that GaAs emitted infrared radiation when electric current was applied and received the patent for the infrared LED. The first practical visible-spectrum (red) LED was developed in 1962 by Nick Holonyak Jr., while working at General Electric Company. In 1976, T. P. Pearsall created the first high-brightness, high efficiency LEDs for optical fiber telecommunications by inventing new semiconductor materials specifically adapted to optical fiber transmission wavelengths.
[0004] The first commercial LEDs were commonly used as replacements for incandescent and neon indicator lamps, and in seven-segment displays, first in expensive equipment such as laboratory and electronics test equipment, then later in such appliances as TVs, radios, telephones, calculators, and even watches (see list of signal applications). These red LEDs were bright enough only for use as indicators, as the light output was not enough to illuminate an area. The invention and development of the high power white light LED led to use for illumination
[0005] Electroluminescence (EL) or the generation of light by the electrical excitation of light emitting phosphors has been around for many years. Electroluminescence was first observed in silicon carbide (SiC) by Captain Henry Joseph Round in 1907 who reported that a yellow light was produced when a current was passed through a silicon carbide detector. The first thin-film EL structures were fabricated in the late 1950s by Vlasenko and Popkov who observed that luminance increased markedly in EL devices when they used a thin film of Zinc Sulfide doped with Manganese (ZnS:Mn). Luminance was much higher in thin film EL (TFEL) devices than in those using powdered substances. Such devices however were still too unreliable for commercial use.
[0006] Organic light-emitting diodes (OLEDs) are transparent when turned off the devices could even be installed as windows or skylights to mimic the feel of natural light after dark—or to serve as the ultimate inconspicuous flat-panel television. In 2006 scientists studying OLEDs made a critical leap from single-color displays to a highly efficient and long-lived natural light source.
[0007] Despite various improvements and progress in the field, some of the major obstacles that still exist to effective use of light sources such as LEDs, ELs and OLEDs are problems of configuration in novel sizes, shapes and patterns, problems in easy connectivity between different light segments, low light output, susceptibility to moisture, problems of easy installation without many peripherals, cost effective manufacture, maximum utilization of minimal power sources and short life.
[0008] Accordingly, improvements are needed in the existing methods and structures that negate the above shortcomings in the existing systems.
[0009] The relevant prior art methods, which will deal with light sources, are as follows:
[0010] U.S. Pat. No. 4,138,620 describes a multi panel electroluminescent panel assembly in which an area extending over several panels may be uniformly illuminated by light produced by the panels, and over which non-illuminated areas, stripes or the like resulting from electrode contracts are eliminated. Each panel is constructed such that the light produced per unit area is substantially uniform throughout the panel, including that from an area immediately adjacent at least one edge thereof.
[0011] U.S. Pat. No. 4,173,035 describes a flexible lighting strip including a circuit of modular construction formed thereon, light emitting diodes connected to said circuit, and the circuit being connectable to control circuitry which provides selected energization to said circuit and the light emitting diodes for effecting a moving light.
[0012] U.S. Pat. No. 4,204,273 describes a flexible conductor of strip configuration including a pair of copper conductors laminated between a pair of insulating material layers. Illuminating comprising a plurality of miniature or sub-miniature light bulbs assembled in a longitudinal array along a preferably flexible and flat conductor.
[0013] U.S. Pat. No. 4,899,086 describes an electroluminescence light emission apparatus based on a switch circuit formed of a switch element and a thyristor connected in series across a DC power source. Electroluminescence light emission apparatus having a simple configuration and a low level of power consumption, while providing a satisfactory level of emitted light brightness and utilizes an electroluminescence element functioning to emit light in response to applied voltage pulses.
[0014] U.S. Pat. No. 5,336,345 describes an elongate electroluminescent light strip. An electroluminescent light element which has a semitransparent film is encapsulated in a moisture impervious material. A process for extruding such a strip is also provided.
[0015] U.S. Pat. No. 5,485,355 describes a cable like electroluminescent light source comprises at least two electrodes mutually disposed in such a way as to crate between them an electric field when a voltage is applied to them; at least one type of pulverulent electroluminophor dispersed in a dielectric binder and disposed in such proximity to the electrodes as to be effectively excited by the electric fields when created and to emit light of a specific color, and a transparent polymer sheath encasing the electrodes and the electroluminophor.
[0016] U.S. Pat. No. 5,552,679 describes an illumination system with a panel that is capable of producing electroluminescence function of the panel. An illumination system can emit electroluminescence light as well as reflect incident light received from an outside light source. A layer of phosphor is excited by a power source, and a reflective layer disposed on top of the phosphor layer reflects.
[0017] U.S. Pat. No. 5,976,613 describes a flexible thick film electroluminescent lamp and method of construction in which a single non-hygroscopic binder is used for all layers thereby reducing delamination as a result of temperature changes and the susceptibility to moisture. Thick film electroluminescent lamps comprise a phosphor between an optically transparent front electrode layer, and a back electrode layer, all covered by protective electrode layer. The two electrodes are generally planar layers, but may be grids of electrically conductive material disposed at right angles to each other so that the phosphor at selected grid coordinates can be excited.
[0018] U.S. Pat. No. 6,849,869 describes the luminous efficiency and radiance of light emitting diodes (LEDs) fabricated with conjugated organic polymer layers.
[0019] U.S. Pat. No. 7,109,661 describes an electroluminescent light emission system having electroluminescent light emitting layer containing electroluminescent light emitting elements. The AC electric field forming material on the one surface side enables an AC electric field to be generated in the electroluminescent light emitting layer with an AC voltage applied between the first electrode layer an the second electrode layer.
[0020] U.S. Pat. No. 7,354,785 describes an electroluminescent device having light emitting layer containing phosphor particles which protrude from a light emitting layer, and an electrode layer which conforms to the protrusions. Methods of constructing a lamp using a temperature above the softening temperature of the insulating layer of the device are also disclosed.
[0021] US Patent Publication no. 20010043472 describes a ribbon light string is formed from a reinforced ribbon carrying a light string. The ribbon may be reinforced with peripheral reinforcing wires so that it may be shaped in decorative ways.
[0022] US Patent Publication no. 20020145873 describes a ribbon light assembly comprising a substrate and at least one light string releasably intertwined with the substrate. Each light string is formed of a plurality of lamp sockets and a plurality of lamp sockets and a plurality of wires connecting the lamp sockets. Each of the lamp sockets is substantially disposed on one substrate surface, and each of the wires is substantially disposed on an opposite surface. An opposite surface which receives at one element thereto, maintain the lamp sockets in a fixed pattern on the substrate.
[0023] US Patent Publication no. 20060244377 describes an electroluminescent light source has an elongated insulating transparent polymer sheaths having longitudinal axis of the sheath and connectable to a power source; a plurality of elongate electroluminescent layers partially surrounding one of the electrodes. Each electrodes having outer surface is partially surrounded by a respective one of the electroluminescent layers and being provided with a light reflecting coating.
[0024] US Patent Publication no. 20070210321 describes an edge light-emitting device having, on a light permeable substrate, a stacked structure including a pair of electrodes and at least one light emitting layer interposed between the electrodes, in which light emission is taken-out from a light emitting edge other than the light emitting edge of the stacked structure.
[0025] US Patent Publication no. 20090296395 describes that the present invention provides a light strip comprises an elongate core layer of insulating material having a plurality of light mounting apertures extending through the core layer. A light strip comprising of light emitting diodes connected at longitudinally spaced positions between a pair of longitudinally extending conductive elements of forming the light strip. A core layer spans in the longitudinal direction adjacent each one of the two opposed faces of the elongate core layer to enclose opposing ends of the light mounting apertures with the light emitting diodes therein.
[0026] US Patent Publication no. 2010057584 describes a light emitting strip structure with light guiding effect, which is hallow light guide strip body made of transparent material. A light guide strip body is formed with an axial internal chamber. Multiple recessed/raised sections are formed on a wall of the internal chamber for deflecting or reflecting light projected into the internal chamber from a light source.
[0027] US Patent Publication no. 20100061089 describes a flexible light strip includes an electrical-conductive layer, a plurality of light emitting units, an insulating layer and a heat-conducting layer. The light emitting units are adhered to the electrical-conductive layer and are electrically connected thereto. The insulating layer is overlapped on one surface of the electrical-conductive layer. The insulating layer is provided with a plurality of through holes for allowing the light emitting units to pass through. The heat conductive layer is adhered on the electrical-conductive layer.
[0028] However the purpose and methodology of all the above inventions that are part of prior art do not envisage the unique embodiment of several light cells that are in LED, or Electroluminescence (EL) or any other efficient light source that constitute a multi-dimensional light source consisting of a mother cell and several sister cells as required that can be arranged in a continuous manner and is capable of unlimited configuration.
[0029] Thus it is desirable to provide a system of light cells that can be effectively used without using PCB motherboard, hard connection electrical wires or welding that could be placed on an adhesive tape, cloth, or hard surface of unlimited dimensions and powered using a single power source.
[0030] It will be apparent to those skilled in the art that the objects of this invention have been achieved by providing mobile terminal with a spin menu, which is unique in nature, unlike existing menu selection models in mobile terminals that are suited only for limited purposes. Various changes may be made in and without departing from the concept of the invention. Further, features of some stages disclosed in this application may be employed with features of other stages. Therefore, the scope of the invention is to be determined by the terminology of the following description, claims, drawings and the legal equivalents thereof.
SUMMARY OF THE INVENTION:
[0031] The present invention may be summarized, at least in part, with reference to its objects.
[0032] It is therefore a primary objective of the present invention to provide a novel arrangement of light cells that can be arranged into a multi-dimensional light source in a continuous manner with one mother cell and as many sister cells as required connected to the mother cell.
[0033] Another objective of the present invention is to provide a novel arrangement of light cells that can be connected to a single power source.
[0034] Another objective of the present invention is to provide a novel arrangement of light cells that is capable of unlimited configuration.
[0035] Another objective of the present invention is to provide a novel arrangement of light cells that could be placed on an adhesive tape, cloth, or hard surface of unlimited dimensions.
[0036] Another objective of the present invention is to provide a novel arrangement of light cells that can be cut with the adhesive tape at any length and dimension and attached to any other part of the tape.
[0037] Another objective of the present invention is to provide a novel arrangement of light cells that requires no hard connectivity, electrical wires, PC Board, soldering or any other conventional electrical wiring.
[0038] Another objective of the present invention is to provide a novel arrangement of light cells that can be used for household and commercial lighting, all kinds of holiday decorations, arts and commercial advertising.
[0039] A further objective of the present invention is to provide a novel arrangement of light cells that is flexible, easily adaptable to newer requirements, moisture proof, and easy to install and maintain.
[0040] The invention described herein thus comprises a novel arrangement of light cells that are in LED or Electroluminescence (EL) or any other efficient light source and are placed adjacent to each other and touching each other to form a continuous and multi dimensional light source without using PCB motherboard, hard connection electrical wires or welding. The present invention can be placed on an adhesive tape, cloth, hard surface or any adhesive tape for unlimited dimensions. A surface such as an adhesive tape containing the present invention can be cut at any length and place it to any part of the surface. When such cutting happens, the present invention does not need to have another source for every such tape and extra tools and materials, a single power source is sufficient.
[0041] The above summary is intended to illustrate exemplary embodiments of the invention, which will be best understood in conjunction with the detailed description to follow, and are not intended to limit the scope of the invention.
[0042] Additional objects and embodiments of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. Thus these and other objects of the present invention will be more readily apparent when considered in reference to the following description and when taken in conjunction with the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a diagram showing the parts of a mother cell of the present invention.
[0044] FIG. 2 is a diagram showing the connection of the mother cell to sister cells on a background material and working of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0045] 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 particular applications of the invention and their requirements.
[0046] The present invention may involve novel systems and processes to implement the said invention. For example, although a series of processes may be described with reference to a diagram, the order of processes may differ in other implementations when the performance of one process is not dependent on the completion of another process. Further, non-dependent processes may be performed in parallel. Thus, the present invention is not intended to be limited to the embodiments shown.
[0047] The present invention can be configured as follows:
[0048] As illustrated in FIG. 1 and FIG. 2 a primary unit of the present invention that is electrically powered, is called the mother cell ( 11 ) comprising of a large ring ( 1 ), non-conductive material rings ( 2 ) and ( 6 ), a small ring ( 4 ), non-conductive material ( 7 ), any efficient light source ( 3 ) including but not limited to an LED or Electroluminescence (EL), copper springs ( 5 ), an electrical wire ( 8 ), and a background holding material ( 10 ) such as adhesive tape.
[0049] In a preferred embodiment of the present invention, the mother cell ( 11 ) is the first cell that connects to power source. A large ring ( 1 ) in a mother cell ( 11 ) has non-conductive material ring ( 2 ) and ( 6 ) on both sides of the large ring ( 1 ). The large ring ( 1 ) in a particular mother cell ( 11 ) acts as a connector to any side of another mother cell ( 11 ). A large ring ( 1 ) thus passes electrical current to the light source ( 3 ) via the electrical wire ( 8 ). A small ring ( 4 ) acts as a connector to any other mother cell and has non-conductive material ( 7 ) on one side of the small ring ( 4 ).
[0050] The small ring ( 4 ) passes electrical current to the light source ( 3 ) via an electrical wire ( 8 ). The copper springs ( 5 ) in the present invention improve electrical connectivity among the various mother cells ( 11 ), and provides flexibility by facilitating bending between mother cells ( 11 ) so that they can be arranged in various configurations not restricted to a straight line and including a spherical or other configuration. This makes it possible to create diverse kinds of unconventional configurations to create a particular larger light pattern. Further due to the copper springs ( 5 ), the mother cells ( 11 ) need not be arranged on a conventional hard background surface but can be arranged on any flexible background material ( 10 ).
[0051] In a preferred embodiment of the present invention, the mother cell ( 11 ) connects to an AC or CD electrical source. From the mother cell ( 11 ), electrical power is transferred to the remaining cells called sister cells ( 12 ) when they are connected to the mother cell ( 11 ). Miniature transformers ensure electrical current transfer to the sister light cells ( 12 ) that are situated away from the mother cell ( 11 ). The large rings ( 1 ) and the small rings ( 4 ) of a mother cell ( 11 ) thus act as a connector of any side and passes the electrical current through the sister cells ( 12 ) to the light source ( 3 ).
[0052] In a preferred embodiment of the present invention, as depicted in FIGS. 1 and 2 , several LED cells or electroluminescent EL cells or any other efficient light sources ( 3 ) are placed adjacent to each other on any background holding material ( 10 ) such as an adhesive tape, cloth, or a hard surface having unlimited dimensions, with each light source ( 3 ) touching each other to form a continuous and multi dimensional light source without using PCB motherboard, hard connection electrical wires or welding. The single mother cell ( 11 ) among the light cells connects to a power source and from there it passes on the electrical power to sister cells ( 12 ). These sister light cells ( 12 ) are arranged in a continuous manner, therefore a sister light cell ( 12 ) gets illuminated by contacting another sister light cell ( 12 ) that is placed on a flexible or hard background. The background can be cut and pasted in any configuration such that one or more light cell ( 12 ) is connected to a sister light cell ( 12 ) to continue the lighting process without using any separate hard connectivity, electrical wires, PC Board, soldering or any other conventional electrical wiring. The entire system can be powered using one source of electrical power. The placing of the cells on the background material ( 10 ) not only keeps the cells adjacent to each other but also helps provide multi dimensional configuration.
[0053] In another embodiment of the present invention, the LED light or Electroluminescence (EL) light source ( 3 ) fits inside the rings to produce light.
[0054] In another embodiment of the present invention, in addition to the copper springs ( 5 ) providing improved electrical connectivity between cells, since the copper springs ( 5 ) are flexible and as described above, facilitate bending between cells, it is also possible to create arrangements where the cells don't have to be even on the any background but are supported in a particular shape formation by the stability provided by the presence of multiple cells.
[0055] In another embodiment of the present invention, when the light cells are placed on a background material ( 10 ) such as an adhesive tape, Velcro or a solid surface, a user can cut or tear such background material ( 10 ) and place the cut or torn off piece of background material containing light cells anywhere adjacent to the main light cell assembly to create different configurations and shapes including but not limited to circular, hexagonal, octagonal or any geometrical or other shape. There is thus no need to build a connection or hard wire or any other modifications to link the main light cell assembly with the cut or torn off light cell section. It is enough to ensure that the light cells in both the main assembly and torn or cut off portion are in contact with each other, with the copper springs ( 5 ) providing improved electrical connectivity between the cells.
[0056] In this application, the terminology ‘embodiment’ can be used to describe any aspect, feature, process or step, any combination thereof, and/or any portion thereof, etc. While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure come within known or customary practice within the art to which the invention pertains and may be applied to the essential features herein before set forth.
[0057] Further it will be apparent to those skilled in the art that the objects of this invention have been achieved by providing the above invention. However various changes may be made in the structure of the invention without departing from the concept of the invention. Therefore, the scope of the invention is to be determined by the terminology of the above description and the legal equivalents thereof.
[0058] 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. | A novel arrangement of light cells on a flexible or solid background into a multi-dimensional light source capable of unlimited configuration, which comprises of a mother cell that is connected to one source of electrical power and gets charged, subsequently charging all the other light cells and thus illuminating the entire light source with unlimited configuration. | 5 |
CROSS-REFERENCE
[0001] This application claims priority to co-pending U.S. provisional patent application entitled “Method and System for Controlling Streamers,” having Ser. No. 61/112,429, filed Nov. 7, 2008, which is entirely incorporated by reference.
BACKGROUND
[0002] The invention relates generally to offshore marine seismic prospecting and, more particularly, to systems and methods for controlling the spread of towed seismic streamers.
[0003] In the search for hydrocarbon deposits beneath the ocean floor, a survey vessel 10 , as shown in FIG. 1 , tows one or more seismic sources (not shown) and one or more streamer cables S 1 -S 4 instrumented with hydrophones and other sensors. In multiple-streamer systems, the streamers are towed underwater behind the survey vessel in a generally parallel arrangement. The tail end of each streamer is tethered to a tail buoy 11 that marks its position. The seismic source periodically emits a seismic wave that propagates into the ocean floor and reflects off geologic formations. The reflected seismic waves are received by the hydrophones in the streamers. The hydrophone data is collected and later processed to produce a map of the earth's crust in the survey area.
[0004] The quality of the survey depends on, among other things, knowledge of the precise position of each hydrophone. Position sensors, such as heading sensors and acoustic ranging devices 12 , located along the lengths of the streamers are used to determine the shapes of the streamers and their relative separations. The acoustic ranging devices are typically acoustic transceivers operating on a range of channels over which they transmit and receive acoustic ranging signals to and from one another to produce accurate ranges 14 between their locations on the streamers. The many ranges—only a few are shown in FIG. 1 —and streamer heading data from the many heading sensors are used to compute a network solution that defines the shapes of the individual streamers and their relative positions. When one point on the streamer array is tied to a geodetic reference, such as provided by a GPS receiver, the absolute position of each hydrophone can be determined.
[0005] Positioning devices, such as depth-keeping birds and lateral steering devices 16 located at nodes along the lengths of the streamers, are used to control the depths of the streamers and their separations from each other. The positioning devices could be equipped with acoustic ranging devices to range with other positioning devices so equipped and with dedicated acoustic ranging devices. Precise positioning of the streamers is important during online survey passes to produce a high-quality map. Cross currents, however, cause the streamers to deviate from straight lines parallel to the towing vessel's course. Instead, the streamers may angle straight from their tow points or assume a curved shape with their tail ends tailing away from the straight lines. This feathering of the streamers is often undesirable in online survey passes. Precise positioning is also important during turns between online survey runs to reduce the time of the turn without entangling the streamers.
[0006] In conventional streamer positioning systems, one of the streamers, outermost port streamer S 1 in this example, is used as a reference streamer. A shipboard controller 18 collects the position sensor data and computes the network solution representing the shapes of the streamers and their separations from each other. From the network solution and the target separations of corresponding steering-device nodes on the streamers referenced directly or indirectly to points on the reference streamer, the shipboard controller derives steering commands for each lateral steering device. The steering commands are transmitted to the steering devices to adjust their control planes, or fins, to drive the streamers laterally, as indicated by arrows 20 , to maintain the target separations.
[0007] In current systems, a human operator steers the reference streamer by sending lateral steering commands to the lateral position controllers to drive the reference streamer to adjust feather. The other streamers are then automatically steered toward the selected separations referenced directly or indirectly from the reference streamer. But the manual positioning of the reference streamer is time-consuming and, in turns, can be hectic as well.
SUMMARY
[0008] This shortcoming and others are addressed by a method, embodying features of the invention, for positioning one or more streamers behind a survey vessel. The method comprises: towing a first actual streamer equipped with lateral steering devices at spaced apart locations along the length of the streamer; defining an imaginary streamer having a shape and position behind the survey vessel; determining the shape and position of the first actual streamer; defining a target lateral separation between the imaginary streamer and the first actual streamer; and sending lateral steering commands to the lateral steering devices to drive the first actual streamer toward the target lateral separation from the imaginary streamer.
[0009] Another aspect of the invention provides a system for controlling the spread of a plurality of streamers towed behind a survey vessel. The system comprises a plurality of actual streamers having head ends laterally offset from each other. Each actual streamer has a plurality of lateral steering devices and position sensors disposed along its length. A controller receives position data from the position sensors. The controller includes auto-steering means that calculates the shape and position of an imaginary streamer towed by the survey vessel. The controller also includes network calculating means that determines the shapes and positions of the actual streamers from the position data and calculates lateral separations for each of the actual streamers referenced to the shape and position of the imaginary streamer received from the auto-steering means. The controller then sends lateral steering commands to the lateral steering devices corresponding to the calculated lateral separations.
[0010] In yet another aspect of the invention, a method for controlling the spread of N actual streamers S 1 -S N , comprises: defining the shape and position of an imaginary streamer G r ; determining the shapes and positions of actual streamers S 1 -S N ; adjusting the separation of actual reference streamer S r from imaginary streamer G r ; and adjusting the separation of actual streamer S n from another actual streamer S i , for every n ε {1, 2, . . . , N} and n≠r and wherein i ε {1, 2, . . . , N}, i≠n, and, in at least one case, i=r.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] These features and aspects of the invention, as well as its advantages, are better understood by referring to the following description, appended claims, and accompanying drawings, in which:
[0012] FIG. 1 is a top plan view of a survey vessel towing a steamer network illustrating conventional acoustic cross-bracing and lateral steering of streamers using a reference streamer;
[0013] FIG. 2 is a top plan view as in FIG. 1 illustrating the use of a virtual streamer to which a reference streamer is referred, according to the invention;
[0014] FIG. 3 is a block diagram of the streamer positioning control system usable with the streamer network of FIG. 2 ; and
[0015] FIGS. 4A-4C are flowcharts of a control sequence for the control system of FIG. 3 .
DETAILED DESCRIPTION
[0016] The operation of a streamer steering system according to the invention is described with reference to an exemplary four-streamer system shown in FIG. 2 . (The streamer arrangement is the same as that in FIG. 1 .) A survey vessel 10 tows four steamers S 1 -S 4 (generally, S 1 -S N for an N-streamer system) whose tail ends 22 are tethered to tail buoys 11 . Head ends 23 of the streamers are attached to a system of tow cables and tethers 24 attached to the rear deck of the vessel. Paravanes 26 are used to maintain a wide spread for the deployed streamer network. Lateral steering devices 16 —disposed at spaced apart locations, or steering nodes, e.g., every 300 m, along the length of each streamer—exert lateral forces 20 to drive the streamer to starboard or port. A shipboard controller 28 connected to the position sensors and the lateral steering devices and the streamers by a communications link, such as a hardwired link 30 running along the tow cables and through the streamers, receives positioning and other data from the position sensors and transmits steering commands to the lateral steering devices over the link.
[0017] Just as for the streamer system of FIG. 1 , the system of FIG. 2 designates one streamer—outermost port streamer S 1 in this example—as a reference streamer S r . The closest neighboring streamer S 2 is steered toward a selected separation D from the reference streamer S 1 . As shown in FIG. 2 , the node for head-end lateral steering device 16 A on streamer S 2 is farther away from the distance of closest approach to reference streamer S i than the selected separation. Consequently, the shipboard controller issues a steering command to the head-end steering device 16 A to drive the streamer to port, as indicated by arrow 32 . Because the tail-end steering node for steering device 16 B on streamer S 2 is closer to the distance of closest approach to reference streamer S 1 than the selected separation, as shown in FIG. 2 , the shipboard controller issues the steering command to the tail-end lateral steering device 16 B on S 2 to force the streamer to starboard, as indicated by arrow 33 . The steering commands contain, for example, control values, such as fin angle values related to the separation error calculated from the desired target separation and the actual separation between the node on the streamer at which the lateral steering device is located and the nearest point on a streamer to which it is referenced. The lengths of the arrows 32 , 33 are proportional to the magnitudes of the changes in the fin angle settings, which control the azimuth of the control surfaces of each lateral steering device. Because streamers S i and S 2 are at the desired separation D about midway along their lengths in FIG. 2 , the fin angle setting for lateral steering device 16 C does not have to change.
[0018] Just as streamer S 2 is steered directly referenced to the shape and position of reference streamer S 1 , S 2 's starboard neighbor S 3 is steered referenced to the position and shape of S 2 . And outermost starboard streamer S 4 is positioned relative to S 3 . This is a preferred mode of operation because the ranges between closely spaced, adjacent streamers as derived from the acoustic ranging devices are typically more accurate than those between farther apart, non-adjacent streamers. In this example, each of the streamers S 2 -S 4 is steered to maintain a desired separation from its port neighbor. Reference streamer S 1 thus serves as a direct reference for streamer S 2 and as an indirect reference for the other streamers.
[0019] In one conventional version of a streamer steering system, the reference streamer S 1 is steered by a human operator giving manual commands via the shipboard controller to adjust the feather of the reference, which causes the streamer to assume a corresponding shape and position. According to the invention, the positioning of the reference streamer is automated by referencing it to a pre-defined imaginary streamer G r . This imaginary, or virtual, or ghost streamer is defined through the shipboard controller according to selectable criteria, such as target feather. Once the criteria are selected, the shipboard controller automatically drives the reference streamer S r to assume a pre-selected separation, which could be zero, from the ghost streamer G r . (In FIG. 2 , r=1.) The other streamers S 2 -S 4 are steered conventionally as already described. As shown in FIG. 2 , the ghost streamer G 1 is selected with its head end 23 ′ coincident with the tow point 34 of reference streamer S 1 . In this example, G 1 is also shown with a certain amount of feather F. (But G 1 could alternatively be selected to be deployed straight behind the vessel or offset from the tow point of S 1 .)
[0020] Generally, for a system of N actual streamers S 1 -S N , one of the streamers is designated a reference streamer S r . In a preferred arrangement, r=1 or N to designate an outermost port or starboard streamer, S 1 or S N , for streamers consecutively positioned from port to starboard S 1 -S N . The associated ghost streamer is then G 1 or G N . If the reference ghost streamer G r =G 1 , then actual streamer S 1 is referenced to G 1 , and S n is referenced to S n−1 for every n ε {2, 3, . . . , N}. More generally, if the reference streamer S r is referenced to ghost streamer G r , then actual streamer S n will be referenced to another actual streamer S i for every n ε {1, 2, . . . , N} and n≠r, and wherein i ε {1, 2, . . . , N}, i≠n, and, in at least one case, i=r.
[0021] A block diagram of the streamer steering control system is shown in FIG. 3 . The shipboard controller, which may comprise one or more processors, executes a number of individual processes to control the shape and separations of the streamers. A control user interface 36 allows an operator to set various lateral steering parameters. The parameters may include:
a) Ghost Streamer ON/OFF—enables or disables steering of the reference streamer to the ghost streamer; b) Reference Streamer—selects which streamer to use as the reference streamer S r during automatic separation control of the streamers; c) Max Fin Angle for S r —maximum value of the fin angle to be used on the reference streamer during online operation (to limit bias in the fin angle control range and to limit flow noise due to lateral displacement of the streamer); d) Mode—sets the online operating mode (fan mode or even spacing mode for streamer shape and separation); and e) Feather—manual setting of the desired feather for a 3D survey line.
[0027] Some of these parameters are sent to a network calculator means 38 that calculates the current positions of all the actual streamers S 1 -S N . (As used in this description and in the claims, “position” means position and shape of the streamer, except when explicitly used with “shape.”) The network calculator then calculates the separations between the actual streamers and their corresponding target streamers.
[0028] During a typical survey, a realtime planner 40 defines the track the vessel is to follow. Each track consists of a series of turns followed by online passes. The planner defines online shot points along the online portion of the track and at the ends of the turns and offline vessel positions during the remainder of the turns. In a 3D survey, the final target feather value coming out of a turn is the value manually entered via the control user interface. In a 4D survey, target feather angles are set and adjusted along the survey line based on feather angles recorded during the baseline survey the new survey is designed to replicate.
[0029] The realtime planner sends the computed track setting, which includes the association of feather matching, to an auto-steering means 42 , which calculates the required future positions of the ghost streamers. The auto-steering means is a process that computes the range and bearing from each positioning-sensor node, as well as from the nodes for other devices, on each streamer to the distance of closest approach to that streamer's target streamer, whether another actual streamer or a virtual, or ghost, streamer associated with the actual streamer. The auto-steering process also computes the shape and position of the ghost streamer G 1 , for example, to which the reference streamer S 1 is referenced. The auto-steering process can also optionally compute the ghost streamers G 2 -G N associated with each of the other actual streamers S 2 -S N from the calculated actual streamer positions received from the network calculator. (See FIG. 2 for an example of one of the other ghost streamers G 4 , shown with no feather for the purposes of illustration.) This allows the ghost and reference streamers to be changed from the outermost port streamer to the outermost starboard streamer, for example. The auto-steering process updates the ghost streamer's shapes and positions at a generally regular interval in turns and offline and, typically, once per shot online.
[0030] A lateral steering interface 43 receives the streamer separation values and, under the control of the control user interface, passes them along to a lateral controller 44 that converts the streamer separation values for each node into streamer steering commands, including, for example, fin angle commands, and transmits them over the communications link 30 to the lateral steering devices 16 , which appropriately adjust their fin angles.
[0031] Sometimes during an online pass, strong currents or navigation or instrumentation problems can cause the streamer spread to inadequately cover the survey area. The survey area is divided into a gridwork of bins. If an insufficient amount of data is collected in some of the bins, the pass will have to be re-run, at least in part, to fill in those bins with more data. The process of re-running parts of online passes in subsequent online passes to complete the data set is known as infill. A realtime binning supervisor process 46 monitors the bins during a line and adjusts the spread of the streamers to minimize the amount of infill needed. The required track derived form the binning data to meet the infill requirements is sent to the auto-steering process, which then calculates a corresponding ghost streamer for the pass.
[0032] Another process is used to supervise the spread of the streamer system during deployment by helping to automate the distribution of streamer separations as the streamers are payed out from the back deck of the survey vessel. A deployment supervisor 48 sends track and deployment data to the auto-steering process, which calculates the ghost streamer position for the network calculator to control the lateral steering devices.
[0033] A flowchart of the streamer steering process that runs once each shot point online or at a regular interval offline and in turns is shown in FIGS. 4A-4C . First, the shipboard controller computes the network solution 50 from ranges gathered from the acoustic ranging devices and headings from the heading sensors. From the network solution, the actual streamer positions are updated 52 . These steps are performed by the network calculator. Next, the auto-steering process updates the ghost streamer position from the desired feather 54 . The network calculator then calculates the ghost-to-reference-streamer separation 56 (for example, between each node on S 1 and its closest point of approach to G 1 ) and the separations from each of the other actual streamers to a neighboring streamer 58 (between nodes on S n and their closest points of approach to S n-1 ). Once the separations at each node in the network are calculated, the lateral steering interface, as controlled by the control user interface sends 60 the separations to the lateral controller.
[0034] The lateral controller calculates 62 lateral separation-error terms corresponding to the separations of a lateral steering device from one or more actual or ghost streamers. 62 . Closed-loop controls, such as proportional-integral (PI) control loops, calculate 64 new fin angles for the devices' control surfaces, or fins. A motor in each steering device drives the fins to the new fin angle 66 . While the lateral steering devices are being controlled to steer the streamers, the shipboard controller triggers a new data acquisition cycle 68 during which the position sensors (heading sensors and acoustic ranging devices) acquire streamer position data (headings and acoustic ranges) 70 . The position sensors then send 72 the position data over the communications link to the controller for the network calculator to compute the network solution during the next positioning data update cycle, typically once per shot online and at some regular rate when running offline or in turns between lines.
[0035] Although the invention has been described with reference to a preferred version, other versions are possible. For example, the PI control loops that run in the shipboard lateral controller could be performed, for example, individually in each of the steering devices on the streamers. In that case, the steering devices would receive the necessary separation values from the shipboard controller in a command message. As yet another example, the system described is adaptable to a multi-vessel survey, in which most of the shipboard controller functions are performed by a master controller aboard one of the vessels linked to slave controllers aboard the other vessels. The slave controllers would be devoted largely to interfacing with the positioning-sensors and lateral steering devices. The master controller would perform most of the other functions, such as computing the complete network solution, defining the track for each streamer, and defining the ghost streamer for each vessel's streamer network. A radio or other wireless communication link would allow the master controller to communicate with the slaves on the other vessels. As another example, the block diagram defines a number of discrete blocks performing specific functions. The names of these blocks and the functions they perform were arbitrarily assigned to simplify the description of the system. The various processes may be distributed across blocks in many ways to similar effect. So, as these few examples suggest, the scope of the claims is not meant to be limited to the preferred version described in detail. | A method and system for controlling the shape and separation of an arrangement of streamers towed behind a survey vessel. Each streamer is steered laterally by lateral steering devices positioned along its length at specific nodes. Each streamer is driven by its lateral steering devices to achieve a specified separation from a neighboring streamer. One of these actual streamers, used as a reference by the other actual streamers, is steered to achieve a specified separation from an imaginary, or ghost, streamer virtually towed with the actual streamers. | 6 |
This application is a continuation of application Serial No. PCT/CH97/00169, filed Apr. 28, 1997.
INTRODUCTION
The PCT/CH97/00168 application of Apr. 28, 1997 (EPA 97'917'205-3) describes ultramicroemulsions from spontaneously dispersible concentrates comprising esters with bioflavonoid compounds having antitumor, antiviral, virucidal and/or antiparasitic efficacy. Thanks to the demonstrated solubilization of the active principles, in the form of thermostable, oil-in-water emulsions possessing very small micelles in the lowest nanosize region, an excellent bioavailability can be achieved for them. In the course of an intensive elaboration of the properties of this class of compounds, it was found that surprisingly also the glycoside peresters of the studied bioflavonoids have comparative pharmacological properties, provided that they are also formulated correspondingly. In such manner they can be used for curative as well as preventive purposes. Because they are non-toxic and yet highly active, members of this group of natural agents, which up-to-now is only scarcely investigated, these findings can be instrumental in opening a broad therapeutic window. The application of the fatty-tail principle for the esterification and the incorporation of the newly obtained glycoside esters into inventive, spontaneously dispersible concentrates form a systematic two step-approach—the extension of a procedure which has already been described in principle in the Swiss patent CH 683'426 (U.S. Pat. No. 5,593,691) and in the CH patent application 2239-95 (PCT/CH96/00280; EPA 96'925'634-6). The subject of the present invention consequently are Flavonol-glycoside peresters as characterized hereafter, their incorporation into pharmaceutically practicable application forms, as well as their use as medicaments having efficacy against tumors, eczemae, psoriasis, viral and parasitic infections and metabolic disorders.
DESCRIPTION OF THE INVENTION
1.0 Definition of Scope
Flavonol-Glycoside-Peresters, as the term is used in this invention, comprise the following compounds:
1. QUERCETIN (R 1 -R 5 =H); Merck-Index 11.8044
2. SPIRAEOSIDE (R 1 , R 3 -R 5 =H; R=Glucose) 4 ′-β-D-Glucopyranosidoquercetin
3. ISOQUERCETIN (R 2 -R 5 =H; R=hu 1 =l =Glucose) 3-β-D-Glucopyranosidoquercetin
4. QUERCITRIN (R 2 -R 5 =H; R=hu 1 =l =Rhamnose); Merck-index 11.8047 3-α-L-Rhamnopyranosidoquercetin; Merck-index 11.8044
5. RUTIN (R 2 -R 5 =H; R=hu 1 =l =Rutinose); Merck-index 11.8276/77 3-[α-L-Rhamnopyranosil (1→6)-β-glucopyranosil]-quercetin=3-α-L-Rutinosylquercetin
6. ERIODICTYOL (R 1 -R 4 =H); Merck-index 11.3616
7. ERIODICTIN (R 1 , R 2 , R 4 =H; R=hu 3 =l =Rhamnose) 7-α-L-Rhamnopyranosido-eriodictyol
8. HESPERIDIN (R 2 , R 4 =H; (R 1 =CH 3 ; R 3 =Rutinose) 7-β-Rutinosyl-4′-methyl-eriodictyol; Merck-Index 11.4591
whereby all R=H stand for a saturated or unsaturated carbonic acid of the type C 6-22 alkyl, C 6-22 alkenyl or C 6-22 alkapolyene.
1.1 Foundations
A selected number of derivatives of QUERCETIN, produced according to formula (I),1 with the glycosides 2, 3, 4, 5, and of its biogenetic precursor ERIODICTYOL (II),6 produced with the glycosides 7 and 8, was made the subject of the present investigation. It can firstly be said that these compounds widely occur in dicotyledones (see the tables 8.15 and 11.1 in “The Flavonoids”, Ed. J. B. Harborne, T. J. Mabry, H. Mabry, Academic Press, New York 1975) and are, in part at least, easily accessible. A second reason is that many of them have quite thoroughly been studied also in medicine (cf. V. Cody, E. Middleton, J. B. Harborne: “Plant Flavonoids in Biology and Medicine”, A. R. Liss, New York, 1986). Note in particular, that the compounds 4, 7 and 8 are components of the once intensely investigated substance “Vitamin P” (the permeability vitamin); see H. Vogel: “Chemie und Technik der Vitamine”, Enke, Stuttgart, 1940. See also H. Wagner in “Recent Advances in Phytochemistry”, Vol. 12, p. 589; Ed. T. Swain, J. B. Harborne, C. F. VanSumere; Plenum Press, New York, 1979. Cf. further Jirina Spilkov{acute over (a)} and Josef Hubik: Biologische Wirkungen von Flavonoiden. Pharmazie in unserer Zeit, January 1988, pp.1-9; Apr. 1992, pp. 174-182.
1.2 Significance of the Appropriate Solubilization of the Active Principles
In CASE CH-2088/95; PCT/CH97/00168 of Apr. 28, 1997 it was demonstrated for selected bioflavonoid esters that the application of the fatty-tail principle to the formation of derivatives leads to important physicochemical changes in their properties, and particularly to a strongly enhanced lipophilic character, coupled with a noteable depression of the melting point (if compared with the starting material). These properties facilitate emulsification and render aqueous ultramicroemulsions of very good stability. As a consequence, the targeted delivery (i.e. the bioavailability) and hence also the bioreactivity of the inventive agents are also decisively potentiated.
1.3 Production of the Peresters
The new procedure is being applied with naturally occurring Flavonolglycosides, which can be found in many plants. The glycoside perester compounds corresponding to the formulae (III) and (IV):
can be prepared in accordance with the following procedures:
1.31 Fatty Acid Esters of Spiraeoside, Conforming to Formula (I), 2
Spiraeoside is a flavonolglycoside, which occurs with ca. 1.2% in the dried leaves of the flowers of Spiraea ulmaria L., sive Filipendula ulmaria (L.) Maxim. It was discovered by E. Steinegger and P. Casparis [Pharm. Acta Helv. 1945, 20, 154, 174]; later investigations revealed its existence in many plants, particularly in species, which since ancient times were known and used in popular medicine, such as, e.g., in a proportion of 1% in onion peels ( Allium cepa L.) [K. Hermann, Naturwiss. 1956, 43, 158; Arch. Pharm. 1958, 291, 238]; of 3% in dried flowers of Hamamelis japonica S. & Z. [L. Hörhammer and R. Griesinger, Naturwiss. 1959, 46, 427], in the seeds of horse-chestnuts Aesculus hippocastanum L. [J. Wagner, Naturwiss. 1960, 47, 158], in the leaves of diverse kinds of hamamelidaceae [K. Egger and H. Reznik, Planta, 1961, 57, 239] and in the flowers of gorse ( Ulex europaeus L. [J. B. Harborne, Phytochem. 1962, 1, 203].
Newer publications mention the presence in flowers of gardening hybrids of Fuchsia [Y. Yasaki, Botanical Magazine (Tokyo) 1976, 89, 45], as well as in numerous hybrids of gardening roses [K. Nayeshiro and C. H. Eugster, Helv. Chim.Acta 1989, 72, 985]. In the last named cases, spiraeoside contributes decisively to the stabilization of the anthocyanine complexes, which are responsible for colouring.
Despite the general presence of spiraeoside in medicinal plants, the compound has rarely been studied scientifically for its role in traditional popular healing, and no effort was made so far to investigate the pharmaceutical properties of the pure substance.
The chemical structure of spiraeoside as 4′-β-D-Glucopyranosylquercetin was determined by E. Steinegger et al. (loc.c.) and by L. Hörhammer and R. H{umlaut over (a)}nsel, Arch.Pharm. 1954, 287, 36, with the help of classical methods. The analytical control, employing modern equipment and methods, was carried out in connection with the purity assay for the freshly isolated starting material which was then esterified as described in the present invention. It confirmed the chemical structure as given in formula (V):
Sufficient quantities of (V) can be obtained from the indicated sources by relatively simple extraction and enrichment steps. In the present case, the commercially available drug ‘Flos Spiraeae ulmariae’ was processed. Following processes of mild extraction, separation, column chromatography and cristallisation, compound (V) was isolated and subsequently esterified using a fatty acid chloride, in order to obtain compound (VI). Of importance is the enhanced stability of the ester function at C(5), as compared to that of Quercetin esters.
Isolation of Spiraeoside (V)
500 g of ‘Flos Spiraeae’ (Dixa St.Gallen, berries) are kept standing in the percolator with 4 L of methanol-water 4:1 during 2 days. The produced, yellowish-brown percolate is evacuated to ca. 250 ml and extracted 4 times in the separatory funnel with 250 ml each time of n-butanol. The pooled butanol solutions are then evacuated at 5 Torr, and the oily residue is taken up in 250 ml of acetic acid-water-methanol-ethylacetate 6:34:20:10 and chromatographically purified with a column of 0.8 kg polyamide powder (Macherey-Nagel, SC6) or optionally with water-pyridine 97.5:2.5 on Sephadex G-10 (Pharmacia). The resulting, spiraeoside-containing fractions are pooled and evaporated i.v.; the residue is cristallized in little hot 15%-acetic acid. Very pure spiraeoside can be obtained by repeated chromatography over cellulose powder (Avicel®, Merck, art. 2331) using 13%-acetic acid. The product has clear yellow needles, mp. (vac., uncorr.) 211.5-212.5° C.
Production and characterization of Octalauroylspiraeoside
In a small three-neck flask, with N 2 -inlet, magnetic stir bar, drop funnel and cooler, one dissolves 214 mg of spiraeoside in 2 ml of waterfree pyridine by warming up lightly, then diluting the solution with 5 ml of 1,2-dichloroethane and 10 mg of 4-dimethylaminopyridine. Subsequently cool down under N 2 to 0° C., slowly add dropwise, under good stirring, a solution of 0.87 ml of lauroylchloride in 5 ml of 1,2-dichlorethane. Then let the temperature rise to RT and stand for 12 h. The clear, almost colourless solution is then diluted with Et 2 O and the produced suspension washed 5 times in the separatory funnel with strongly diluted H 2 SO 4 and at the end with brine. Treating the solution with diluted hydrogencarbonate solution may lead to considerable emulsification, if the batch contains excessive lauroyl chloride. In order to avoid foaming in a simple way, slowly filter the dried solution using a short column with calcium carbonate, eluent: Et 2 O or a mixture of dichloromethane/ethyl acetate. After drying over Na 2 SO 4 and processing as usual, one obtains a pale yellowish, vesicular foam, yield 0.94 g. It can be crystallized from CH 2 Cl 2 /CH 3 CN or from 2-propanol: weakly yellowish crystals are formed, mp. 82.5-85° C.
[α] D : −11.7° (c=1.034; CHCl 3 ).
UV: (CH 2 Cl 2 ): 232 (26'900), 254 (20'400), 311 (26'100)
IR: (CH 2 Cl 2 ): 3048w, 2932ss, 2853s, 1762s, 1651m, 1622m, 1510m.
1 H-NMR: (CDCl 3 , 300 MHz): 0.8-2.7 (proton signals of the ester component); 3.8 to 5.8 (signals of the protons on the sugar part); 6.76 (d, J=2.4, H-C(5)). 7.02 {d, J=8.8, H-C(5′)}; 7.22 {d, J=2.4, H-C(8)}; 7.44 {d, J=2.2, H-C(2′)}; 7.59 (dd, J=8.8 and 2.2, H-C(5′)); The original OH-protons at 8.59/9.50/10.79 and 12.41 ppm have disappeared.
13 C-NMR: (CDCl 3 , 75 MHz): i.a. 9 carbonyl signals at 173.1/172.6/171.9 (three-fold intensity)/171.1/170.7/170.4/169.9 ppm.
Elemental analysis (incineration):
C 117 H 196 O 20 (1922,74) Calc. C 73,08 H 10,28% Found C 72,89 H 10,91%
In a comparative manner, also the peresters formed with capronic acid, undec-10-enoic acid, palmitic acid and stearic acid chlorides can be produced.
1.32 Fatty acid esters of Vitamin P (Quercetin-3-rutinoside)
Production of Rutindecalaurate
Commercial Rutintrihydrate in accordance with formula (VI), in which R=H:
was dried during 20 h at 100° C./0.01 Torr. 0.92 g of waterfree Rutin were then dissolved in 5 ml of abs. pyridine and 5 ml of abs. dimethylformamide by warming up and diluting subsequently with 10 ml of 1,2-dichloroethane. After cooling down under N 2 and stirring, add dropwise 3.59 ml of lauroylchloride in 10 ml of 1,2-dichloroethane. Subsequently let the batch slowly rise to RT and then stand it for 20 h, with constant stirring. Add a sufficient amount of ether, so that the washing operation with strongly diluted H 2 SO 4 and water renders a clearly separated upper phase. After drying over Na 2 SO 4 and customary processing, including drying the residue in high vacuum, one obtains a honey-like clear brownish oil. Yield ca. 90%. Analytical data:
UV: (hexane, qualitatively): λ max 202 nm, 250, sh 293, sh 306
[α] D :=−28.5° (c=0.82 in chloroform)
IR: (dichloroethane): no bands in the OH-range; 3045w, 2625ss, 2855s, 1750s, 1646m, 1629m, 1504w.
2.0 Production of Spontaneously Dispersible Concentrates and of Aqueous Ultramicroemulsions
Because of their pronounced lipophilic properties, the described compounds according to the formulae (I) to (VI) are insoluble in water. In order to enable them to penetrate the membrane barrier of tumor or host cells and of the protein hull of viruses or parasites and then to spread in the cell plasma and inside the virus/parasite, these compounds must first be solubilized in appropriate manner in the aqueous medium. This is achieved over 2 steps: first the production of spontaneously dispersible concentrates, which comprise the active principles as an integrative, micellar component of the system, and second the addition of distilled water, 5%-glucose solution or physiological sodium salt solution (Ringer solution) in a proporition 1:20 to 1:1'000'000.
By preparing thermodynamically stable oil-in-water ultramicroemulsions, employing selected cotensides (i.e. hydrotropic agents) on the one hand, and appropriate tensides (surfactants) on the other hand, it becomes possible to achieve an optimal degree of solubilization of these ester compounds and of their biolociical delivery and hence a high bioavailability and bioreactivity at or in the target cell.
All experimental observations gained with stable ultramicroemulsions of this kind can be uniformly interpreted by means of the concept that the inventive solubilization system produces in the aqueous phase organized aggregates, which are MICELLES. These micelles possess a more or less globular shape, having a hydrodynamic radius of less than 10 nm. They are thermodynamically stable. The tensides and cotensides are capable at the phase-boundary of the microemulsion of hindering SELF-DIFFUSION. This means that no mixing takes place between the outer aqueous phase of the microemulsion and its inner, oily phase, which contains the ester compounds according to the formulae (I) to (VI), solubilized in the coemulgator, i.e. the biotenside solvent employed as an essential component of the spontaneously dispersible concentrate. In the inner, oily phase, the molecules of the selected esters are thus present in monomeric or in oligomeric form. The micelles, which comprise in their micellar core the solubilized active substances, are coated by a tenside layer or bilayer and are thus rendered elastic. This enables them to penetrate through the plasma membrane of the tumor cell or the virus- or parasite-infected host cell, and also through the envelope of the virus. This diffusion process takes place on account of thermal molecular movements exclusively. In biological systems they are not related to metabolic energy. The fractal dimensions of these membranes allow the build-up of considerable gradients, i.e of differentials in concentration. The velocity of the ensuing diffusion process and the volume of transport through the membrane of the target cells are a function of:
1. the concentration difference in the two compartments outside and inside the cell
2. the radius of the particles (i.e. the micelles) enclosing the diffusing active substance
3. the viscosity of the diffusing aqueous solution (emulsion)
4. the temperature.
The proper solubilization of the active substances, which are practically insoluble in water, by means of surfactants (coemulgator plus tensides) is a conditio sine qua non for achieving self-diffusion and hence active transport of the biologically effective substances across the membranes of living cells. As can be seen from the table, one globular “micelle” having a hydrodynamic radius of one centimeter possesses a volume of 4.189 cm 3 and a phase surface of 12.564 cm 2 . In contradistinction: a number of 10 18 micelles having each a hydrodynamic radius of 10 −6 cm(=10 nm) only, together possess the same volume of 4.189 cm 3 and yet cover up a total phase surface of 1'256.4 m 2 .
MICELLES: PROPORTION between VOLUME and SURFACE AREA
NUMBER
Hydrodynamic
TOTAL
of the
RADIUS
VOLUME
SURFACE AREA
MICELLES
of the micelles
Of the micelles
of the micelles
1
1 cm
4.189 cm 3
12.564 cm 2
10 3
0.1 cm = 1 mm
″
125.64 cm 2
10 6
0.01 cm
″
1'256.4 cm 2
10 9
0.001 cm
″
12'564 cm 2
10 12
0.0001 cm = 1 μm
″
125'640 cm 2
= 1'000 nm
10 15
0.00001 cm =
″
1'256'400 cm 2
100 nm
10 18
10 nm
″
1'256.4 m 2
10 21
1 nm
″
12'564 m 2
Spheric volume=4/3 πr 3
Spheric surface=4 πr 2
Conclusion
Due to the enormous total surface area, which is taken up in the inventive ultramicroemulsions by the micelles having a hydrodynamic radius of 2.2 to 3.0 nm, in addition to the increased diffusion capability, also the Theological distribution (the “spreading”) is significantly enhanced. Hence, the bioavailability, as well as the bioreactivity of the antitumor agents carried in the core of the micelles (and maintained there in monomeric or oligmeric solution), are also notably improved. This will allow a considerable reduction of the critical dosage required. This, in turn, causes a reduction or complete elimination of unwanted, disturbing side-effects.
The “packing density” achieved with the spontaneously dispersible, stable MARIGENOL®-concentrates obeys the exponential relationship illustrated above: the smaller the particle size of the micelles, the greater the packing density obtainable. Of decisive importance is the correct formation of the inner phase, its balanced proportion with respect to the entire concentrate and the choice of the suitable tensides.
2.1 The inventive spontaneously dispersible concentrates comprise:
0.1 to 5% by weight of one of the esters according to the formulae (I) or (II), or of a combination of such esters, and
0.1 to 5% by weight of a known pharmaceutical, dermatological and/or cosmetic active substance,
5 to 25% by weight of a hydrotropic agent, which is the pharmaceutically acceptable coemulgator or solvent,
0 to 5% by weight of a Good-buffer or of 3-[(3-Cholamido-propyl)-dimethylammonio]-propansulfonate (CHAPS) and/or DMSO (Dimethylsulfoxyde),
up to 90% by weight of a pharmaceutically acceptable surfactant or surfactant mixture, and optionally
up to 10% by weight of a vitamin or provitamin,
up to 10% by weight of a penetration enhancer, radical scavenger and/or stabilizer.
The inventive aqueous ultramicroemulsions comprise:
0.1 to 5% by weight of a spontaneously dispersible concentrate as defined above,
85 to 99.9% by weight of distilled water, physiological sodium salt solution (Ringer solution) or 5% glucose solution,
up to 10% by weight of carriers, customary excipients and/or diluents.
These aqueous ultramicroemulsions are characterized by the following properties: a reduced surface tension of 28-32 mNm −1 , a low inner viscosity (showing a dynamic viscosity η at 20° C. around 1.0 cP=10 −3 Pa.s), a very small and homogenous particle size and a good thermodynamic stability (no coalescence, no agglomeration of the micelles, no autocondensation of the tensides; that is to say that no “self assembly” is occurring as due to the chemical degradation of the tensides). The active principles are found in monomeric or oligomeric solution, packed in the micellar core. Due to the balanced proportions, even with very high degrees of dilution, the tenside coated umbrella of the micelles is preserved. This also prevents so-called “instability or Marangoni effects”. Thanks to these properties, the inventive ultramicroemulsions permit high capillary diffusion. Their penetration potential at the cell membrane of defective or abnormal cells is excellent and is followed by very good spreading (rheological distribution) inside the cell. The consequence is that the described solubilization system makes for a high bioavailability and hence also bioreactivity of the active principles which are carried in it, coupled with a reduced or no toxicity at all.
The surfactants or surfactant mixtures to be employed according to the invention can be anionic, cationic, amphoteric or non-ionic. Ideally, they are non-ionic and have an HLB-value (i.e. a hydrophilic-lipophilic balance) of between 2 and 18; preferably, it is between 2 and 6 on the one hand and 10 and 15 on the other hand. HLB values describe the hydrophilic and lipophilic properties of an emulsifier. In this context see “Hydrophile-Lipophile Balance: History and recent Developments” by Paul Becher in Journal of Dispersion Science and Technology, 5 (1), 81-96 (1984).
Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic compounds. Suitable soaps are the alkali metal salts, alkaline earth metal salts or optionally substituted ammonium salts of higher fatty acids (C 12-22 ), for example the natural Na or K salts of oleic or stearic acids, or of natural mixtures of fatty acids which can be obtained, inter alia, from coconut oil or tallow oil. Other surfactants which may be mentioned are fatty acid methyltaurine salts, and modified and non-modified phospholipids. However, more frequently used surfactants are so-called synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl-sulfonates. The fatty sulfonates and fatty sulfates are usually present in the form of alkali metal salts, alkaline earth metal salts or optionally substituted ammonium salts and generally have an alkyl radical containing 8 to 22 C atoms, alkyl also encompassing the alkyl moiety of acyl radicals. Examples are the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric ester and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonyl groups and one fatty acid radical containing about 8 to 22 C atoms. Alkylarylsulfonates are, for example, the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutyl-naphthalene-sulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product. The non-ionic surfactants are mainly chosen from amongst the polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 C atoms in the (aliphatic) hydrocarbon radical and 6 to 18 C atoms in the alkyl radical. Other suitable non-ionic surfactants are the water-soluble polyethyleneoxy-adducts onto polypropylene glycol and alkyl polypropylene glycol with 1 to 10 C atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene ether groups. The compounds which have been mentioned customarily contain 1 to 5 ethylene units per propylene glycol unit. The following may be mentioned as examples of non-ionic surfactants: nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxy-ethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol. Moreover, fatty acid esters of polyoxyethylene-sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable. The cationic surfactants are mainly quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 C atoms as the N-substituent and which have lower, optionally halogenated alkyl radicals, benzyl radicals or lower hydroxyalkyl radicals as further substituents. The salts are mainly present in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi-(2-chloro-ethyl)-ethyl-ammonium bromide.
When preparing the inventive spontaneously dispersible concentrates, special preference is given on the one hand to phosphoric acid ester tensides, such as:
Tristyrylphenolpolyoxyethylene-18-phosphoric-acid-ester-triethylamine, (TEA)-salt tenside, with formula:
Soprophor FL (RH{circumflex over (O)}NE-POULENC)
Nonylphenol-10-polyoxyethylene-mono/dimethylphosphoric-acid-ester [Diphasol® 3873, (CIBA-GEIGY); or the identical Sermul® EA 188 (SERVO)]:
Diphasol® 3873 (CIBA-GEIGY)
Tenside 508, (CIBA-GEIGY);
Tinovetin® JU (CIBA-GEIGY), a hydroxybiphenyl-10-ethoxy-phosphoric acid ester
Butyl-mono-4-ethoxy-phosphoric acid ester (Zerostat® AT, CIBA-GEIGY), and
Zerostat® AN (CIBA-GEIGY), respectively
and on the other hand to betain compounds, i.e. amphoteric, salt- and water-free imidazole derivatives, having an isoelectric/isoionic point near 7, such as, e.g., the compound:
Amphonyl CA-AA (CHEMAG).
Furthermore, so-called “multi-functional glucose derivatives”, such as, e.g., Glucate® SS (Methylglucose-sesquistearate) and Glucamate® SSE-20 (PEG-20-methylglucose-sesquistearate) of Amerchol, Edison, N.J., are also being used. In certain cases, good results can also be achieved when non-ionic surfactants of the “TWEEN®”-class are used (Atlas Chem. Ind. Inc. or ICI Speciality Chemicals), so-called polyoxyethylene-sorbiton-monoesters or “Polysorbate” 20-85 in the CTFA classification.
The following compounds may be employed as the pharmaceutically acceptable solvent which acts as the hydrotropic agent (i.e. the coemulsifier), for example: esters of an aliphatic alcohol (C 3-18 ) with an aliphatic carboxylic acid (C 10-22 ), such as isopropyl laurate, hexyl laurate, decyl laurate, isopropyl myristate and lauryl myristate; hydrocarbons having a straight carbon chain (C 12-32 ) which is substituted by 6 to 16 methyl groups and which can have up to 6 double bonds, examples which may be mentioned being terpenes, such as polymethylbutanes and polymethylbutenes. Monoesters of ethylene glycol or propylene glycol with an aliphatic carboxylic acid (C 6-22 ), such as propylene glycol monolaurate and propylene glycol monomyristate. Esters of an aliphatic alcohol (C 12-22 ) with lactic acid, such as, for example, myristyl lactate or, preferably, lauryl lactate. Monoesters or diesters of glycerol with an aliphatic carboxylic acid (C 6-22 ), such as, for example, glyceryl caprylate or Miglyol® 812 neutral oil (Oleum neutrale). Esters of a poly(2-7)ethylene glycol glycerolether having at least one free hydroxyl group with an aliphatic carboxylic acid (C 6-22 ), such as, for example, aliphatic alcohols (C 12-22 ), thus, inter alia, dodecanol, tetradodecanol, oleyl alcohol, 2-hexyldecanol and 2-octyldecanol. Esters containing at least one free hydroxyl group, of poly-(2-10)glycol with an aliphatic carboxylic acid (C 6-22 ), monoethers of a polyethylene glycol with an aliphatic alcohol (C 12-18 ), such as, for example, polyoxyethylene-(C10) octylether. Heterocyclic compounds such as 1-methyl-2-pyrrolidon. Biotenside terpinyl esters according to the general formula (VII):
R 3 —COO—R 4 (VII)
in which R 3 is a C 6-31 alkyl or a C 9-31 alkenyl/alkapolyene group and R 4 is citronellyl-, farnesyl-, geranyl-, isophytyl- or phytyl-.
Before their application into spontaneously dispersible concentrates all technical tensides have been cleaned by filtration or by chromatography over aluminum-oxide with an inert solvent as eluent, such as tetrahydrofurane, ethyl alcohol or dichlormethane.
2.2 COMPOSITION EXAMPLES for inventive, spontaenously dispersible concentrates, which comprise active principles according to formulae (I) to (II) and which, if diluted with distilled water or 5%-glucose solution or physiological sodium salt solution (Ringer solution), form thermodynamically stable ULTRAMICROEMULSIONS, having micelles of a hydrodynamic radius of 2.2 to 3.0 nm.
a) 0.1 to 5% by weight of one or several active principles in accordance with formulae (I) or (II),
0 to 5% by weight of a known, synergistically active pharmaceutical, dermatological and/or cosmetic substance,
5 to 25% by weight of isopropyl myristate, isopropyl palmitate or of neutral oil, such as Miglyol® 812 (Dynamit Nobel or H{umlaut over (u)}ls),
0 to 5% by weight of a Good-buffer or of 3-[(3-Cholamido-propyl)-dimethylammonio]-propansulfonate (CHAPS) and/or DMSO (Dimethylsulfoxyde),
0 to 45% by weight of a phosphoric acid ester surfactant, as e.g. Diphasol® 3873 (CIBA-GEIGY), Tenside 508 (CIBA-GEIGY), Zerostat® AN or AT (CIBA-GEIGY), Tinovetin® JU (CIBA-GEIGY), Soprophor® FL (RH{circumflex over (O)}NE-POULENC),
5 to 90% of Invadin JFC 800% (CIBA-GEIGY), and/or TWEEN® 20-85 (ICI Surfactants), a polyoxyethylene-(20)-sorbitan ester tenside, and optionally
up to 10% by weight of a vitamin or provitamin,
up to 10% by weight of a stabilizer, penetration enhancer, excipient, diluent, or a combination thereof.
b) 0.1 to 2% by weight of one or several active principles in accordance with formulae (I) to (II),
5 to 25% by weight of one or several biotenside terpinyl esters conforming to the general formula (VII)
R 3 —COO—R 4 (VII)
in which R 3 is a C 6-31 alkyl or a C 9-31 alkenyl/alkapolyene group and R 4 is citronellyl-, farnesyl-, geranyl-, isophytyl- or phytyl-,
30 to 45% by weight of Invadin® JFC 800% and/or of a Tween® surfactant and/or Amphonyl® CA-AA,
the rest up to 100% by weight of Soprophor® FL or Diphasol® 3873.
c) 1% by weight of an agent according to formulae (I) or (II),
4 to 9% by weight of 2-pentanol or glycerol waterfree or DMSO
15 to 20% by weight of citronellyl-10-undecenoate (C 11:1 -(±)-β-Citronellyl ester) or of citronellyl-laurate (C 12:0 -(±)-β-Citronellyl ester),
30% by weight of Invadin® JFC 800% and/or TWEEN®-20,
the rest up to 100% by weight of Soprophor® FL and/or Diphasol 3873.
N.B.: INVADIN® JFC 800% (CIBA-GEIGY) is a waterfree tert. octylphenyl-polyoxyethylene ether tenside, having 9 to 10 oxyethylene groups. TWEEN®-surfactants No. 20-85 (ICI Speciality Chemicals) are non-ionic polyoxyethylene sorbitan ester tensides, CTFA classification: Polysorbate 20-85.
Example for the pharmaceutical production of a system's preparation containing the inventive concentrates in the form of “multiple units”.
a) Granulation (granules and pellets)
Metolose ® 90 SH-4000 (Shin-Etsu Chemical)
90.0
g
Avicel ® PH-101
80.3
g
Inventive, spontaneously dispersible concentrate
139.4
g
Aerosil ® 200
80.3
g
Σ
390.0
g
Granulation in the high speed mixer or the fluidized bed, with the addition of 110 g ethanol, sieving on a 18 to 42 mesh screen with crushing, drying for 24 h at 40° C.
b) Enteric and sustained release coating: prepared in the fluidized bed with AQOAT® AS-HG (Shin-Etsu Chemical) and talc.
c) Composition of finished granules or micropellets
Core Material
44%
by weight
Inventive concentrate
25%
by weight
Enteric coating
31%
by weight
Σ
100%
by weight
N.B. The pellets or granules according to a) can also be filled without prior coating into capsules which are made of AQOAT® (HPMC-AS-M or HPMC-AS-N), have been sealed with acetone/ethanol 1:1 and can thus perform the functions of pH-control and slow release.
3.0 Biological Assays
The antitumour/antiviral/antiparasitic activity of the spontaneously dispersible concentrates comprising active substances prepared according to the composition examples a) to c) given in 2.2 above, is confirmed by the following test results:
3.1 In-Vitro Assays Using Suitable Tumour Cell Lines
A biological assay system using microtiter plates and serial dilutions has been developed. Batches of 10 4 tumour cells per ml were set up in culture medium RPMI 1640 and inactivated with 10% of fetal calf serum (GIBCO); they are spread at a density low enough to enable them to grow during the assay, in so-called non-confluent monolayers. Samples are added after 6 to 24 h, with 100 μl per row, to which 100 μl of medium are added in the first well. Half of this mixture is withdrawn, transferred into the next well and again treated with 100 μl of medium, etc. This results in an n½ geometrical serial dilution.
In the plaque assay, the samples are incubated at 37° C. for 3 to 5 days under 3½% of CO 2 . They are then stained and fixed using 0.1% crystal violet (Fluka, Buchs) in a solution of 70% of methanol, 1% of formaldehyde and 29% of water. The samples are evaluated under the microscope, magnification 300×. The greatest cytotoxic dilution is determined. The samples can also be evaluated quantitatively by means of scanning and absorption measurement in a spectrophotometer.
3.2 Testing Cell Toxicity
3.21 Cell tocicity of the MARIGENOL®-CONCENTRATES tested with Py6-Cells (Polyoma virus transformed 3T3 mouse-fibroblasts)
Py6 cytotoxicity-test
Apr. 24-28, 1995
24 h
48 h
72 h
Exposure
Exposure
Exposure
Concentrate
Concentrate
Concentrate
1%-concentrate
A.S.
A.S.
A.S.
OCTALAUROYL-
32'000
64'000
128'000
SPIRAEOSIDE
3.2 Mio.
6.4 Mio.
12.8 Mio.
(with CHAPS
OCTALAUROYL-
16'000
64'000
128'000
SPIRAEOSIDE
1.6 Mio.
6.4 Mio.
12.8 Mio.
(with Tween-20)
Greatest cytotoxic dilution:
calculated on the concentrate and active substance-content
N.B.: On the subject of the eternalized Py6cells cf.: “Biochemistry”, Coordinating Editor Geoffrey L. Zubay, Addison-Wesley Publishing Company, 1983, p.1079.
See also “Molecular Cell Biology”, second Edition, by J. Darnell, H. Lodish, D. Baltimore; Scientific American Books, Chapter 5: Viruses, Structure and Functions, pp. 177-188. New York, 1990 (W.H. Freeman & Co.)
3.22 Cell tocicity of the MARIGENOL®-CONCENTRATES (continued)
Py6 cytotoxicity-test
Mar. 28-Apr. 2, 1996
72 h
48 h
72 h
Greatest still cyto-
Exposure
Exposure
toxic Dilution
Concentrate
Concentrate
A.S.-Concentration
1%-Concentrates
A.S.
A.S.
in μMol
QUERCETIN-
40'000
80'000
PENTALAURATE
4 Mio.
8 Mio.
0.103
OCTALAUROYL-
160'000
320'000
SPIRAEOSIDE
16 Mio.
16 Mio.
0.016
RUTINDECA-
160'000
160'000
LAURATE
16 Mio.
16 Mio.
0.014
Greatest cytotoxic dilution:
calculated on the concentrate and active substance-content;
Final test concentration indicated in μMol.
N.B. Composition of 1%-concentrates:
1% by weight of active principle
12% by weight of C 11:1 -(±)-β-CITRONELLYL-ESTER
87% by weight of Invadin JFC 800%/Soprophor FL 1:1
4.0 Antiparasitic Tests
SWISS TROPICAL INSTITUTE, BASEL
In-vitro assays, WHO-screening as SOP
Parasite
Strain
Stage
Standard
Test N°
T.b.rhodesinense
STIB 900
trypomastigotes
Melarsoprol
T9611
L.donovani
MHOM-ET-
amastigotes
Pentostam
L9604/05
67/L82
T.cruzi
MHOM/Br/00/Y
trypomastigotes
Benznidazol
C0606/08
The assays were conducted at the Swiss Tropical Institute, Basel (Prof.Dr. Ronald Kaminsky and Mrs. Yvonne Grether). The aim was to find out whether there was selective activity in-vitro against Trypanosoma rhodesiense (the agent of sleeping sickness), against Trypanosoma cruzi (the agent of Chagas-disease) and against Leishmania donovani (the agent of leishmaniasis). Tests were conducted at concentrations which don't induce basal cytotoxicity on murine muscle cells or macrophages. The action observed in this screening is specific against Leishmania donovani .
Test
L.
Cytotoxicity
score*
T.b. rhodesiense
T. cruzi
donovani
L-6
Macroph
r,d,c,
TDR-Code
MIC
IC 50
MIC
IC 50
MIC
MIC
t,-,
Standards
0.011
0.0004
3.7
30
>100
>90
EP10
100
—
100
<30
100
90
d
EP17
100
—
100
20
>100
90
d
EP19
100
—
100
20
>100
90
d
4 N
33
17
100
20
>100
>90
d
7N
11
6,9
33
8
100
90
d
T1
>100
18,0
100
<30
100
90
d
T5
100
17
100
6
100
90
d
T6
100
17
100
<30
100
90
d
T7
100
16
100
<30
100
90
d
T9
100
16
100
<30
100
90
d
T10
100
16
100
<30
100
90
d
T11
100
18
100
<30
100
90
d
T12
100
20
<30
90
d
Legend:
EP 10
1%-concentrate
β-SITOSTERYL-BEHENATE
EP 17
1%-concentrate
VITAMIN D 3 -UNDECENOATE
EP 19
1%-concentrate
VITAMIN D 3 -OLEATE
4N
1%-concentrate
QUERCETIN-OCTALAUROYL-GLUCOSIDE
7N
1%-concentrate
Z-Gly-Phe-VITAMIN D 3 -ESTER
T1
1%-concentrate
COEMULGATOR + TENSIDE
T5
1%-concentrate
14-OH-10-DEACETYLBACCATIN-III
T6
1%-concentrate
3,28-LAUROYL-BACCATIN-III
T7
1%-concentrate
QUERCETIN-PENTALAURATE
T9
1%-concentrate
DECALAUROYL-RUTINOSIDE
T10
1%-concentrate
β-SITOSTERYL-PALMITATE
T11
1%-concentrate
β-SITOSTERYL-ARACHIDATE
T12
1%-concentrate
ERGOSTERYL-LAURATE | Spontaneously dispersible concentrates capable of forming ultramicroemulsions are described. The concentrates include esters of formula (I) and (II):
wherein (a) R 1 , R 3 , R 4 , and R 5 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene and R 2 is glucose:(1,2); (b) R 2 , R 3 , R 4 , and R 5 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene and R 1 is glucose:(1,3); (c) R 2 , R 3 , R 4 , and R 5 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene and R 1 is rhamnose:(1,4); or (d) R 2 , R 3 , R 4 , and R 5 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene and R 1 is rutinose:(1,5);
wherein
(a) R 1 , R 2 , and R 4 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene and R 3 is rhamnose:(11,7); or (b) R 2 and R 4 each independently represents a C 6-22 alkyl, a C 6-22 alkenyl or a C 6-22 alkapolyene, R 1 is methyl, and R 3 is rutinose:(11,8). | 0 |
This is a division of application Ser. No. 08/319,681, filed Oct. 7, 1994, now U.S. Pat. No. 5,585,387.
FIELD OF THE INVENTION
This invention relates to synthesis of pharmaceutically active compounds, and to intermediates for use in such synthesis. From a more specific aspect, it relates to methods for making the pharmaceutical cisapride, intermediates useful in such a synthesis and methods for making such intermediates.
BACKGROUND OF THE INVENTION AND PRIOR ART
Cisapride, the full chemical name of which is cis-4-amino-5-chloro-N-[1-[3-(4-fluorophenoxy)propyl]-3-methoxy-4-piperidinyl]-2-methoxy-benzamide, and the chemical structural formula of which is: ##STR1## is a known compound, the preparation and properties of which are described in Canadian Patent 1,183,847 Van Daele, issued Mar. 12, 1985. It is also the subject of Entry No. 2318 of The Merck Index, 11th Edition. According to the disclosure of Canadian Patent 1,183,847, it has pharmacological properties as a stimulator of motility of the gastrointestinal system, rendering it useful as a peristaltic stimulant in the treatment of disorders associated with the gastrointestinal tract.
Three basic methods for the chemical synthesis of cisapride and related benzamide derivative compounds are described, in greater or lesser detail, in aforementioned Canadian patent 1,183,847. In general terms, these three methods are:
in the first method, reaction of an appropriately substituted piperidine-amine with an appropriately substituted benzoic acid or functional equivalent thereof, to form the amide linkage, thus: ##STR2##
in the second method, reaction of a 7-oxo-3-azabicyclo[4,1,0]-heptane with an appropriately substituted benzamide, followed by O-alkylation of the piperidine ring, thus: ##STR3##
in the third method, reductive N-alkylation of an appropriate piperidinone with an appropriately substituted benzamide, thus: ##STR4##
In all of these general formulae, L, R' and R each represent one of a wide variety of radicals according to the patent, but in the specific case of cisapride preparation, they represent respectively 3-(4-fluorophenoxy)propyl, methyl and hydrogen or an amino protectant group.
Other syntheses involving the conversion of one member of the class of benzamide derivatives of Canadian patent 1,183,847 to another member of the same class, and syntheses for compounds of the class having groupings different from those of cisapride, are also disclosed in the aforesaid Canadian patent.
These prior art syntheses for cisapride all involve the formation of an amide bond between the piperidine moiety and the benzoic acid derived moiety, with the appropriate substituents on each moiety already in place. The first of these methods is disadvantageous because the 4-aminopiperidine starting material must be produced by a reductive amination which produces a mixture of cis with some trans stereoisomer. Since only the cis isomer is pharmaceutically important, in the pharmaceutically important case of cisapride, the cis isomer must at some stage be separated from the cis-trans mixture. This is inefficient and wasteful of material since several recrystallizations may be required. The second of these methods results in substantial amounts of trans isomer, which is not useful in producing such materials such as cisapride. The third method is not fully detailed in the patent disclosure, and turns out to be impractical on a larger scale.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel process for preparing cisapride and similar benzamide derivatives, highly stereoselectively and in a predominantly cis configuration.
It is a further object to provide novel chemical compounds useful as intermediates in such preparation.
From a first aspect, the present invention provides novel substituted 4-oxo-piperidine compounds, namely 1-aryloxyalkyl- or 1-aralkyl- 3-arylcarbonyloxy-4-oxo-piperidines of the general formula A given below: ##STR5## which are convertible to novel 1-aryloxyalkyl- or 1-aralkyl-3-hydroxy-4-lower alkoxy-4-arylamido piperidines of the general formula B given below: ##STR6## The process of converting compounds of formula A into compounds of formula B, which constitutes another aspect of the present invention, is a novel and totally surprising nuclear substituent rearrangement involving acyl transfer under aminal forming conditions.
Piperidines of general formula B,. it has been found, can be readily converted to the corresponding 3-oxo-4-arylamido compounds of general formula C: ##STR7## by reaction with strong organic acid, for example trihaloacetic acid, methanesulfonic acid, trifluoromethane sulfonic acid and the like.
In the above general formulae A, B and C, L in each case represents aralkyl or aryloxyalkyl in which the alkyl portion has from 1 to 6 carbon atoms and the aryl nucleus is optionally substituted with up to 3 substituents independently selected from halo, lower alkyl and lower alkoxy, or alkyl having from 1 to 6 carbon atoms; R' represents alkyl of from 1 to 6 carbon atoms, or benzyl; and R represents a phenyl group optionally substituted with up to 3 substituents independently selected from halo, amino, protected amino, alkyl of 1 to 6 carbon atoms, and alkoxy of 1 to 6 carbon atoms.
The success of the reaction to convert the 3-hydroxy-piperidine compounds to the corresponding 3-oxo piperidine compounds, i.e. compound B to compound C, is most surprising, since the scientific literature rarely describes compounds with the 3-oxo piperidine sub-structure, and where they appear they are indicated to be quite unstable. Their formation as a stable intermediate for subsequent utilization in an organic chemical synthesis process is accordingly contra-indicated. However, it has now been found that this instability is not manifested, at least under the strongly acidic conditions employed in the processes of the present invention. Once compound C has been formed, its subsequent reduction to the corresponding 3-hydroxy compound, deprotection and methylation at the 3-position of the piperidine ring to form compounds such as cisapride is relatively straightforward, and in fact significantly advantageous. The step of hydride reduction of the oxo group to form a hydroxyl group can be conducted stereo specifically to form an intermediate in which the 3-hydroxyl group and the 4-amido group on the piperidine nucleus are disposed in the cis relationship to one another, as required in cisapride, with no formation of contaminant trans isomer. Deprotection is routine.
A further aspect of the invention relates to the discovery of a special method for the selective methylation of the 3-hydroxyl group.
BRIEF REFERENCE TO THE DRAWINGS
The single FIGURE of accompanying drawings illustrates the most preferred synthetic process according to the invention, namely that specifically applied to the synthesis of cisapride.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred compounds of formula A according to the present invention are those in which L represents (halo-substituted phenyl)oxypropyl, especially 4-fluorophenyl-oxypropyl, and in which R represents a substituted phenyl group, especially 2-methoxy-4-amino-5-chlorophenyl and N-protected versions thereof such as carbobenzoxy-protected versions thereof. The especially preferred compound A, the structural formula of which is shown and labelled "A" on the FIGURE of drawings, is specifically useful in cisapride synthesis.
Compound A itself can be prepared by a reaction sequence which starts from ethyl 4,4-dimethoxy-3-hydroxy-1-piperidine carboxylate, a known compound (see European patent 76530 Janssen, or European patent 121,972 Janssen, priority date Oct. 17, 1984). As shown diagrammatically on the FIGURE, this compound 10 is decarboxylated e.g. by alkaline hydrolysis, to form the corresponding piperidine compound 12 with free secondary amine group at position 1. This is reacted with 1-chloro-3-(4-fluorophenoxy)propane under basic conditions, to form compound 14 as shown on the FIGURE. Reaction of compound 14 with 2-methoxy-4-carbobenzoxyamino-5-chloro-benzoic acid (or acyl halide thereof) forms compound 16 shown on the FIGURE. Conversion of compound 16 to the especially preferred embodiment of compound A according to the invention may be accomplished by acid hydrolysis using a strong mineral acid such as sulphuric acid, in a solvent such as methylene chloride.
The reaction of compound A to form compound B is one of nuclear substituent rearrangement, and is a reaction for which no similar precedent is known to exist. Important preconditions for it appear to be the piperidine ring substituted by oxo at the 4-position and -O-CO-aryl at either the 3-position or the 5-position, the presence of ammonium carboxylate, a carboxylic acid and the use of a nucleophilic alcoholic solvent. The reaction mechanism, although not fully elucidated and not to be construed as binding or in any way limiting on the scope of the present invention, is believed to involve an initial attack by the ammonia supplied from the ammonium carboxylate on the hemiketal formed by the reaction of the ketone with the solvent alcohol, accompanied by transacylation of the transiently formed aminal by the proximate ester at the 3 or 5 position. The result is the insertion of an alkoxy substituent as well as an amide substituent at position 4 of the piperidine. At the same time the oxygen group left at position 3 becomes protonated to form a hydroxyl group at that position, giving the compound B as shown on the FIGURE.
The conversion of compound B to compound C takes place by reaction with strictly anhydrous solutions of strong organic acids, for example trichloroacetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or methanesulfonic acid. The use of strongly acidic conditions for conducting this reaction appears to be essential. The resulting product compound C is a 3-oxo-piperidine, a class of compounds which are rarely reported because they are apparently unstable under most conditions used to generate them. The formation and isolation of such an intermediate would not therefore be expected to occur to yield a useful amount of product. According to the process of this invention, however, the reaction not only occurs, but proceeds under mild conditions to give high (over 80%) yield of product C, which can be isolated as a solid. The use of the strongly acidic conditions may be the key to the successful preparation of the product. At the same time as the conversion of the 3-hydroxyl group to a 3-oxo group, the alkoxy (normally methoxy) group is removed from the 4-position of the piperidine ring. With the discovery of the surprisingly facile and efficient route from A to B to the surprisingly stable product C, a new area of chemical synthetic routes to cisapride and similar benzamide derivatives of pharmaceutical and scientific interest is opened up.
The next step in the synthesis according to the invention, as applied in its most preferred embodiment to the manufacture of cisapride, is the conversion of the 3-oxo compound C to the corresponding 3-hydroxy compound D. The problem of stereoselectively reducing cyclic ketones to alcohols is well known in the art. This is done by selection of an appropriately bulky hydride donor selected from such common reagents such as lithium aluminum hydride, lithium trialkoxyaluminum hydrides, lithium n- or t-butyldiisobutylaluminum hydride, sodium bis(2-methoxyethoxy) aluminum hydride, tetramethylammonium borohydride, 9-borabicyclo[3,3,1] nonane ate complexes, calcium borohydride, chlorobis(cyclopentadienyl)-tetraboratozirconium (IV), lithium borohydride, lithium cyanoborohydride, lithium 9,9-dibutyl-9-borabicyclo[3,3,1] nonane, lithium dimesitylborohydride bisdimethoxymethane, lithiumperhydro-9b-boraphenalylhydride, lithiumtri-sec-butyl borohydride, lithium triethyl-borohydride, lithium tris-i-amyl borohydride, potassium 9-(2,3-dimethyl-2-butoxy)-9-boratobicyclo[3,3,1]nonane, potassium tri-sec-butylborohydride, potassium triisopropoxyborohydride, sodium acetanilidoborohydride, sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, sodium trimethoxyborohydride, tetrabutylammonium borohydride, tetrabutylammonium cyanoborohydride, tetrabutylammonium octahydrotriborate, tetramethylammonium borohydride or zinc borohydride. Alternatively, the reduction can be performed using an appropriately bulky hydrogen donor such as borane-alkylamines, dicyclohexylborane, diisocamphylborane, diisoamyl borane or t-hexylborane. Potassium tri-sec-butylborohydride (potassium selectide) is a preferred reagent. The reaction takes place substantially quantitatively and stereoselectively, to produce compounds in which the amide group at position 4 of the piperidine ring and the hydroxyl group at position 3 of the piperidine ring are disposed cis to one another, the disposition required in the end-product cisapride.
The protecting group is removed from the amino group at position 4 of the tri-substituted benzene ring, by methods well known in the art. A particularly suitable method is hydrogenation, e.g. using hydrogen gas over a palladium catalyst. This process yields compound E shown on the FIGURE, which is convertible to cisapride as the final step in the overall synthetic process.
A particularly advantageous way of conducting this final conversion, and one which forms a specific preferred embodiment of the present invention, involves the reaction of one equivalent of compound E with two equivalents of sodium hydride followed by quenching with 1 equivalent of dimethylsulfate. This reaction is best conducted in tetrahydrofuran or similar solvent, and at temperatures from about -30° to 0° C. Selective methylation of the 3-hydroxy group occurs under such conditions.
SPECIFIC DESCRIPTION OF THE MOST PREFERRED EMBODIMENTS
The invention will be further described for illustrative purposes, by reference to the following specific working, non-limiting examples.
EXAMPLE 1
This example illustrates the conversion of compound 10 to compound 12, on the accompanying FIGURE.
55 g of 1-ethoxycarbonyl-4,4-dimethyl-3-hydroxypiperidine, compound 10, was dissolved in 550 ml isopropanol, then 56 g of potassium hydroxide was added. The reaction mixture was heated to reflux for 7 hours.
The product mixture was filtered, and the product was rinsed with isopropanol. It was concentrated using a rotovap, and 500 ml methylene chloride was added to dissolve it. Then it was washed twice, with 100 ml portions of water, the aqueous layers were back extracted with 3×150 ml methylene chloride, and all the organic layers combined. This organic phase was dried using magnesium sulphate, concentrated using a rotovap and vacuum for 1/2 hour. The product, 3-hydroxy-4,4-dimethoxy-piperidine, compound 12, was obtained as an oil, in a yield of 19 gm.
EXAMPLE 2
This example illustrates the preparation of compound 14 on the accompanying FIGURE, 4,4-dimethoxy-1-[3-(fluorophenoxy)propyl]-3-hydroxypiperidine, from compound 12 prepared according to Example 1 above.
This procedure was conducted in a 2L 3-necked flask with a condenser and a nitrogen bubbler and stirrer. The reaction was conducted under an atmosphere of nitrogen.
To the flask was added 200 ml methyl isobutyl ketone (MIBK), 74.6 gm potassium carbonate, followed by 67.8 gm of 1-chloro-3-(4-fluorophenoxy)propane in a further 100 ml MIBK. Then 72.5 gm of the starting material, compound 12, in an additional 400 ml MIBK was added, followed by sodium iodide catalyst (0.6 gm).
The reaction took place under reflux overnight, then an additional 28 gm of potassium carbonate was added and the refluxing was continued for a further 5 hours.
The reaction mixture was then cooled to room temperature, the solid was filtered off and washed with 200 ml of MIBK. The organic layers were combined and concentrated on a rotary evaporator, to yield 110 gm of a brownish solid. Five hundred and fifty (550) mL of hexane was added and the solid triturated overnight. The light brown solid was filtered and washed with 100 mL of hexane, and dried in vacuum at 50° C. to give 70 grams of compound 14.
EXAMPLE 3
This example illustrates the preparation of compound 16 on the accompanying FIGURE, 1-(4-fluorophenyl)oxypropyl-4,4-dimethoxy-3-(2-methoxy-4-carbobenzoxyamino-5-chlorobenzyloxy)piperidine, from compound 14 prepared as described in Example 2.
To a flame dried flask under a nitrogen atmosphere, there was added 400 ml of methylene chloride, 15.6 gm of compound 14 followed by 6.7 gm of 4-dimethylaminopyridine (DMAP). This mixture was stirred at room temperature for 5 minutes, and then there was added 17.71 gm of (2-methoxy-3-carbobenzoxyamino-4-chlorobenzoyl chloride. The reaction mixture was stirred at room temperature overnight. A chromatographic check indicated a certain amount of starting material 14 still remaining, and so another 0.3 equivalent (5.3 gm) of the benzoyl chloride was added. The reaction mixture was stirred at room temperature for sixty-four hours, quenched with 500 ml water, the methylene chloride fraction was separated, and the aqueous layer was extracted with 200 ml methylene chloride, twice. The methylene chloride extracts were combined and washed with brine (200 ml), separated, and the aqueous phase backwashed with 100 ml methylene chloride.
The combined methylene chloride fractions were dried over magnesium sulfate, and the solid filtered off after 5 minutes. The organic phase was concentrated under aspirator pressure, to give a dark brownish oil. The crude product was subjected to purification on a silica gel column, eluted with hexane:ethylacetate mixtures, and the fractions containing the product were concentrated under reduced pressure. An 85% (27 gm) yield of the product 16 was obtained.
NMR spectra data confirming the structure of compound 16:
H NMR (CDCl, 300 MH ) (ppm):1.80-2.15(m.5H), 2.26 (brt, 1H, J=15 Hz), 2.40-2.70 (m, 3H), 2.78 (brd, 1H, J=15 Hz), 3.10 (brd, 1H, J=15 Hz), 3.20 (S,3H), 3.28 (S,3H), 3.95 (brS, 5H), 5.14 (brS, 1H), 5.28 (S,2H), 6.70-6.78 (m, 2H), 6.86-6.96 (m,2H), 7.38-7.50 (m, 5H), 7.90 (S,1H), 8.05 (S,1H).
C NMR(CDCl, 75 MH, (ppm): 26.83, 28.78,47.48,48.02, 49.76, 53.42, 53.84, 56.28, 66.53, 67.71, 69.04, 98.09, 102.66, 112.06, 114.22, 115.23, 115.33, 115.72, 128.49, 128.69, 128.7.3, 132.32, 135.30, 139.35, 152.61, 154.97, 155.30, 158.45, 159.87, 163.19.
EXAMPLE 4
In this example, compound A' shown on the attached FIGURE, 1-(4-fluorophenyl)oxypropyl-4-oxo-3-[(2-methoxy-4-carbobenzoxyamino-5-chlorobenzoyloxy] piperidine was prepared from compound 16 made according to Example 3.
5.50 gm of compound 16 from Example 3 was dissolved in 5 ml of methylene chloride and cooled to 0° C. 20 ml of 50% sulphuric acid was added, and the mixture removed from an ice bath and warmed to room temperature over 1 hour. Then there was slowly added over a period of 11/2 hours 5 ml of concentrated sulphuric acid, in three intermittent additions, with stirring, at room temperature. The mixture was then transferred into an ice bath, basified with 25% sodium hydroxide solution, with the temperature being kept below 10° C. The product mixture was extracted with 2 aliquots of 200 ml methylene chloride, the methylene chloride extracts were washed with brine, separated and dried over magnesium sulfate. There was obtained 4.8 gm of crude material, in the form of a viscous yellowish semi-solid.
The product was precipitated by addition of methylene chloride (1 ml) and methanol (10 ml) and stirred to form a white precipitate. The solid which was filtered off was washed with 1 ml of methylene chloride, dried in an oven at 40° C. to give 2.2 gm (43%) of white solid.
Spectral data confirming the structure of compound A':
H NMR (CDCl, 300 MHz) (ppm): 1.60-1.80 (brS, 1H), 2.00-2.12 (m, 2H), 2.40-2.60 (m, 3H), 2.70-2.90 (m,3H), 3.14-3.27 (m, 1H), 3.42-3.51 (m, 1H),3.92 (S,3H), 4.03 (t,2H,J=7 Hz), 5.25 (s,2H), 5.52 (dd, 1H,J=7.5,11.5 Hz), 6.80-6.88 (m, 2H), 6.93-7.02 (m, 2H), 7.35-7.56 (m, 5H), 7.95 (s,1H), 8.05 (s,1H).
C NMR (CDCl, 75 Mz) (ppm): 27.18, 39.88, 53.15, 56.22, 57.09, 66.15, 67.56, 73.76, 102.62,112.03, 113.27, 115.25, 115.35, 115.51, 115.82, 128.35, 128.55, 128.60, 132.26, 135.20, 139.49, 152.48, 154.92, 155.51, 158.66, 159.78, 162.43, 202.39.
EXAMPLE 5
In this example, the product A' obtained according Example 4 was subjected to acylating nuclear rearrangement, to prepare compound B' shown on the attached FIGURE, 1-(4-fluorophenyl) oxypropyl-3-hydroxy-4-methoxy-4-[[2-methoxy-4-carbobenzoxyamino-5-chlorobenzoyl]amino]-piperidine.
To a flask containing 2.10 gm of starting material compound A there was added 50 ml of methanol to obtain a white suspension. To this was added 5.2 gm of ammonium acetate and 2 ml of acetic acid, and the mixture stirred at room temperature overnight. Then most of the solvent was evaporated off, under reduced pressure, 50 ml of methylene chloride was added, and the mixture was basified with 4% sodium hydroxide until pH 10 was achieved. The product was extracted with 2 aliquots of methylene chloride, then all the methylene chloride extracts were combined and washed with brine. The organic layer was separated and dried over magnesium sulfate, and the filtrate liquid was concentrated under a high vacuum pump to give a yellowish oil product, weight 2.01 gm, compound B' (which was predominantly a single stereoisomer by NMR).
Spectral data confirming the structure of compound B':
H NMR (CDCl, 300 MHz) (ppm): 1.30 (brs,1H), 1.40-1.80(m, 1H), 1.90-2.20 (m,4H), 2.30-3.0 (m, 6H), 3.38 (s,3H), 3.90-4.05 (m, 6H) , 5.24(s,2H) ,6.75-6.85 (m, 2H), 6.90-7.05 (m, 2H), 7.32-7.52 (m, 5H), 8.06 (s,1H), 8.18 (s,1H), 8.28 (s,1H).
C NMR (CDCl, 75 MHz) (ppm): 26.93, 30.23, 49.86, 50.03, 54.29, 55.48, 56.46, 66.72, 67.66, 70.58, 85.56, 102.44, 113.59, 115.39, 115.50, 115.57, 115.88, 117.23, 128.4, 128.67, 128.72, 132.36, 135.34, 138.39, 152.74, 155.08, 155.62, 157.03, 158.77, 164.05.
EXAMPLE 6
This example illustrates the conversion of compound B', prepared according to Example 5 above, into the corresponding 3-keto compound, namely 1-[3-(4-fluorophenoxy]propyl]-3-oxo-4-[[(2-methoxy-4-carbobenzoxyamino-5-chlorobenzoyl]amino]-piperidine, compound C' on the attached FIGURE.
To a flame dried flask with molecular sieves, under a nitrogen atmosphere, there was added 1.472 gm of starting material compound B, along with 50 ml of methylene chloride. The mixture was cooled to 0° C. and 1.13 ml of trifluoroacetic acid was added dropwise. The mixture was slowly warmed to room temperature overnight, and then 20 ml of 4% sodium hydroxide was slowly added. The mixture was extracted with 3 50 ml aliquots of methylene chloride, the organic extracts were combined, and washed with 50 ml of brine. The organic layer was separated and dried over magnesium sulfate. After 5 minutes, the solid was filtered off, and the mother liquid was concentrated under aspirator pressure and pumped under vacuum. There was obtained 1.133 (81% yield) of a yellowish solid, compound C'.
Spectral data confirming the structure of compound C' so prepared:
H NMR (CDCl, 300 MHz) (ppm): 1.60-1.88 (m, 1H), 1.90-2.05 (m, 2H), 2.60-2.90 (m, 4H), 2.95 (brd, 1H, J=12 Hz), 3.05 (brd, iH, J=15 Hz), 3.42 (brd, 1H, J=12 Hz), 4.00 (t, 2H, J=7 Hz), 4.04 (s,3H), 4.10-4.18 (m, 1H), 4.62-4.75 (m, 1H), 5.26 (s, 2H), 6.78-6.84 (m,2H), 6.92-7.00 (m, 2H), 7.38-7.52 (m, 5H), 8.10 (s, 1H), 8.18 (s, 1H), 8.78 (d, 1H, J=7 Hz).
C NMR (CDCl, 75MHz) (ppm): 26.86, 32.54, 51.40, 54.39, 56.47, 57.35, 63.55, 66.27, 67.66, 102.37, 113.68, 115.38, 115.49, 115.62, 115.92, 116.35, 128.45, 128.68, 128.74, 132.15, 135.36, 138.37, 152.74, 155.02, 155.65, 157.33, 158.81, 163.51, 202.69.
EXAMPLE 7
This example illustrates the conversion of compound C' prepared according to Example 6, to compound D' shown on the attached FIGURE, namely cis-1-[3-(4-fluorophenoxy]propyl-3-hydroxy-4-[(2-methoxy-4-carbobenzoxyamino-5-chlorobenzoyl]amino]piperidine.
To a flame dried flask under nitrogen atmosphere there was added and dissolved 5.41 gm of the starting material compound C' in 100 ml of tetrahydrofuran. The solution was cooled to -30° C., and then potassium selectide (10.4 ml of a 1M solution in THF) was added dropwise. The mixture was stirred at -30° C. for 1 hour, whereupon it was quenched with 200 ml of 4% sodium hydroxide and 20 ml water. The mixture was warmed to room temperature, extracted with 2 portions of 50 ml ethyl acetate, and the organic extracts were combined. The organic phase was washed with 50 ml brine, separated, collected and dried over magnesium sulfate. The solid was filtered off, and the mother liquid was concentrated under reduced pressure, to obtain a yellowish oil. The crude product was purified using a silica gel column, eluting with 200 ml ethyl acetate then with 600 ml 10% methanol in ethyl acetate. Fractions containing the were collected, and concentrated to obtain a yellowish solid, weight 3.81 gm, compound D'.
Spectral data confirming the structure of compound D' so prepared:
H NMR (CDCL, 300 MHz) (ppm): 1.48-1.72 (m, 1H), 1.80-1.98 (m, aH), 2.10 (brt, 1H, J=15 Hz), 2.26 (brd, 1H, J=15 Hz), 2.40-2.60 (m, 2H), 2.80 (brd, 1H, J=15 Hz), 2.95 (brd, 2H, J=15 Hz), 3.80 (brs, 1H), 3.92 (s, 3H), 3.93-4.05 (m, 3H), 5.18 (s, 2H), 6.70-6.80 (m, 2H), 6.90-7.00 (m, 2H), 7.28-7.45 (m, 5H), 7.98 (s, 1H), 8.14 (s, 1H), 8.22 (d, 1H, J=7 Hz).
C NMR (CDCl, 75MHz) (ppm): 26.80, 27.08, 48.48, 51.90, 54.29, 56.27, 58.39, 66.46, 67.33, 67.47, 102.23, 113.51, 115,23, 115.33, 115.50, 115.80, 118.75, 128.30, 128.51, 128.59, 132.01, 135.26, 137.91, 152.62, 154.91, 155.49, 156.93, 158.64, 163.02.
EXAMPLE 8
Compound D' prepared as described in Example 7 was deprotected to yield compound E' as shown on the attached FIGURE, namely cis-4-amino-5-chloro-N-[1-[3-(4-fluorophenoxy)propyl]-3-hydroxy-4-piperidinyl]-2-methoxy-benzamide.
0.41 gm of the starting material compound D from Example 7 was dissolved in 30 ml acetic acid, transferred into a hydrogenation flask, and 0.1 gm of 5% palladium on carbon black, 50% water of hydration was added. The flask was connected to the hydrogenation equipment and flashed with hydrogen 3 times at 15 psi, the reaction being left to proceed for 1/2 an hour. The hydrogenation was stopped, the product filtered off the catalyst and washed with methanol. The product slowly was concentrated, and to it was added 10 ml methylene chloride and 4% sodium hydroxide to basify it. It was extracted with 2 aliquots of 10 ml methylene chloride. All of the organic extracts were combined, washed with brine, separated and the organic phase dried over magnesium sulfate. The solid was filtered off. The mother liquid was concentrated under aspirator pressure, to give a slightly yellow solid, of weight 0.33 gm. The crude was subjected under vacuum pump for 5 hours, to obtain a final yield of 0.30 gm, 92%, compound E'.
Spectral data confirming the structure of compound E' so prepared:
H NMR (CDCl, 300 MHz) (ppm): 1.60-1.80 (m, 1H), 1.90-2.02 (m, 3H), 2.20 (brt, 1H, J=15 Hz), 2.32 (brd, 1H, J=15 Hz), 2.45-2.60 (m, 2H), 2.80-3.10 (m, 3H), 3.84 (brs, 1H), 3.90 (s, 3H), 4.00 (t, 2H, J=7 Hz), 4.10-4.20 (m, 1H), 4.38 (s,2H), 6.28 (s, 1H), 6.75-6.85 (m,2H), 6.90-7.05 (m, 2H), 8.10 (s, 1H), 8.18 (d, 1H, J=7 Hz).
C NMR (CDCl, 75 MHz) (ppm): 26.82, 27.20, 49.29, 51.89, 54.26, 55.96, 58.40, 66.48, 67.53, 97.73, 111.26, 112.34, 115.23, 115.33, 115.48, 115.79, 132.78, 146.63, 154.93, 155.47, 158.62, 163.81.
EXAMPLE 9
Compound E' prepared according to Example 8 above was converted to cisapride.
To a 200 ml 3 neck round bottom flask under nitrogen atmosphere there was added 0.975 gm (0.024M) of sodium hydride in 100 ml of dried tetrahydrofuran, 5 gm (0.011M) of compound E' from Example 8 dissolved in 50 ml of tetrahydrofuran, and the mixture was stirred at room temperature for about 30 minutes, then cooled to about -25° C. 1.10 ml of dimethyl sulfate was added, and the temperature was kept between -20° and -25° C. whilst the reaction proceeded. The product was worked up by adding isopropanol to the reaction mixture, concentrating the entire mixture under the rotovap, to cause some solid precipitation. A mixture of 1:1 isopropanol:water was added, and the mixture stirred at room temperature for 2 hours. The solid was filtered off, washed with isopropanol, dried at 40° C. in a vacuum oven. A yield of 68% of cisapride was obtained.
Spectral data confirming the structure of cisapride so formed:
H NMR (CDCl, 300 MHz) (ppm): 1.40-1.80 (brs, 1H), 1.87-2.10 (m, 4H), 2.20-2.36 (m, 2H), 2.44-2.60 (m, 2H), 2.74-2.84 (m, 1H), 3.00-3.14 (m, 1H), 3.45 )s,3H), 3.92 (s, 3H), 4.00 (t, 2H, J=7 Hz), 4.10-4.30 (m, 1H), 4.40 (brs, 2H), 6.32 (s,1H), 6.80-6.90 (m, 2H), 6.95-7.10 (m, 2H), 8.12 (s,1H), 8.20 (d, 1H, J=7 Hz).
C NMr (CDCl, 75 MHz) (ppm): 26.71, 27.67, 47.98, 51.67, 53.49, 54.96, 55.83, 56.77, 66.84, 76.49, 97.85, 111.41, 112.60, 115.33, 115.41, 115.71, 132.80, 146.57, 154,97, 155.48, 157.47, 158.63, 163.64. | Cisapride, i.e. cis-4-amino-5-chloro-N-[1-[3-(4 fluoro-phenoxy)propyl]-3-methoxy-4-piperidinyl]-2-methoxy-benzamide, and similar benzamide derivatives, are prepared from novel 1-aryloxyalkyl- or 1-aralkyl-3-arylcarbonyloxy-4-oxo-piperidines, by nuclear substituent re arrangement involving acyl transfer under animal forming conditions, to give the corresponding 1-aryloxyalkyl- or 1-aralkyl-3-hydroxy-4-lower alkoxy-4-arylamido piperidine. This in turn is readily converted to the corresponding 3-oxo-4-arylamido-piperidine by reaction with strong organic acid, which can then be reduced, deprotected and 3-methylated to give the final compound, e.g. cisapride. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to gas-permeable contact lenses. More particularly, the present invention relates to cellulose acetate butyrate contact lenses which have been rendered more hydrophilic and, hence, have improved surface wettability and in some cases improved soiling resistance.
BRIEF SUMMARY OF THE INVENTION
Present day contact lenses are of the following general types: the so-called hard lenses usually containing polymethylmethacrylate which is hydrophobic in nature; the moderately hydrophilic gas-permeable lenses one type of which is composed of cellulose acetate butyrate, and the soft lenses which are at least partially hydrophilic and may be composed of crosslinked ethylene glycol monomethacrylate.
Semi-rigid, gas-permeable contact lenses of generally concave-convex cross-section formed of transparent, optically clear cellulose acetate butyrate are known to be art. See, for example, U.S. Pat. No. 3,900,250.
The present invention is based upon the discovery that the moderately hydrophilic properties of cellulose acetate butyrate contact lenses can be greatly improved by an increase in wettability and, hence, comfort of the lens to the wearer without adversely affecting the dimensional stability or light transmission quality of the treated lenses. The resulting contact lenses also retain their gas permeability which is an important factor for contact lenses as it facilitates the ready interchange of oxygen and carbon dioxide gases between the cornea and the surrounding atmosphere, thereby permitting the normal and essential metabolic processes to continue within the cornea. The present invention accomplishes these desirable results by treatment of the lenses, after machining and polishing fabrication, by one of several procedures detailed more particularly below, the net result being an increase in the surface wettability of the lenses.
In one embodiment of the present invention, this desirable result may be achieved by surface hydrolysis of the lenses. This reaction regenerates the hydroxyl groups of the cellulose which may be readily accomplished by the action of bases, such as ammonia, for example, as described more in detail hereinafter, or by the use of alkali metal hydroxides such as sodium hydroxide or by treatment with acids such as a strong mineral acid e.g. hydrochloric acid, sulfuric acid, etc. or by benzene sulfonic acid. An extremely important factor of this aspect of the present invention is that this process results in confining the reaction to the very surface of the lenses only.
In another embodiment of the present invention, the desired result of increased surface wettability of the lenses may be accomplished by surface reduction of the ester groups of the cellulose by the use of complex hydrides such as sodium borohydride, for example, in water. The result of this reaction, after hydrolysis of the reaction product, is again regeneration of the hydroxyl groups of the cellulose.
In still another embodiment of the present invention, the surface reaction of the ester groups of the cellulose may be accomplished by treatment with organometallic compounds such as n-butyl lithium, in non-polar solvents such as pentane, for example. Hydrolysis of the reaction product also results in the regeneration of the cellulose hydroxyl groups.
In the most preferred embodiment of the present invention, the desirable result of surface wettability of the lenses may be accomplished by immersion of the lenses, after machining and fabrication, in an ammoniacal salt solution. This process involves the de-esterification of the cellulose acetate butyrate with subsequent regeneration of the cellulose on the lens surface and to some depth into the lens thereby exposing more hydroxyl groups on the surface and the lens is therefore rendered more hydrophilic with the result of an increase in surface wettability of the lenses exhibited by a lower contact angle.
In order to impart a charge to the surface of the lenses and to render the lenses even more hydrophilic compared to a hydroxylated surface, the hydroxyl groups regenerated by one or more of the procedures outlined above may be further reacted with substances like chloroacetic acid salts. The products of this reaction are salts of carboxymethyl derivatives of hydroxy compounds.
The most critical factor of all of the surface modifications of the lenses described above is the confining of the reaction to the very top layers of the lenses. An irregular surface reaction or deeper penetration of the reactant under the surface would adversely affect both the optical properties and shape of the lenses.
The surface modification of the cellulose acetate butyrate lenses will be described more in detail in conjunction with the surface hydrolysis by the use of an ammoniacal salt solution.
DETAILED DESCRIPTION OF THE INVENTION
In carrying out the present invention, the contact lenses composed of cellulose acetate butyrate are machined and polished in the customary way. Upon completion of the lens fabrication, and after cleaning the lenses in the usual manner by placing them in an ultrasonic cleaner with an appropriate cleaning solution such as, for example, 0.4% Alconox followed by rinsing in purified water, the lenses are immersed in an ammonia solution comprising a saturated sodium chloride solution prepared by mixing 370 grams sodium chloride, U.S.P. grade, per liter of deionized water with stirring until the sodium chloride no longer goes into solution, and to which is added 0.585 liters of ammonium hydroxide with an ammonia content of 27% by weight, or equivalent, to each 0.415 liters saturated sodium chloride solution. The ammonia concentration may vary over a wide range but a concentration of between about 10-18% provides for a fast and still controllable process. The ammonia concentration is preferably 14.0±0.5%. This can be readily accomplished by the addition of more saturated sodium chloride solution if the ammonia concentration is above the desired level or, if the ammonia concentration is below the desired amount, additional ammonium hydroxide may be added. The concentration of the strong non-associating electrolyte such as sodium chloride, potassium chloride, sodium sulfate, etc. should be maintained at the level which will help better to confine the reaction to the surface of the lenses. It is preferable to keep the concentration of the strong electrolyte high enough, preferably up to saturation, to maintain comfortably the concentration of ammonia at the level mentioned above. Obviously, sources of ammonia may be employed other than by the use of ammonium hydroxide as, for example, by bubbling ammonia through the salt solution, in order to maintain the ammonia concentration at a desired level, but the use of ammonium hydroxide is preferred as it offers a convenient way of attaining the desired concentration of ammonia.
After the desired ammonia concentration is reached and maintained for the requisite period of time, the lenses are soaked in the described ammoniacal salt solution for a sufficient period of time to soften the lens surface and increase surface wettability. Usually a period of time from a few to several hours, e.g. 48 hours, is sufficient to accomplish the desired improved wettability of the lenses.
The lenses are thereafter rinsed in tap water for a minimum of 8 hours and again rinsed with purified water. The lenses are thereafter immersed in a 4.0% solution of Alconox, cleaned in the ultrasonic cleaner and washed again in purified water.
Testing of the so-treated lenses has demonstrated that immersion in the ammoniacal salt solution does not adversely affect the safety or effectiveness of the lenses and makes the lenses more comfortable to the wearer by providing a more wettable surface as shown by the following wetting angle measurements:
The soak state wetting angle of contact lens material was measured using the Captured Bubble method. The first measurement is the average of ten bubbles measured left and right sides. The second number, in parentheses, is the standard deviation.
Reference: CLMA's (Tentative) Standard Method for Determining Wetting Angle.
TABLE 1______________________________________CAPTURED BUBBLE WETTING ANGLES DISC 1 DISC 2 30 Hours 16 Hours______________________________________SOAK STATE 18.3° 13.2° (3.9°) (2.7°)1 WEEK 14.7° 12.2°SOAK STATE (1.0°) (0.6°)______________________________________
Average wetting angle of the treated two discs twenty measurements, is 13.5°.
The following table demonstrates that by subjecting the lenses to the described treatment, the lenses meet material specifications as to hardness and absorptivity. Test and control pieces were manufactured according to the standard acceptance procedures. Test pieces were treated with the described ammoniacal salt solution. Control pieces were exposed to buffered 0.9% saline for an equivalent time period. The same method of rinsing was used for both the test and control pieces.
TABLE 2______________________________________HARDNESSAverage of three readings/blank; twelve blanks/group BEFORE AFTER______________________________________CONTROL BLANKS 79 76TEST BLANKS 79 76______________________________________
The hardness decreased equally for the control blanks and test blanks after their respective treatments.
The refractive index was determined at 25° C. after treatment of the discs.
______________________________________ n .sub.D.sup.25° C.______________________________________CONTROL1 1.47392 1 4732TEST3 1 47584 1.4754______________________________________ABSORPTIVITY (LIGHT TRANSMISSION METHOD 010) BEFORE SOAK AFTER SOAK______________________________________CONTROL1 0.195 0.1812 0.155 0.145TEST3 0.189 0.1754 0.172 0.165______________________________________
All absorptivity values meet the current specification limit of 0.208 maximum. There is a slight improvement in light transmission indicated by lower absorptivity.
______________________________________ABSORPTIVITY AT 610nm (COLOR-METHOD 076) BEFORE SOAK AFTER SOAK CHANGE______________________________________CONTROL1 0.225 0.209 -0.0162 0.179 0.171 -0.008TEST3 0.219 0.212 -0.0074 0.198 0.185 -0.013______________________________________
Only two discs were measured and a meaningful standard deviation cannot be calculated. There is no difference between control and test discs.
As examples of other treatments in accordance with the present invention there may be mentioned the following:
As an example of sodium hydroxide hydrolysis the finished lenses are gently stirred in 20% solution of this reagent for four hours at room temperature. After the treatment, the lenses are washed as before.
As another example, the finished lenses are treated in a 5% water solution of sodium borohydride at room temperature for four days. The lenses are transferred into 1% hydrochloric acid and stirred gently until no bubbles of hydrogen are generated. Finally, the lenses are washed to a lasting neutral reaction. Sodium borohydride may be replaced by a faster reacting lithium borohydride.
In still another example, the finished lenses are treated in a 0.05 molar solution of n-butyl lithium in pentane for fifteen minutes at room temperature. The subsequent step consists of rinsing the lenses in pentane, stripping of the solvent in vacuum, and decomposing the reaction product in 1% hydrochloric acid for thirty minutes at room temperature. The lenses are washed in water to a lasting neutral reaction.
As a still further example, the lenses hydrophilized by one or more of the processes described above are treated in a solution of sodium chloroacetate and sodium hydroxide (116 g of sodium chloroacetate and 80 g of sodium hydroxide per one liter of solution) for two hours at a temperature below 30° C. After the treatment, the lenses are washed to a lasting neutral reaction. | This disclosure describes the treatment of cellulose acetate butyrate contact lenses which are rendered hydrophilic by contacting said lenses with a treating agent which increases the hydrophilicity of said lenses. The treating agent is ammoniacal salt, alkali-metal hydroxide, strong mineral acid, benzene sulfonic acid, alkali metal borohydride or organometallic compound. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to the following U.S. applications filed on or about the same day as the present application Ser. No. 12/780,871, entitled “PERSONAL VAPORIZING INHALER WITH MOUTHPIECE COVER”, Ser. No. 12/780,872, entitled “ACTIVATION TRIGGER FOR A PERSONAL VAPORIZING INHALER”, Ser. No. 12/780,873, entitled “PERSONAL VAPORIZING INHALER CARTRIDGE”, Ser. No. 12/780,874, entitled “ATOMIZER-VAPORIZER FOR A PERSONAL VAPORIZING INHALER”, now U.S. Pat. No. 8,550,068; Ser. No. 12/780,876, entitled “DATA LOGGING PERSONAL VAPORIZING INHALER”, and, Ser. No. 12/780,877, entitled “PERSONAL VAPORIZING INHALER ACTIVE CASE”, now U.S. Pat. No. 8,314,591; whose applications are hereby incorporated herein by reference for all purposes.
TECHNICAL FIELD
This invention relates to personal vapor inhaling units and more particularly to an electronic flameless vapor inhaler unit having an internal light source visible on the outside that may simulate a cigarette or deliver nicotine and other medications to the oral mucosa, pharyngeal mucosa, tracheal, and pulmonary membranes.
BACKGROUND
An alternative to smoked tobacco products, such as cigarettes, cigars, or pipes is a personal vaporizer. Inhaled doses of heated and atomized flavor provide a physical sensation similar to smoking. However, because a personal vaporizer is typically electrically powered, no tobacco, smoke, or combustion is usually involved in its operation. For portability, and to simulate the physical characteristics of a cigarette, cigar, or pipe, a personal vaporizer may be battery powered. In addition, a personal vaporizer may be loaded with a nicotine bearing substance and/or a medication bearing substance. The personal vaporizer may provide an inhaled dose of nicotine and/or medication by way of the heated and atomized substance. Thus, personal vaporizers may also be known as electronic cigarettes, or e-cigarettes. Personal vaporizers may be used to administer flavors, medicines, drugs, or substances that are vaporized and then inhaled.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a personal vaporizer unit.
FIG. 2 is a side view of a personal vaporizer unit.
FIG. 3 is an end view of the proximal end of a personal vaporizer unit.
FIG. 4 is an end view of the distal end of a personal vaporizer unit.
FIG. 4A is an end view of the distal end of a personal vaporizer unit having an embossed cartridge.
FIG. 5 is a figure map of FIGS. 6 and 7 .
FIG. 6 is a cross-section of the proximal portion of a personal vaporizer unit along the cut line shown in FIG. 2 .
FIG. 7 is a cross-section of the distal portion of a personal vaporizer unit along the cut line shown in FIG. 2 .
FIG. 8 is an exploded side view of components of a personal vaporizer unit.
FIG. 9 is an exploded cross-section of components of a personal vaporizer unit along the cut line shown in FIG. 2 .
FIG. 10 is a perspective view of a mouthpiece cover of a personal vaporizer unit.
FIG. 11 is a distal end view of the mouthpiece cover of FIG. 10 .
FIG. 12 is a cross-section of the mouthpiece cover along the cut line shown in FIG. 11 .
FIG. 13 is a perspective view of a mouthpiece of a personal vaporizer unit.
FIG. 14 is a side view of the mouthpiece of FIG. 13 .
FIG. 15 is a cross-section of the mouthpiece along the cut line shown in FIG. 14 .
FIG. 16 is a perspective view of a mouthpiece insulator of a personal vaporizer unit.
FIG. 17 is a distal end view of the mouthpiece insulator of FIG. 16 .
FIG. 18 is a side view of the mouthpiece insulator of FIG. 16 .
FIG. 19 is a cross-section of the mouthpiece insulator along the cut line shown in FIG. 18 .
FIG. 20 is a perspective view of a main housing of a personal vaporizer unit.
FIG. 21 is a distal end view of the main housing of FIG. 20 .
FIG. 22 is a proximal end view of the main housing of FIG. 20 .
FIG. 23 is a side view of the main housing of FIG. 20 .
FIG. 24 is a cross-section of the main housing along the cut line shown in FIG. 23 .
FIG. 25 is a perspective view of a main housing of a personal vaporizer unit.
FIG. 26 is a second perspective view of the main housing of FIG. 25 .
FIG. 27 is a distal end view of the main housing of FIG. 25 .
FIG. 28 is a proximal end view of the main housing of FIG. 25 .
FIG. 29 is a side view of the main housing of FIG. 25 .
FIG. 30 is a cross-section of the main housing along the cut line shown in FIG. 29 .
FIG. 31 is a perspective view of a printed circuit board (PCB or PC-board) assembly of a personal vaporizer unit.
FIG. 32 is a distal end view of the PCB assembly of FIG. 31 .
FIG. 33 is a perspective exploded view of the PCB assembly of FIG. 31 .
FIG. 34 is a side exploded view of the PCB assembly of FIG. 31 .
FIG. 35 is a perspective view of a proximal wick element of a personal vaporizer unit.
FIG. 35A is a perspective view of a heating element disposed through a proximal wick element of a personal vaporizer unit.
FIG. 35B is a perspective view of a heating element of a personal vaporizer unit.
FIG. 36 is a distal end view of the wick element of FIG. 35 .
FIG. 37 is a cross-section of the wick element along the cut line shown in FIG. 35 .
FIG. 38 is a perspective view of a distal wick element of a personal vaporizer unit.
FIG. 39 is a distal end view of the wick element of FIG. 38 .
FIG. 40 is a cross-section of the wick element along the cut line shown in FIG. 39 .
FIG. 41 is a perspective view of a distal wick element of a personal vaporizer unit.
FIG. 42 is a distal end view of the wick element of FIG. 41 .
FIG. 43 is a cross-section of the wick element along the cut line shown in FIG. 42 .
FIG. 44 is a perspective view of an atomizer housing of a personal vaporizer unit.
FIG. 45 is a distal end view of the atomizer housing of FIG. 44 .
FIG. 46 is a side view of the atomizer housing of FIG. 44 .
FIG. 47 is a top view of the atomizer housing of FIG. 44 .
FIG. 48 is a cross-section of the atomizer housing along the cut line shown in FIG. 47 .
FIG. 49 is a perspective view of an atomizer housing of a personal vaporizer unit.
FIG. 50 is a distal end view of the atomizer housing of FIG. 49 .
FIG. 51 is a side view of the atomizer housing of FIG. 49 .
FIG. 52 is a top view of the atomizer housing of FIG. 49 .
FIG. 53 is a cross-section of the atomizer housing along the cut line shown in FIG. 52 .
FIG. 54 is a perspective view of an atomizer housing and wicks of a personal vaporizer unit.
FIG. 55 is an exploded view of the atomizer housing, wire guides, and wicks of FIG. 54 .
FIG. 56 is a side view of the atomizer housing and wicks of FIG. 54 .
FIG. 57 is a distal end view of the atomizer housing and wicks of FIG. 54 .
FIG. 58 is a cross-section of the atomizer housing and wicks along the cut line shown in FIG. 57 .
FIG. 59 is a perspective view of the proximal end wick and wire guides of FIGS. 54-58 .
FIG. 59A is a perspective view showing a heating element disposed through the proximal end wick and around the wire guides of FIGS. 54-58 .
FIG. 59B is a perspective view of the heating element of a personal vaporizer unit.
FIG. 60 is a distal end view of the wick element of FIGS. 54-58 .
FIG. 61 is a cross-section of the wick element and wire guides along the cut line shown in FIG. 60 .
FIG. 62 is a perspective view of a light pipe sleeve of a personal vaporizer unit.
FIG. 63 is an end view of the light pipe sleeve of FIG. 62 .
FIG. 64 is a cross-section of the light pipe sleeve along the cut line shown in FIG. 63 .
FIG. 65 is a perspective view of a cartridge of a personal vaporizer unit.
FIG. 66 is a proximal end view of the cartridge of FIG. 65 .
FIG. 67 is a side view of the cartridge of FIG. 65 .
FIG. 68 is a top view of the cartridge of FIG. 65 .
FIG. 69 is a cross-section of the cartridge along the cut line shown in FIG. 66 .
FIG. 70 is a side view of a battery of a personal vaporizer unit.
FIG. 71 is an end view of the battery of FIG. 70 .
FIG. 72 is a perspective view of a battery support of a personal vaporizer unit.
FIG. 73 is a perspective view of a personal vaporizer unit case.
FIG. 74 is a perspective view of a personal vaporizer unit case.
FIG. 75 is a block diagram of a computer system.
DETAILED DESCRIPTION
In an embodiment a personal vaporizer unit comprises a mouthpiece configured for contact with the mouth of a person. At least part of this mouthpiece has an antimicrobial surface. This mouthpiece may also comprise silicone rubber, thermoplastic elastomer, organosilane, silver impregnated polymer, silver impregnated thermoplastic elastomer, and/or polymer. The mouthpiece may be removed from the personal vaporizing for washing or replacement, without using a tool. The mouthpiece may be provided in different colors. Designs or other patterns may be visible on the outside of the mouthpiece.
In an embodiment, a personal vaporizer unit comprises a first conductive surface configured to contact a first body part of a person holding the personal vaporizer unit, and a second conductive surface, conductively isolated from the first conductive surface, configured to contact a second body part of the person. When the personal vaporizer unit detects a change in conductivity between the first conductive surface and the second conductive surface, a vaporizer is activated to vaporize a substance so that the vapors may be inhaled by the person holding unit. The first body part and the second body part may be a lip or parts of a hand(s). The two conductive surfaces may also be used to charge a battery contained in the personal vaporizer unit. The two conductive surfaces may also form, or be part of, a connector that may be used to output data stored in a memory.
In an embodiment, a personal vaporizer unit comprises a chamber configured to receive a cartridge. The cartridge may hold a substance to be vaporized. The chamber may be configured at the distal end of the personal vaporizer unit. A user may inhale the vaporized substance at the proximal end of the personal vaporizer unit. At least one space between the exterior surface of the cartridge, and an interior surface of the chamber, may define a passage for air to be drawn from outside the personal vaporizer unit, near the distal end, through the personal vaporizer unit to be inhaled by the user along with the vaporized substance. The personal vaporizer unit may also include a puncturing element that breaks a seal on the cartridge to allow a substance in the cartridge to be vaporized. An end surface of the cartridge may be translucent to diffuse light produced internally to the personal vaporizer unit. The translucent end may be etched or embossed with letters, symbols, or other indicia that are illuminated by the light produced internally to the personal vaporizer unit.
In an embodiment, a personal vaporizer unit comprises a first wick element and a second wick element having a porous ceramic. The first wick element is adapted to directly contact a liquid held in a reservoir. The reservoir may be contained by a cartridge that is removable from the personal vaporizer unit. A heating element is disposed through the second wick element. An air gap is defined between the first wick element and the second wick element with the heating element exposed to the air gap. Air enters the first wick element through a hole in a housing holding the first wick element.
In an embodiment, a personal vaporizer unit comprises a light source internal to an opaque cylindrical housing that approximates the appearance of a smoking article. A cylindrical light tube is disposed inside the opaque cylindrical housing to conduct light emitted by the light source to an end of the opaque cylindrical housing. This allows the light to be visible outside of the opaque cylindrical housing of the vaporizer.
In an embodiment, a personal vaporizer unit comprises a microprocessor, memory, and a connector. The connector outputs data stored in the memory. The microprocessor may gather, and store in the memory, information including, but not limited to, the number of cycles the device has been triggered, the duration of the cycles, the number cartridges of fluid that are delivered. The microprocessor may also gather and store times and dates associated with the other information gathered and stored. The microprocessor may detect an empty cartridge by detecting a specific change in resistance between a wick and a housing that is equivalent to a “dry wick”, and thus signifies an empty cartridge.
In an embodiment, a case comprises a cradle adapted to hold a personal vaporizer unit. The personal vaporizer unit has dimensions approximating a smoking article. The case includes a battery and at least two contacts. The two contacts may form an electrical contact with the personal vaporizer unit when the personal vaporizer unit is in the cradle. The two contacts may conduct charge from the battery to the personal vaporizer unit to charge the personal vaporizer unit. The case may also download and store data retrieved from the personnel vaporizing unit. The case may download and store this data via the at least two contacts. The case may send this data to a computer via wired or wireless links. The case may have more than one cradle and sets of contacts (e.g., two sets of two contacts in order to hold and charge two personal vaporizer units).
FIG. 1 is a perspective view of a personal vaporizer unit. In FIG. 1 , personal vaporizer unit 100 comprises outer main shell 102 , mouthpiece cover 114 , mouthpiece 116 , and mouthpiece insulator 112 . The mouthpiece 116 and mouthpiece cover 114 define the proximal end of personal vaporizer unit 100 . The opposite end of personal vaporizer unit 100 will be referred to as the distal end. A cartridge 150 may be inserted into the distal end of personal vaporizer unit 100 . Cartridge 150 may hold the substance to be vaporized by personal vaporizer unit 100 . The substance after vaporizing may be inhaled by a user holding the personal vaporizer unit 100 . The substance may be in the form of a liquid or gel.
FIG. 2 is a side view of a personal vaporizer unit. FIG. 2 illustrates personal vaporizer unit 100 as viewed from the side. FIG. 2 illustrates personal vaporizer unit 100 comprising outer main shell 102 , mouthpiece cover 114 , mouthpiece 116 , and mouthpiece insulator 112 . FIG. 2 also illustrates cartridge 150 inserted into the distal end of personal vaporizer unit 100 .
FIG. 3 is an end view of the proximal end of a personal vaporizer unit. FIG. 3 shows the proximal end view of personal vaporizer unit 100 comprising mouthpiece cover 114 . FIG. 4 is an end view of the distal end of a personal vaporizer unit. FIG. 4 shows the distal end view personal vaporizer unit 100 comprising the visible portion of cartridge 150 . FIG. 4A is an alternative end view of personal vaporizer unit 100 comprising a visible portion of cartridge 150 that has visible logos, letters, or other symbols. These visible logos, letters, or other symbols may be illuminated or backlit by a light source internal to the personal vaporizer unit 100 . The light source may be activated intermittently under the control of a microprocessor or other electronics internal to personal vaporizer unit 100 . The light source may be activated in such a manner as to simulate the glowing ash of a cigar or cigarette.
FIG. 5 is a figure map of FIGS. 6 and 7 . FIG. 6 is a cross-section of the proximal portion of a personal vaporizer unit along the cut line shown in FIG. 2 . In FIG. 6 , the proximal portion of personal vaporizer unit 100 comprises mouthpiece cover 114 , mouthpiece 116 , mouthpiece insulator 112 , outer main shell 102 , battery support 106 , and battery 104 . The mouthpiece cover 114 surrounds and is engaged with the distal end of mouthpiece 116 . Mouthpiece 116 and outer main shell 102 are preferably made of an electrically conductive material(s). Mouthpiece 116 is separated from outer main shell 102 by mouthpiece insulator 112 . Mouthpiece 116 and outer main shell 102 are thus electrically isolated from each other by mouthpiece insulator 112 .
In an embodiment, personal vaporizer unit 100 is configured such that other main shell 102 comprises a first conductive surface configured to contact a first body part of a person holding personal vaporizer unit 100 . Mouthpiece 116 comprises a second conductive surface, which is conductively isolated from the first conductive surface. This second conductive surface is configured to contact a second body part of the person. When personal vaporizer unit 100 detects a change in conductivity between the first conductive surface and the second conductive surface, a vaporizer internal to personal vaporizer unit 100 is activated to vaporize a substance in cartridge 150 so that the vapors may be inhaled by the person holding personal vaporizer unit 100 . The first body part and the second body part may be a lip or parts of a hand(s). The two conductive surfaces of outer main shell 102 and mouthpiece 116 , respectively, may also be used to charge battery 104 contained in the personal vaporizer unit 100 . The two conductive surfaces of outer main shell 102 and mouthpiece 116 , respectively, may also be used to output (or input) data stored (or to be stored) in a memory (not shown).
Battery support 106 functions to hold battery 104 in a position which is fixed relative to our main shell 102 . Battery support 106 is also configured to allow air and vaporized substance to pass from the distal end of personal vaporizer unit 100 past battery 104 along one or more passageways. After air and the vapors of the vaporized substance pass by battery 104 , they may pass through openings in mouthpiece 116 , mouthpiece cover 114 , and mouthpiece insulator 112 , to be inhaled by a user.
FIG. 7 is a cross-section of the distal portion of a personal vaporizer unit along the cut line shown in FIG. 2 . In FIG. 7 , the distal end portion of personal vaporizer unit 100 comprises outer main shell 102 , light pipe sleeve 140 , and atomizer housing 132 , distal wick 134 , proximal wick 136 , PC board 123 , PC board 124 , spacer 128 , and main housing 160 . FIG. 7 also illustrates cartridge 150 inserted into the distal end of personal vaporizer unit 100 . As can be seen in FIG. 7 , cartridge 150 may hold a substance (e.g., a liquid or gel) in direct contact with distal wick 134 . The substance may be drawn through distal wick 134 to be vaporized inside atomizer assembly. The atomizer assembly comprises atomizer housing 132 , distal wick 134 , proximal wick 136 , and a heating element (not shown).
FIG. 8 is an exploded side view of components of a personal vaporizer unit. FIG. 9 is an exploded cross-section of components of a personal vaporizer unit along the cut line shown in FIG. 2 .
In FIGS. 8 and 9 , personal vaporizer unit 100 comprises (from left to right) mouthpiece cover 114 , mouthpiece 116 , mouthpiece insulator 112 , battery 104 , battery support 106 , PC board 123 , spacer 128 , PC board 124 , main housing 160 , proximal wick 136 , distal wick 134 , atomizer housing 132 , light pipe sleeve 140 , and cartridge 150 . Mouthpiece cover 114 surrounds and covers the proximal end of mouthpiece 116 . The distal end of mouthpiece 116 is inserted into mouthpiece insulator 112 . Battery 104 is held in place by battery support 106 . PC board 123 , spacer 128 and PC board 124 are disposed within main housing 160 . Proximal wick 136 and distal wick 134 are disposed within atomizer housing 132 .
Atomizer housing 132 (and therefore proximal wick 136 , distal wick 134 ) are disposed inside light pipe sleeve 140 and main shell 102 . (Note: for clarity, main shell 102 is not shown in FIGS. 8 and 9 .) Light pipe sleeve 140 is disposed within main shell 102 . Light pipe sleeve 140 is positioned such that light emitted from a light source mounted on PC board 124 may be conducted via light pipe sleeve 140 to a location where it is visible on the outside of personal vaporizer unit 100 .
Cartridge 150 is disposed within light pipe sleeve 140 . When assembled, a substance contained within cartridge 150 is held in direct contact with distal wick 134 . When cartridge 150 is inserted into personal vaporizer unit 100 atomizer housing 132 or distal wick 134 may puncture a seal or cap that contains the substance to be vaporized within cartridge 150 . Once punctured, the substance held within a reservoir of cartridge 150 may come in direct contact with distal wick 134 .
FIG. 10 is a perspective view of a mouthpiece cover of a personal vaporizer unit. FIG. 11 is a distal end view of the mouthpiece cover of FIG. 10 . FIG. 12 is a cross-section of the mouthpiece cover along the cut line shown in FIG. 11 . As can be seen in FIGS. 10-12 , mouthpiece cover 114 has an opening 114 - 1 that allows air and the vaporized substance to be drawn through mouthpiece cover 114 . Mouthpiece cover 114 is configured for contact with the mouth of a person. In an embodiment, at least part of the mouthpiece cover has an antimicrobial surface. This antimicrobial surface of mouthpiece cover 114 may comprise, but is not limited to: silicone rubber, thermoplastic elastomer, organosilane, silver impregnated polymer, silver impregnated thermoplastic elastomer, and/or polymer. Mouthpiece cover 114 is also configured to be removable from personal vaporizer unit 100 by a user without the use of tools. This allows mouthpiece cover 114 to be replaced and/or washed. In an embodiment, mouthpiece cover 114 may be held in place on personal vaporizer unit 100 by annular ridge 114 - 2 which interfaces with a groove on mouthpiece 116 of personal vaporizer unit 100 to secure mouthpiece cover 114 in place. In another embodiment, mouthpiece cover 114 may be held in place on personal vaporizer unit 100 by a friction fit.
FIG. 13 is a perspective view of a mouthpiece of a personal vaporizer unit. FIG. 14 is a side view of the mouthpiece of FIG. 13 . FIG. 15 is a cross-section of the mouthpiece along the cut line shown in FIG. 14 . As can be seen in FIGS. 13-15 , mouthpiece 116 has a passageway 116 - 1 that allows air and the vaporized substance to be drawn through mouthpiece 116 . Mouthpiece 116 may comprise a conductive surface or material configured to contact a first body part of a person holding personal vaporizer unit 100 . This first body part may be part of a hand, or at least one lip of the person holding personal vaporizer unit 100 . In an embodiment, mouthpiece 116 has an annular groove 116 - 2 around an outside surface. This groove is configured to receive annular ridge 114 - 2 . Thus, annular groove 116 - 2 helps secure mouthpiece cover 114 to personal vaporizer unit 100 .
FIG. 16 is a perspective view of a mouthpiece insulator of a personal vaporizer unit. FIG. 17 is a distal end view of the mouthpiece insulator of FIG. 16 . FIG. 18 is a side view of the mouthpiece insulator of FIG. 16 . FIG. 19 is a cross-section of the mouthpiece insulator along the cut line shown in FIG. 18 . As discussed previously, mouthpiece insulator 112 is disposed between main shell 102 and mouthpiece 116 . As can be seen in FIGS. 16-18 , mouthpiece insulator 112 has a passageway 112 - 1 that allows air and the vaporized substance to be drawn through mouthpiece insulator 112 . Because mouthpiece insulator 112 is disposed between main shell 102 and mouthpiece 116 , mouthpiece insulator 112 can electrically isolate main shell 102 and mouthpiece 116 . Thus, in an embodiment, mouthpiece insulator 112 comprises, or is made of, a non-electrically conductive material. This electrical isolation between main shell 102 and mouthpiece 116 allow electrical impedance changes between main shell 102 and mouthpiece 116 to be detected.
For example, a first conductive surface on mouthpiece 116 may be configured to contact a first body part of a person holding personal vaporizer unit 100 . A second conductive surface on main shell 102 (which is conductively isolated from said first conductive surface by mouthpiece insulator 112 ) may be configured to contact a second body part of the person. Personal vaporizer unit 100 may then activate in response to detecting a change in conductivity between the first conductive surface and the second conductive surface. In an embodiment, this change in conductivity may comprise a drop in impedance between the first conductive surface and the second conductive surface. In an embodiment, the change in conductivity may comprise a change in capacitance between the first conductive surface and the second conductive surface. The first body part may be a finger. The second body part may be a lip. The second body part may be a second finger. In an embodiment, the first conductive surface and the second conductive surfaces may be used to pass a charging current to battery 104 . The first and second conductive surfaces may also be used to transfer data to or from personal vaporizer unit 100 .
FIG. 20 is a perspective view of a main housing of a personal vaporizer unit. FIG. 21 is a distal end view of the main housing of FIG. 20 . FIG. 22 is a proximal end view of the main housing of FIG. 20 . FIG. 23 is a side view of the main housing of FIG. 20 . FIG. 24 is a cross-section of the main housing along the cut line shown in FIG. 23 . Main housing 160 is configured to hold PC-boards 123 and 124 , and spacer 128 . Main housing 160 is configured to fit within main shell 102 via a friction fit. Main housing 160 has several holes 166 that allow light generated by a light source(s) on PC-board 124 to pass. Once this light passes through holes 166 , it may be coupled into light pipe sleeve 140 where it is conducted to a visible location on the outside of personal vaporizer unit 100 .
Main housing 160 also has a hole 165 that allows an electrical conductor (not shown) to run from PC-board 123 or PC-board 124 through main housing 160 . This electrical conductor may be, or connect to, a heating element (not shown). This heating element may help vaporize the substance to be inhaled by the user of personal vaporizer unit 100 . This heating element may be controlled by circuitry on PC-board 123 or PC-board 124 . This heating element may be activated in response to a change in conductivity between the first conductive surface and the second conductive surface, described previously.
The exterior of main housing 160 may also have a flat surface 164 (or other geometry) forming a galley that is configured to allow the vaporized substance and air to pass between the main housing 160 and the main shell 102 . Once the vaporized substance and air pass by main housing 160 , they may travel through passageway 112 - 1 , passageway 116 - 1 , and opening 114 - 1 to be inhaled by a user of personal vaporizer unit 100 . The exterior of main housing 160 may also have one or more standoffs 167 (or other geometries) that are configured to allow air and the vaporized substance to reach the passageway formed by flat surface 164 and main shell 102 .
FIG. 25 is a perspective view of a main housing of a personal vaporizer unit. FIG. 26 is a second perspective view of the main housing of FIG. 25 . FIG. 27 is a distal end view of the main housing of FIG. 25 . FIG. 28 is a proximal end view of the main housing of FIG. 25 . FIG. 29 is a side view of the main housing of FIG. 25 . FIG. 30 is a cross-section of the main housing along the cut line shown in FIG. 29 . Main housing 260 may be used as an alternative embodiment to main housing 160 .
Main housing 260 is configured to hold PC-boards 123 and 124 , and spacer 128 . Main housing 260 is configured to fit within main shell 102 via a friction fit. Main housing 260 has several holes 266 that allow light generated by a light source(s) on PC-board 124 to pass. Once this light passes through holes 266 , it may be coupled into light pipe sleeve 140 where it is conducted to a visible location on the outside of personal vaporizer unit 100 .
Main housing 260 also has a hole 265 that allows an electrical conductor (not shown) to run from PC-board 123 or PC-board 124 through main housing 260 . This electrical conductor may be, or connect to, a heating element (not shown). This heating element may help vaporize the substance to be inhaled by the user of personal vaporizer unit 100 . This heating element may be controlled by circuitry on PC-board 123 or PC-board 124 . This heating element may be activated in response to a change in conductivity between the first conductive surface and the second conductive surface, described previously.
The exterior of main housing 260 may also have flat surfaces 264 (or other geometry) that form a galley that is configured to allow the vaporized substance and air to pass between the main housing 260 and the main shell 102 . Once the vaporized substance and air pass by main housing 260 , they may travel through passageway 112 - 1 , passageway 116 - 1 , and opening 114 - 1 to be inhaled by a user of personal vaporizer unit 100 . The exterior of main housing 260 may also have one or more standoffs 267 (or other geometries) that are configured to allow air and the vaporized substance to reach the passageway formed by flat surfaces 264 and main shell 102 .
FIG. 31 is a perspective view of a printed circuit board assembly of a personal vaporizer unit. FIG. 32 is a distal end view of the PCB assembly of FIG. 31 . FIG. 33 is a perspective exploded view of the PCB assembly of FIG. 31 . FIG. 34 is a side exploded view of the PCB assembly of FIG. 31 . As can be seen in FIGS. 31-34 , the PCB assembly is comprised of PC-board 123 and PC-board 124 separated by a spacer 128 . PC-board 124 may have mounted upon it light emitting diodes (LEDs) 125 - 127 or other light sources. LEDs 125 - 127 are configured and positioned such that when they produce light, that light passes through holes 166 or 266 in main housings 160 and 260 , respectively. This light may then be conducted by light pipe sleeve 140 to a location where it will be visible exterior to personal vaporizer unit 100 .
PC-board 123 may have mounted on it a microprocessor, memory, or other circuitry (not shown) to activate or otherwise control personal vaporizer unit 100 . This microprocessor may store data about the operation of personal vaporizer unit 100 in the memory. For example, the microprocessor may determine and store the number of cycles personal vaporizer unit 100 has been triggered. The microprocessor may also store a time and/or date associated with one or more of these cycles. The microprocessor may cause this data to be output via a connector. The connector may be comprised of the first and second conductive surfaces of mouthpiece 116 and/or main shell 102 .
In an embodiment, the microprocessor may determine a duration associated with various cycles where personal vaporizer unit 100 has been triggered. These durations (or a number based on these duration, such as an average) may be stored in the memory. The microprocessor may cause these numbers to be output via the connector. The microprocessor may determine an empty cartridge condition and stores a number associated with a number of times said empty cartridge condition occurs. The microprocessor, or other circuitry, may determine an empty cartridge condition determined based on a resistance between atomizer housing 132 or 232 and a wick 134 , 234 , 136 , or 236 . The microprocessor may also store a time and/or date associated with one or more of these empty cartridge conditions. The number of times an empty cartridge condition is detected, and or times and/or dates associated with these empty cartridge conditions may be output via the connector.
Battery 104 , PC-board 123 , PC-board 124 , and all electronics internal to personal vaporizer unit 100 may be sealed in a plastic or plastic and epoxy compartment within the device. This compartment may include main housing 160 or 260 . All penetrations in this compartment may be sealed. Thus, only wires will protrude from the compartment. The compartment may be filled with epoxy after the assembly of battery 104 , PC-board 123 , PC-board 124 , and LEDs 125 - 127 . The compartment may be ultrasonically welded closed after assembly of battery 104 , PC-board 123 , PC-board 124 , and LEDs 125 - 127 . This sealed compartment is configured such that all vapor within personal vaporizer unit 100 does not come in contact with the electronics on PC-boards 123 or 124 .
FIG. 35 is a perspective view of a proximal wick element of a personal vaporizer unit. FIG. 35A is a perspective view of a heating element disposed through a proximal wick element of a personal vaporizer unit. FIG. 35B is a perspective view of a heating element of a personal vaporizer unit. FIG. 36 is a distal end view of the wick element of FIG. 35 . FIG. 37 is a cross-section of the wick element along the cut line shown in FIG. 35 . Proximal wick 136 is configured to fit within atomizer housing 132 . As can be seen in FIGS. 35-37 , proximal wick 136 includes internal wire passageway 136 - 1 and external wire passageway 136 - 2 . These wire passageways allows a conductor or a heating element 139 to be positioned through proximal wick 136 (via internal wire passageway 136 - 1 ). This conductor or heating element 139 may also be positioned in external wire passageway 136 - 2 . Thus, as shown in FIG. 35A , a conductor or heating element 139 may be wrapped around a portion of proximal wick 136 by running the conductor or heating element 139 through internal wire passageway 136 - 1 , around the distal end of proximal wick 136 , and through external wire passageway 136 - 2 to return to approximately its point of origin. The heating element 139 may, when personal vaporizer 100 is activated, heat proximal wick 136 in order to facilitate vaporization of a substance.
FIG. 38 is a perspective view of a distal wick element of a personal vaporizer unit. FIG. 39 is a distal end view of the wick element of FIG. 38 . FIG. 40 is a cross-section of the wick element along the cut line shown in FIG. 39 . Distal wick 134 is configured to fit within atomizer housing 132 . As can be seen in FIGS. 38-40 , distal wick 134 comprises two cylinders of different diameters. A chamfered surface transitions from the smaller diameter of the distal end of distal wick 134 to a larger diameter at the proximal end of distal wick 134 . The cylinder at the distal end terminates with a flat surface end 134 - 1 . This flat surface end 134 - 1 is the end of distal wick 134 is a surface that is placed in direct contact with a substance to be vaporized when cartridge 150 is inserted into the distal end of personal vaporizer 100 . The proximal end of distal wick 134 is typically in contact with proximal wick 136 . However, at least a part of proximal wick 136 and distal wick 134 are separated by an air gap. When distal wick 134 and proximal wick 136 are used together, this air gap is formed between distal wick 134 and proximal wick 136 by stand offs 136 - 3 as shown in FIG. 37 .
FIG. 41 is a perspective view of a distal wick element of a personal vaporizer unit. FIG. 42 is a distal end view of the wick element of FIG. 41 . FIG. 43 is a cross-section of the wick element along the cut line shown in FIG. 42 . Proximal wick 234 may be used as an alternative embodiment to distal wick 134 . Proximal wick 234 is configured to fit within atomizer housing 232 . As can be seen in FIGS. 41-43 , proximal wick 234 comprises two cylinders of different diameters, and a cone or pointed end 234 - 1 . A chamfered surface transitions from the smaller diameter of the distal end of proximal wick 234 to a larger diameter at the proximal end of proximal wick 234 . The cylinder at the distal end terminates with a pointed end 234 - 1 . This pointed end 234 - 1 is the end of proximal wick 234 that is in direct contact with a substance to be vaporized. This pointed end 234 - 1 may also break a seal on cartridge 150 to allow the substance to be vaporized to come in direct contact with proximal wick 234 . The proximal end of proximal wick 234 is typically in contact with proximal wick 136 . However, at least a part of proximal wick 136 and proximal wick 234 are separated by an air gap. When distal wick 134 and proximal wick 236 are used together, this air gap is formed between proximal wick 234 and proximal wick 136 by stand offs 136 - 3 as shown in FIG. 37 .
FIG. 44 is a perspective view of an atomizer housing of a personal vaporizer unit. FIG. 45 is a distal end view of the atomizer housing of FIG. 44 . FIG. 46 is a side view of the atomizer housing of FIG. 44 . FIG. 47 is a top view of the atomizer housing of FIG. 44 . FIG. 48 is a cross-section of the atomizer housing along the cut line shown in FIG. 47 . Atomizer housing 132 is configured to fit within main shell 102 . As can be seen in FIGS. 44-48 , atomizer housing 132 comprises roughly two cylinders of different diameters. A chamfered surface 132 - 3 transitions from the smaller diameter of the distal end of atomizer housing 132 to a larger diameter at the proximal end of atomizer housing 132 . The larger diameter at the proximal end of atomizer housing 132 is configured to be press fit into light pipe sleeve 140 . The cylinder at the distal end terminates with a spade shaped tip 132 - 2 . This spade shaped tip 132 - 2 may break a seal on cartridge 150 to allow the substance to be vaporized to come in direct contact with distal wick 134 . Other shaped tips are possible (e.g., needle or spear shaped).
Chamfered surface 132 - 3 has one or more holes 132 - 1 . These holes allow air to pass, via suction, through atomizer housing 132 into distal wick 134 . This suction may be supplied by the user of personal vaporizer 100 sucking or inhaling on mouthpiece cover 114 and/or mouthpiece 116 . The air that is sucked into distal wick 134 enters distal wick 134 on or near the chamfered surface between the two cylinders of distal wick 134 . The air that is sucked into distal wick 134 displaces some of the substance being vaporized that has been absorbed by distal wick 134 causing it to be atomized as it exits distal wick 134 into the air gap formed between distal wick 134 and proximal wick 136 . The heating element disposed around proximal wick 136 may then vaporize at least some of the atomized substance. In an embodiment, one or more holes 132 - 1 may range in diameter between 0.02 and 0.0625 inches.
In an embodiment, placing holes 132 - 1 at the leading edge of the chamfered surface places a set volume of the substance to be vaporized in the path of incoming air. This incoming air has nowhere to go but through the large diameter (or “head”) end of the distal end wick 134 . When the air enters this area in distal end wick 134 it displaces the substance to be vaporized that is suspended in distal end wick 134 towards an air cavity between distal end wick 134 and proximal end wick 136 . When the displaced substance to be vaporized reaches the surface of distal end wick 134 , it is forced out of the wick by the incoming air and the negative pressure of the cavity. This produces an atomized cloud of the substance to be vaporized. In an embodiment, the diameter of the head of distal end wick 134 may be varied and be smaller than the diameter of the proximal end wick 136 . This allows for a tuned volume of air to bypass proximal end wick 136 and directly enter the cavity between distal wick 134 and distal wick 136 without first passing through distal wick 136 .
FIG. 49 is a perspective view of an atomizer housing of a personal vaporizer unit. FIG. 50 is a distal end view of the atomizer housing of FIG. 49 . FIG. 51 is a side view of the atomizer housing of FIG. 49 . FIG. 52 is a top view of the atomizer housing of FIG. 49 . FIG. 53 is a cross-section of the atomizer housing along the cut line shown in FIG. 52 . Atomizer housing 232 is an alternative embodiment, for use with proximal wick 234 , to atomizer house 132 . Atomizer housing 232 is configured to fit within main shell 102 and light pipe sleeve 140 . As can be seen in FIGS. 49-53 , atomizer housing 232 comprises roughly two cylinders of different diameters. A chamfered surface 232 - 3 transitions from the smaller diameter of the distal end of atomizer housing 232 to a larger diameter at the proximal end of atomizer housing 232 . The larger diameter at the proximal end of atomizer housing 232 is configured to be press fit into light pipe sleeve 140 . The cylinder at the distal end terminates with an open cylinder tip 232 - 2 . This open cylinder tip 232 - 2 allows the pointed end 234 - 1 of proximal wick 234 to break a seal on cartridge 150 to allow the substance to be vaporized to come in direct contact with proximal wick 234 .
Chamfered surface 232 - 3 has one or more holes 232 - 1 . These holes allow air to pass, via suction, through atomizer housing 232 into proximal wick 234 . The air that is sucked into proximal wick 234 enters proximal wick 234 on or near the chamfered surface between the two cylinders of proximal wick 234 . The air that is sucked into proximal wick 234 displaces some of the substance being vaporized that has been absorbed by proximal wick 234 causing it to be atomized as it exits proximal wick 234 into the air gap formed between proximal wick 234 and proximal wick 136 . The heating element disposed around proximal wick 136 may then vaporize at least some of the atomized substance being vaporized. In an embodiment, one or more holes 232 - 1 may range in diameter between 0.02 and 0.0625 inches.
In an embodiment, placing holes 232 - 1 at the leading edge of the chamfered surface places a set volume of the substance to be vaporized in the path of incoming air. This incoming air has nowhere to go but through the head of the distal end wick 234 . When the air enters this area in distal end wick 234 it displaces the substance to be vaporized that is suspended in distal end wick 234 towards an air cavity between distal end wick 234 and proximal end wick 236 . When the displaced substance to be vaporized reaches the surface of distal end wick 232 , it is forced out of the wick by the incoming air and the negative pressure of the cavity. This produces an atomized cloud of the substance to be vaporized. In an embodiment, the diameter of the head of distal end wick 234 may be varied and be smaller than the diameter of the proximal end wick 236 . This allows for a tuned volume of air to bypass distal wick 236 and directly enter the cavity between proximal wick 234 and distal wick 236 without first passing through distal wick 236 .
FIG. 54 is a perspective view of an atomizer housing and wicks of a personal vaporizer unit. FIG. 55 is an exploded view of the atomizer housing, wire guides, and wicks of FIG. 54 . FIG. 56 is a side view of the atomizer housing and wicks of FIG. 54 . FIG. 57 is a distal end view of the atomizer housing and wicks of FIG. 54 . FIG. 58 is a cross-section of the atomizer housing and wicks along the cut line shown in FIG. 57 . The atomizer housing and wicks shown in FIGS. 54-58 is an alternative embodiment for use with proximal wick 236 . The embodiment shown in FIGS. 54-58 use atomizer housing 232 , proximal wick 234 , proximal wick 236 , wire guide 237 , and wire guide 238 . Proximal wick 236 is configured to fit within atomizer housing 232 . As can be seen in FIGS. 54-58 , proximal wick 236 includes internal wire passageway 236 - 1 . This wire passageway 236 - 1 allows a conductor or a heating element (not shown) to be positioned through proximal wick 236 (via internal wire passageway 236 - 1 ). The conductor or heating element may be positioned around wire guide 237 and wire guide 238 . Thus, a conductor or heating element may run the through wire passageway 236 - 1 , around wire guides 237 and 238 , and then back through wire passageway 236 - 1 to return to approximately its point of origin. The heating element may, when personal vaporizer unit 100 is activated, heat proximal wick 236 in order to facilitate vaporization of a substance.
FIG. 59 is a perspective view of the proximal end wick assembly of FIGS. 54-58 . FIG. 59A is a perspective view showing a heating element disposed through the proximal end wick and around the wire guides of FIGS. 54-58 . FIG. 59B is a perspective view of the heating element of a personal vaporizer unit. FIG. 60 is a distal end view of the wick element and wire guides of FIGS. 54-58 . FIG. 61 is a cross-section of the wick element and wire guides along the cut line shown in FIG. 60 . As can be seen in FIG. 59A , a conductor or heating element 239 may run through wire passageway 236 - 1 , around wire guides 237 and 238 , and then back through wire passageway 236 - 1 to return to approximately its point of origin.
In an embodiment, distal wicks 134 , 234 , and proximal wicks 136 , 236 , may be made of, or comprise, for example a porous ceramic. Distal wicks 134 , 234 , and proximal wicks 136 , 236 , may be made of, or comprise aluminum oxide, silicon carbide, magnesia partial stabilized zirconia, yttria tetragonal zirconia polycrystal, porous metal (e.g., steel, aluminum, platinum, titanium, and the like), ceramic coated porous metal, woven metal, spun metal, metal wool (e.g., steel wool), porous polymer, porous coated polymer, porous silica (i.e., glass), and/or porous Pyrex. Distal wicks 134 , 234 , and proximal wicks 136 , 236 , may be made of or comprise other materials that can absorb a substance to be vaporized.
The conductor or heating element that is disposed through proximal wick 136 or 236 may be made of, or comprise, for example: nickel chromium, iron chromium aluminum, stainless steel, gold, platinum, tungsten molybdenum, or a piezoelectric material. The conductor or heating element that is disposed through proximal wick 136 can be made of, or comprise, other materials that become heated when an electrical current is passed through them.
FIG. 62 is a perspective view of a light pipe sleeve of a personal vaporizer unit. FIG. 63 is an end view of the light pipe sleeve of FIG. 62 . FIG. 64 is a cross-section of the light pipe sleeve along the cut line shown in FIG. 63 . Light pipe sleeve 140 is configured to be disposed within main shell 102 . Light pipe sleeve 140 is also configured to hold cartridge 150 and atomizer housing 132 or 232 . As discussed previously, light pipe sleeve 140 is configured to conduct light entering the proximal end of light pipe sleeve 140 (e.g., from LEDs 125 - 127 ) to the distal end of light pipe sleeve 140 . Typically, the light exiting the distal end of light pipe sleeve 140 will be visible from the exterior of personal vaporizer 100 . The light exiting the distal end of light pipe sleeve 140 may be diffused by cartridge 150 . The light exiting the distal end of light pipe sleeve 140 may illuminate characters and/or symbols drawn, printed, written, or embossed, etc., in an end of cartridge 150 . In an embodiment, light exiting light pipe sleeve 140 may illuminate a logo, characters and/or symbols cut through outer main shell 102 . In an embodiment, light pipe sleeve 140 is made of, or comprises, a translucent acrylic plastic.
FIG. 65 is a perspective view of a cartridge of a personal vaporizer unit. FIG. 66 is a proximal end view of the cartridge of FIG. 65 . FIG. 67 is a side view of the cartridge of FIG. 65 . FIG. 68 is a top view of the cartridge of FIG. 65 . FIG. 69 is a cross-section of the cartridge along the cut line shown in FIG. 66 . As shown in FIGS. 65-69 , cartridge 150 comprises a hollow cylinder section with at least one exterior flat surface 158 . The flat surface 158 forms, when cartridge 150 is inserted into the distal end of personal vaporizer unit 100 , an open space between the exterior surface of the cartridge and an interior surface of light pipe sleeve 140 . This space defines a passage for air to be drawn from outside personal vaporizer unit 100 , through personal vaporizer unit 100 to be inhaled by the user along with the vaporized substance. This space also helps define the volume of air drawn into personal vaporizer unit 100 . By defining the volume of air typically drawn into the unit, different mixtures of vaporized substance to air may be produced.
The hollow portion of cartridge 150 is configured as a reservoir to hold the substance to be vaporized by personal vaporizer unit 100 . The hollow portion of cartridge 150 holds the substance to be vaporized in direct contact with distal wick 134 or 234 . This allows distal wick 134 or 234 to become saturated with the substance to be vaporized. The area of distal wick 134 or 234 that is in direct contact with the substance to be vaporized may be varied in order to deliver different doses of the substance to be vaporized. For example, cartridges 150 with differing diameter hollow portions may be used to deliver different doses of the substance to be vaporized to the user.
Cartridge 150 may be configured to confine the substance to be vaporized by a cap or seal (not shown) on the proximal end. This cap or seal may be punctured by the end of atomizer housing 132 , or the pointed end 234 - 1 of proximal wick 234 .
When inserted into personal vaporizer unit 100 , cartridge standoffs 157 define an air passage between the end of light pipe sleeve 140 and main shell 102 . This air passage allows air to reach the air passage defined by flat surface 158 .
The hollow portion of cartridge 150 also includes one or more channels 154 . The end of these channels are exposed to air received via the air passage(s) defined by flat surface 158 . These channels allow air to enter the hollow portion of cartridge 150 as the substance contained in cartridge 150 is drawn into a distal wick 134 or 234 . Allowing air to enter the hollow portion of cartridge 150 as the substance contained in cartridge 150 is removed prevents a vacuum from forming inside cartridge 150 . This vacuum could prevent the substance contained in cartridge 150 from being absorbed into distal wick 134 or 234 .
In an embodiment, cartridge 150 may be at least partly translucent. Thus cartridge 150 may act as a light diffuser so that light emitted by one or more of LEDs 125 - 127 is visible external to personal vaporizer unit 100 .
FIG. 70 is a side view of a battery of a personal vaporizer unit. FIG. 71 is an end view of the battery of FIG. 70 . FIG. 72 is a perspective view of a battery support of a personal vaporizer unit. As can be seen in FIG. 72 , battery support 106 does not form a complete cylinder that completely surrounds battery 104 . This missing portion of a cylinder forms a passageway that allows air and the vaporized substance to pass by the battery from the atomizer assembly to the mouthpiece 116 so that it may be inhaled by the user.
FIG. 73 is a top perspective view of a personal vaporizer unit case. FIG. 74 is a bottom perspective view of a personal vaporizer unit case. Personal vaporizer case 500 is configured to hold one or more personal vaporizer units 100 . Personal vaporizer case 500 includes a connector 510 to interface to a computer. This connector allows case 500 to transfer data from personal vaporizer unit 100 to a computer via connector 510 . Case 500 may also transfer data from personal vaporizer unit 100 via a wireless interface. This wireless interface may comprise an infrared (IR) transmitter, a Bluetooth interface, an 802.11 specified interface, and/or communicate with a cellular telephone network. Data from a personal vaporizer unit 100 may be associated with an identification number stored by personal vaporizer unit 100 . Data from personal vaporizer unit 100 may be transmitted via the wireless interface in association with the identification number.
Personal vaporizer case 500 includes a battery that may hold charge that is used to recharge a personal vaporizer unit 100 . Recharging of personal vaporizer unit 100 may be managed by a charge controller that is part of case 500 .
When case 500 is holding a personal vaporizer unit 100 , at least a portion of the personal vaporizer unit 100 is visible from the outside of case 500 to allow a light emitted by personal vaporizer unit 100 to provide a visual indication of a state of personal vaporizer unit 500 . This visual indication is visible outside of case 500 .
Personal vaporizer unit 100 is activated by a change in impedance between two conductive surfaces. In an embodiment, these two conductive surfaces are part of main shell 102 and mouthpiece 116 . These two conductive surfaces may also be used by case 500 to charge battery 104 . These two conductive surfaces may also be used by case 500 to read data out of personal vaporizer unit 100 .
In an embodiment, when a user puts personal vaporizer unit 100 in his/her mouth and provides “suction,” air is drawn into personal vaporizer unit 100 though a gap between the end of main shell 102 and cartridge 150 . In an embodiment, this gap is established by standoffs 157 . Air travels down galley(s) formed by flat surface(s) 158 and the inner surface of light pipe sleeve 140 . The air then reaches a “ring” shaped galley between atomizer housing 132 , cartridge 150 , and light pipe sleeve 140 . Air travels to distal wick 134 via one or more holes 132 - 1 , in chamfered surface(s) 132 - 3 . Air travels to distal wick 234 via one or more holes 232 - 1 , in chamfered surface(s) 232 - 3 . Air is also allowed to enter cartridge 150 via one or more channels 154 . This air entering cartridge 150 via channels 154 “back fills” for the substance being vaporized which enters distal wick 134 . The substance being vaporized is held in direct contact with distal wick 134 or 234 by cartridge 150 . The substance being vaporized is absorbed by and may saturate distal wick 134 or 234 and proximal wick 136 or 236 .
The incoming air drawn through holes 132 - 1 displaces from saturated distal wick 134 the substance being vaporized. The displaced substance being vaporized is pulled from wick elements 134 into a cavity between distal wick 134 and 136 . This cavity may also contain a heating element that has been heated to between 150-200° C. The displaced substance being vaporized is pulled from wick elements 134 in small (e.g., atomized) droplets. These atomized droplets are vaporized by the heating element.
In an embodiment, when a user puts personal vaporizer unit 100 in his/her mouth and provides “suction,” air is drawn into personal vaporizer unit 100 though a gap between the end of main shell 102 and cartridge 150 . In an embodiment, this gap is established by standoffs 157 . Air travels down galley(s) formed by flat surface(s) 158 and the inner surface of light pipe sleeve 140 . The air then reaches a “ring” shaped galley between atomizer housing 232 , cartridge 150 , and light pipe sleeve 140 . Air travels to proximal wick 234 via one or more holes 232 - 1 , in chamfered surface(s) 232 - 1 . Air is also allowed to enter cartridge 150 via one or more channels 154 . This air entering cartridge 150 via channels 154 “back fills” for the substance being vaporized which enters proximal wick 234 . The substance being vaporized is held in direct contact with proximal wick 234 by cartridge 150 . The substance being vaporized is absorbed by and may saturate distal wick 243 and proximal wick 236 .
The incoming air drawn through holes 232 - 1 displaces from saturated proximal wick 234 the substance being vaporized. The displaced substance being vaporized is pulled from wick elements 234 into a cavity between wick distal wick 234 and proximal wick 236 . This cavity may also contain a heating element that has been heated to between 150-200° C. The displaced substance being vaporized is pulled from distal wick 234 in small (e.g., atomized) droplets. These atomized droplets are vaporized by the heating element.
In both of the previous two embodiments, the vaporized substance and air are drawn down a galley adjacent to battery 104 , through mouthpiece insulator 112 , mouthpiece 116 , and mouthpiece cover 114 . After exiting personal vaporizer unit 100 , the vapors may be inhaled by a user.
The systems, controller, and functions described above may be implemented with or executed by one or more computer systems. The methods described above may be stored on a computer readable medium. Personal vaporizer unit 100 and case 500 may be, comprise, or include computers systems. FIG. 75 illustrates a block diagram of a computer system. Computer system 600 includes communication interface 620 , processing system 630 , storage system 640 , and user interface 660 . Processing system 630 is operatively coupled to storage system 640 . Storage system 640 stores software 650 and data 670 . Processing system 630 is operatively coupled to communication interface 620 and user interface 660 . Computer system 600 may comprise a programmed general-purpose computer. Computer system 600 may include a microprocessor. Computer system 600 may comprise programmable or special purpose circuitry. Computer system 600 may be distributed among multiple devices, processors, storage, and/or interfaces that together comprise elements 620 - 670 .
Communication interface 620 may comprise a network interface, modem, port, bus, link, transceiver, or other communication device. Communication interface 620 may be distributed among multiple communication devices. Processing system 630 may comprise a microprocessor, microcontroller, logic circuit, or other processing device. Processing system 630 may be distributed among multiple processing devices. User interface 660 may comprise a keyboard, mouse, voice recognition interface, microphone and speakers, graphical display, touch screen, or other type of user interface device. User interface 660 may be distributed among multiple interface devices. Storage system 640 may comprise a disk, tape, integrated circuit, RAM, ROM, network storage, server, or other memory function. Storage system 640 may be a computer readable medium. Storage system 640 may be distributed among multiple memory devices.
Processing system 630 retrieves and executes software 650 from storage system 640 . Processing system may retrieve and store data 670 . Processing system may also retrieve and store data via communication interface 620 . Processing system 650 may create or modify software 650 or data 670 to achieve a tangible result. Processing system may control communication interface 620 or user interface 670 to achieve a tangible result. Processing system may retrieve and execute remotely stored software via communication interface 620 .
Software 650 and remotely stored software may comprise an operating system, utilities, drivers, networking software, and other software typically executed by a computer system. Software 650 may comprise an application program, applet, firmware, or other form of machine-readable processing instructions typically executed by a computer system. When executed by processing system 630 , software 650 or remotely stored software may direct computer system 600 to operate as described herein.
The above description and associated figures teach the best mode of the invention. The following claims specify the scope of the invention. Note that some aspects of the best mode may not fall within the scope of the invention as specified by the claims. Those skilled in the art will appreciate that the features described above can be combined in various ways to form multiple variations of the invention. As a result, the invention is not limited to the specific embodiments described above, but only by the following claims and their equivalents. | A personal vapor inhaling unit is disclosed. An electronic flameless vapor inhaler unit that may simulate a cigarette has a cavity that receives a cartridge in the distal end of the inhaler unit. The cartridge brings a substance to be vaporized in contact with a wick. When the unit is activated, and the user provides suction, the substance to be vaporized is drawn out of the cartridge, through the wick, and is atomized by the wick into a cavity containing a heating element. The heating element vaporizes the atomized substance. The vapors then continue to be pulled by the user through a mouthpiece and mouthpiece cover where they may be inhaled. | 0 |
This application claims priority to U.S. Provisional Application No. 60/574,602, filed May 26, 2004, herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
The present invention is directed to increasing resveratrol concentrations in peanuts and peanut products.
The antioxidative activity (AOA) provided by phenolic compounds has been shown to inhibit the oxidation of low density proteins (2), thereby decreasing heart disease risks (3). Phenolic compounds have also been shown to have anti-inflammatory (4) and anti-carcinogic activity (5).
Resveratrol (trans-3,5,4′-trihydroxystilbene), a stilbene phytoalexin, is a phenolic compound possessing antioxidant activity. Resveratrol has been shown to provide health-promoting activities such as lowering the incidence of coronary heat disease (6), provides cancer chemopreventive activity (7) and is a phytoestrogen exhibiting variable degrees of estrogen receptor agonism (8).
Resveratrol can be found in two isomeric forms trans- and cis-resveratrol. Trans-resveratrol is the isomer most abundantly found in nature. However trans-resveratrol is transformed into the cis-isomer after exposure to UV light. Production of resveratrol in plants occurs as a defense response to exterior stress.
Various biotic and abiotic treatments have been shown to increase AOA, total phenolic compounds, and resveratrol concentration in plant material. Biotic factors such as cultivar type (9-11), maturity level (9-11) and microbial exposure have been tested for their elicitation effect on peanuts. In addition abiotic factors such as wounding by slicing in peanut (11, 17, 18), ultraviolet (UV) light exposure on grape and peanut leaves (15, 16, 19-21), ultrasound (22) exposure applied to Panax ginseng cells, and processing methods, such as roasting of peanuts (23), have also been studied as elicitors. Among these methods only the effect of slicing on resveratrol synthesis was studied on peanut kernels.
In one study, the AOA of methanolic extracts of peanut hulls was found to be 94.8 to 93.9% in peanuts harvested at 74 to 144 d after planting (9). In a later study (10), the AOA of methanolic extracts of peanut hulls from Spanish, Valencia, and Runner, and Virginia cultivars were found to be 96.1, 96.8, 96.1 and 96.6%, respectively. These studies show that neither maturity level (9) nor cultivar (10) significantly affects the AOA of methanolic extracts of peanut hulls.
In another study, UV light held at a distance of 110 mm from the surface of methanolic extracts of peanut hull powder for 0, 3, and 6 days resulted in an AOA of 99.7, 96.5, and 96.5%, respectively (24). The findings indicated that UV light had no significant effect on AOA (24). In yet another study, Hwang et al. (23) showed that peanuts roasted at 180° C. for up to 60 min provided remarkable AOA for linoleic acid in emulsion and their antioxidative effect relatively increased with roasting time from 10 to 60 min.
The total phenolic compound concentration of peanut kernels has not been reported in the literature. However, the total phenolic compound concentration has been determined in peanut hulls (9, 10) and defatted peanut flour (25). Yen and Duh (10) concluded that the difference in the amount of total phenolic compounds due to cultivar type was negligible, and that the difference was due to maturity, with more mature peanuts having higher concentrations of total phenolics. Duh and Yen (24) determined the effect of UV light exposure on extracts of peanut hull powder. They found that UV light exposure significantly decreased (p<0.05) the amount of total phenolic compounds to 7.80, 7.53 and 7.05 mg/g after exposure to UV light for 0, 3, and 6 d, respectively (24).
Red wine is one of the most common food sources of resveratrol, at an amount of 0.99-5.01 mg/L (26). Trans-resveratrol has also been identified in peanut kernels and processed peanut products. Roasted peanuts contain the lowest content of resveratrol, 0.055±0.023 μg/g, peanut butter contains a significantly higher amount, 0.324±0.129 μg/g, and boiled peanuts have the highest concentration, 5.138±2.849 μg/g (27).
Peanut kernels inoculated with microorganisms are usually sliced (12, 13) or ground (14) prior to treatment. Ingham (12) found that after slicing the ends of peanut kernels, inoculating with Helminthosporium carbonum increased resveratrol from 0 to 38-55 μg/ml after incubation for 24 h at 22° C. Aguamah et al. (13) reported that three phytoalexins increased in peanut kernels soaked in water overnight, sliced, exposed to their natural microflora and incubated. Sobolev et al. (14) later found that fully-imbibed peanut kernels ground into 3-5 mm pieces and inculcated with Aspergillus flavus and A. parasiticus , contained 30 μg/g of resveratrol after incubation.
Microbial exposure has been shown to be an effective elicitor for resveratrol in peanut kernels (12-14). However, such treatment can leave the final product unsafe and inedible. To eliminate microbial influence on the synthesis of resveratrol in peanuts stressed by size-reduction, kernels were surface sterilized with 20% hydrogen peroxide (H 2 O 2 ) (18) and 5% sodium hypochlorite (11) prior to stress application. Cooksey et al. (17) found surface sterilized (20% H 2 O 2 ) fully-imbibed peanuts sliced 2 mm thick increased resveratrol concentration. These findings indicate that the occurrence of phytoalexins in peanuts is of potential significance as a defense response against mycotoxigenic fungi of the Aspergillus flavus group (17). Arora and Strange (11) also found that sterilized (5% sodium hypochlorite) fully-imbibed, sliced (1-2 mm) peanut kernels increased resveratrol concentration after incubation for 48 h at 20° C.
Exposure to UV light increased synthesis of resveratrol in grape leaves from 0 to 50-100 μg/g after incubation (16). Grapes exposed to UV light contained 50-233.38 and 150.03-400.08 μg/g, respectively (19). Cantos et al. (20) found that mature grapes exposed for 30 min to UV light at a wavelength of 254 nm and incubated for 10 d at 0° C., followed by 5 additional days at 5° C. synthesize higher resveratrol concentrations of 100 μg/g compared to peanuts exposed to UV light at 340 nm resulting in 65 μg/g of resveratrol.
In a more recent study, Cantos et al. (21) developed and characterized an induction modeling method for resveratrol synthesis using UV irradiation pulses on Napoleon table grapes with industrial applicability. The authors found that grapes exposed to UV light at a distance of 40 cm produced higher resveratrol concentrations than at 20 cm, indicating that the UV signal was too strong at the lower distance and the resveratrol “biosynthetic system” was damaged (21). At a distance of 60 cm the induction of resveratrol was delayed compared to that at 40 cm, making the method less feasible for industrial application. Results also showed that the time to achieve the maximum resveratrol level exponentially decreased versus irradiation power. Final selection of optimum conditions was based on economic criteria and included a wavelength of 254 nm (510 W) for 30 s at a distance of 40 cm, which increased resveratrol from 10 μg/g to 115 μg/g (21).
Ultrasound has not been applied specifically as a resveratrol elicitor; however ultrasound has been successfully used in Panax ginseng cells (power density below 82 mW/cm 3 , 1-4 min) to stimulate the biosynthesis of a secondary metabolite, ginsenoside saponins (22). Cells exposed to ultrasound at a power density of 3.4, 13.7, 34.1, 61.4 and 81.8 mW/cm 3 increased saponin concentration from 0.0436 g/L in control cells to a maximum of 0.747, 0.783, 0.775, 0.830 and 0.640 g/L, respectively, after 14 d at 25° C. (22). This study showed that the total ultrasound emitted (i.e., the product of ultrasound power and exposure time) showed a significant correlation with secondary metabolite production.
SUMMARY OF THE INVENTION
The present invention is directed to methods for increasing anitoxidative activity of peanuts and peanut products by increasing total phenolic compounds. Illustratively, the AOA is increased by increasing resveratrol concentration.
In one illustrative aspect of the present invention, a method for increasing the amount of resveratrol in a peanut material is provided, comprising the steps of providing a peanut kernel, size-reducing the peanut kernel, abiotically stressing the size-reduced peanut kernel, and incubating the abiotically stressed size-reduced peanut kernel under conditions capable of increasing the amount of resveratrol in the size-reduced peanut kernel. The method may further comprise any combination of the additional steps of surface-sterilizing peanut kernel, water imbibing the peanut kernel, and removing the testa of the peanut kernel. Optionally, the peanut kernel is sized-reduced by a method selected from the group consisting of chopping, slicing, and grinding, illustratively by slicing into slices about 2 to 8.5 mm in thickness. Optionally, the size-reduced peanut kernel is stressed by a method selected from the group consisting of exposure to UV light, exposure to ultrasound, and a combination of exposure to UV light and ultrasound. In another optional embodiment, the incubating step comprises storing the size-reduced and stressed peanut kernel at about 25° C., illustratively for about 24 to 48 hours. Any combination of size reduction, stressing, and incubation are within the scope of the present invention.
In another illustrative aspect of the present invention, compositions are provided comprising a resveratrol-enriched peanut material produced by a process comprising the steps of size-reducing peanut kernels, abiotically stressing the size-reduced kernels, and incubating the stressed peanut kernels under conditions suitable for increasing the level of resveratrol in the kernels. Optionally, the resveratrol-enriched kernels may be roasted. In yet another optional embodiment, the roasted kernels may be ground, illustratively to produce peanut butter.
In yet another aspect of the present invention, compositions are provided comprising a resveratrol-enriched peanut material produced by a process comprising slicing peanut kernels into slices, exposing the slices to ultrasound, and incubating the stressed slices.
Additional features of the present invention will become apparent to those skilled in the art upon consideration of the following detailed description of preferred embodiments exemplifying the best mode of carrying out the invention as presently perceived.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A-C show mean values for trans-resveratrol concentration in peanut kernels exposed to post-harvest stress by size reduction, grinding, chopping, slicing or whole, and (A) without post size reduction stress or with post size-reduction stress by exposure to (B) UV light or (C) ultrasound over incubation time from 0 to 48 h.
FIG. 2 shows means of trans-resveratrol in peanuts stressed by size-reduction, ultrasound exposure and incubation for 44 h at 25° C. Trans-resveratrol was analyzed before incubation, indicated by the white bars, after incubation for 44 h, indicated by the bar with vertical lines, then after they were dried and roasted to a medium roast with the skin on and off, indicated by the dark gray and black bars, respectively.
DETAILED DESCRIPTION
Increases in AOA, total phenolic compounds, and trans-resveratrol in peanut kernels are desirable. Accordingly, exposure to post-harvest stress in peanut kernels has been studied to determine the effect of size-reduction methods such as slicing, chopping, or grinding; to determine the effect of stress application, illustratively by UV light or ultrasound exposure; and to determine the effect of incubation time on AOA, total phenolic compounds, and trans-resveratrol concentration in peanut kernels.
Illustratively, the size-reduction takes place by slicing surface-sterilized, fully imbibed peanut kernels into slices of about 1 mm to about 8.5 mm in thickness, more illustratively about 2 mm, about 4 mm, about 6 mm, about 7 mm, and about 1 cm, and various thicknesses between these thicknesses. In an illustrative example, slices of about 2 mm in thickness were used. In other work, it has been found that slicing to about 7 mm produces excellent results. However, it is understood that other thickness may be used and other methods of size reduction may be used.
Illustratively, the stress is applied using UV light or ultrasound. When UV light is used to apply stress, a light of 254 nm for 2-25 minutes, illustratively for 10 minutes is used. However, this light frequency and time are illustrative only. When ultrasound is used to apply stress, a variety of power densities for various lengths of time may be used. In one embodiment, ultrasound is applied at a power density of 39.2 mW/cm 3 is used for about 2-8 minutes at 25°. In one embodiment, ultrasound is applied at this power density for about 4 minutes. However, it is understood that other times and power densities may be used. A combination of UV light and ultrasound may be used as well.
Illustratively, incubation takes place subsequent to stress application, illustratively for about 24 to 72 hours, more particularly about 36 to 48 hours, illustratively at about 25° C.
In one suitable example, surface-sterilized, imbibed peanut kernels are sliced to about 5 mm, stressed, and incubated for about 48 hours. UV light, ultrasound, or a combination of UV light and ultrasound may be used to apply the stress.
EXAMPLE I
Size Reduction and Stress Analysis
Experimental Design. Raw peanut kernels were subjected to post-harvest treatments using a 4×3×4 factorial design. Factors studied were size-reduction methods: chopping, slicing, grinding, and no size-reduction treatment; post size-reduction stress applications: UV light, ultrasound, and no stress application; and incubation times: 0, 24, 36 and 48 h. Three replications of the 48 treatments were conducted for at total of 144 samples. Peanut samples were analyzed for AOA and total phenolic compound concentration in each duplicate for a total of 288 samples per analyses. Duplicate analysis for AOA and total phenolic compounds was conducted generally. However, triplicate analysis was conducted when large variation occurred between results. Trans-resveratrol analyses were conducted in triplicate. Control samples were prepared from untreated raw peanuts.
Sample Preparation. Peanuts used in the analysis were Georgia green medium runners (McCleskey Mills Inc.) harvested in Smithville, Ga. in 2002. The 22.68 kg bag (50 lb.) had been stored under refrigerated storage in a seed storage room at 7° C. for approximately 2 wk prior to the study. Approximately 3.6 kg of raw peanuts were surface sterilized in 4 L of 20% hydrogen peroxide (Sigma, St. Louis, Mo.) for 15 minutes (17) then rinsed in a sterile colander with 4 L of sterilized deionized water, sterilized by passing through a 0.2 μm nylon filter (Millipore Corporation, Bedford, Mass.). The sterilized peanuts were soaked in 4 L of sterile deionized water for 16 h to reach the maximum water holding capacity of the peanut as determined by preliminary studies. The entire process was conducted under yellow light to avoid resveratrol isomerization (28). It is understood that sterilization using hydrogen peroxide is illustrative, and that other methods of sterilization may be used if necessary, as is appropriate for the particular application.
Size-reduction. Approximately 1.2 kg of sterilized fully-imbibed peanut kernels were reduced by one of the four size-reduction methods as follows. Peanuts were ground into 1-2 mm pieces using a food processor (Model 14181, Sunbeam Oskar, China) for 20 s in 6 batches of 200 g each. Kernels were chopped into 0.5 cm pieces in two batches of 600 g each using a commercial food cutter (Model 84142, Hobart, Troy, Ohio) at 1725 rpm for 30 s. Peanuts were sliced into 2 mm thick pieces, by hand, with a razor blade, a ruler was used as a guide for size. Whole peanut kernels were also collected to represent samples with no size-reduction treatment. Each of the size-reduction batches were collected and mixed by hand with a spoon. All equipment used was sterilized prior to use with 20% hydrogen peroxide.
Post Size-reduction Stress Application. Peanuts from each of the size-reduction treatments were divided into 3 batches of 400 g each then stressed with UV light, ultrasound, or had no further stress application. Peanuts arranged 1 cm in depth on a plastic tray were exposed to UV light for 10 min (20, 21) using a germicidal lamp (254 nm, 30 W, Model UVSL-58, Ultra Violet Products, Inc., San Gabriel, Calif.) placed 40 cm (21) above the surface of the peanuts. Peanuts were stirred after 5 minutes to ensure exposure of UV light to all sides of the kernels.
Ultrasound treatment was performed in a sonic cleaner (Model FS60120V, 29.5 L×15.5 W×14.5 D cm, 260 W, 2.2 A, 50/60 Hz; Fisher Scientific, Fair Lawn, N.J.) with a power density of 39.2 mW/cm 3 . Approximately 400 g of peanuts were placed into a 1 L glass beaker containing 800 ml of sterile deionized water. The beaker was placed into the sonic cleaner filled with enough water to completely surround the beaker and sonicated for 4 min at room temperature (22). After the sample was sonicated the water was drained from the peanuts by placing them into a sterile colander for 5 min.
Approximately 100 g of sample was stored in half-pint glass mason jars (Ball Corporation, Muncie, Ind.) with two piece lids (Alltrista Corporation, Muncie, Ind.). The mason jars were wrapped with aluminum foil to protect samples from light exposure. Samples receiving none of the stress treatments were immediately placed in jars and incubated. Stress application was done in dim light to prevent trans-resveratrol isomerization (28).
Sample Incubation. Mason jars were incubated at 25° C. (Environmental Growth Chamber, Chargrin Falls, Ohio) for 24, 36 and 48 h. After incubation, the samples were stored at −23° C. until analysis for approximately 1 month.
Extraction of Antioxidants and Total Phenolic Compounds. Each peanut sample was extracted for antioxidants and total phenolic compounds in duplicate. Ten g of each peanut sample was ground and 5 g was placed in a 250 ml centrifuge tube (Nalgene, Rochester, N.Y.) with 50 ml of methanol (Fisher Scientific, Fair Lawn, N.J.). Tubes were shaken for 12 hrs with a wrist action shaker (Model 75, Burrell Corporation, Pittsburgh, Pa.) at ambient temperature, 25° C. The extracts were filtered (Whatman No. 42, England) into a round bottom flask and the residue was extracted again under the same conditions. The combined filtrate in round bottom flask was placed in a water bath (Buchi 461 Water Bath, Switzerland) at 40° C. and evaporated under vacuum in a rotary evaporator (Brinkmann RE 111, Buchi, Switzerland), approximately 30 min, to a final volume of 5 ml.
Analysis of AOA. The AOA of the 144 peanut extracts was determined according to the thiocyanate method of Osawa and Namiki (29) for Eucalyptus leaves as adapted by Duh and Yen (10). AOA was calculated as percent inhibition of oxidation of linoleic acid relative to the control after a 60 min incubation according to Emmons et al. (31).
Analysis of Total Phenolic Compounds. The concentration of total phenolic compounds present in the peanut sample was determined using a spectrophotometric method with Folin-Denis reagent (32) established by Yen and Duh (9). The blue color was measured at 726 nm (33) using a spectrophotometer (Model 8451A, Diode Array Spectrophotometer, Hewlett Packard, Palo Alto, Calif.). Absorbance was measured in triplicate for all peanut samples and standard solutions.
Analysis of Trans-resveratrol. Trans-resveratrol was analyzed using an HPLC method. Trans-resveratrol was extracted following a procedure established by Sanders et al. (34) modified by Rudolf et al. (35) using phenolphthalein as the internal standard. Approximately 35 g of peanut sample was prepared as described by Rudolf et al. (35). The entire procedure was conducted under yellow light to prevent resveratrol isomerization (28).
The dried peanut residue was prepared for HPLC analysis by adding 0.40 ml of 10% ethanol to a vial mixed and filtered into a 300 μL polypropylene plastic insert (National Scientific Co., Lawrenceville, Ga.), to minimize sample volume, which was placed in a 2 ml HPLC amber vial (National Scientific Co., Lawrenceville, Ga.). The vial was sealed with a screw cap that was fitted with a Teflon/silicone septum (National Scientific Co., Lawrenceville, Ga.).
HPLC analyses were performed using a Waters (Waters Corporation, Milford, Mass.) system with a W717 sample injector, W2695 separations module, and W996 photodiode array detector (PDA) set to monitor the UV spectrum from 240 to 400 nm. An Econosphere (Alltech Associates, Inc., Deerfield, Ill.) C 18 reversed-phase column (250 L×4.6 i.d. mm, 5 μm particle size) preceded by an Econosphere C18 (Alltech Associates, Inc., Deerfield, Ill.) guard column (7.5 L×4.6 i.d. mm, 5 μm particle size) was used for analysis.
Trans-resveratrol was analyzed using a reversed-phase HPLC method developed by Rudolf et al. (35). The mobile phase was 0.1% acetic acid (J. T. Baker, Phillipsburg, N.J.) in double deionized water that was filtered through a 0.2 μm nylon filter by vacuum, as solvent A, and 100% acetonitrile (HPLC Grade, Aldrich, Milwaukee, Wis.) as solvent B, with a flow-rate of 1.5 ml/min and the column temperature maintained at 25° C., ambient. The gradient elution increased acetonitrile linearly from 5 to 41.8% over 23 min then increased to 77% over 5 min and finally returned to 5% over 1 min and held for an additional 5 min. Waters Millenium 32 software, version 3.05 was used to control the HPLC auto sampler, gradient conditions, PDA and data acquisition. Peanut samples were injected at a volume of 80 μL.
Peak areas of trans-resveratrol and phenolphthalein were quantified at 307 nm (27) and 254 nm (35), respectively. Ratios of trans-resveratrol and phenolphthalein peak areas from analysis of peanut samples and standards were used to calculate the concentration of trans-resveratrol using the following equation (35):
Equation 2 : μg of i in sample = [ ( μg of i in standard PA of i in standard ) × PA of i in sample ( μg of IS in standard PA of IS in standard ) × PA of IS in sample ] × μg of IS in sample
where i is trans-resveratrol, IS is phenolphthalein (internal standard) and PA is the peak area. The five levels of standards, 5, 3.125, 1.250, 0.625 and 0.375 ppm (μg/ml), for trans-resveratrol and phenolphthalein were analyzed at the beginning of each HPLC sample set. Trans-resveratrol concentrations were reported as μg/g of peanut on a dry weight basis.
Statistical Analysis. Data was analyzed using SAS (37) statistical software Version 8. Regression analysis (PROC REG) was used to relate total phenolic compound concentrations as the dependant variable with peak area as the independent variable. The General Linear Model (PROC GLM) was used to detect significant differences in stress treatments for AOA, total phenolic compounds and trans-resveratrol concentration. Fishers Least Significant Difference (LSD) test was used to compare means of stress treatments on AOA, total phenolic compounds and trans-resveratrol concentration. Pearson's product correlation coefficients (PROC CORR) were calculated between mean AOA, total phenolic compounds and trans-resveratrol concentration.
Results and Discussion
AOA. Results from analysis of variance are presented in Table 1. Incubation time was the only significant factor (p<0.01) that affected AOA. Size-reduction and post size-reduction stress did not significantly affect AOA. Means and their significant differences of AOA are shown in Table 2.
TABLE 1
Results of analysis of variance of the effect of size reduction,
stress, incubation time, and their interaction on
antioxidant activity in peanut kernels.
Source of variation
F-value
Prob > F
Size reduction
0.57
0.6358
Post size reduction stress
1.1
0.3339
Incubation time
27.18
0.0001**
Size reduction * incubation time
0.42
0.5191
Size reduction * stress
0.54
0.4618
Incubation time * stress
0.31
0.5765
Size reduction * incubation time * stress
0.55
0.4587
*Significant at α < 0.05
**Significant at α < 0.01
TABLE 2
Mean values for percent antioxidant activity (AOA), measured
spectrophotometrically at 500 nm, in peanut kernels treated with 4 size reduction
methods and 3 stresses then incubated. a,b
Post size
reduction
Incubation
AOA c (%)
stress
time (h)
Ground
Chopped
Sliced
Whole
None
0
42.30 ± 1.91a
39.93 ± 1.66
40.45 ± 1.41
40.81 ± 1.40
24
38.41 ± 0.46b
38.35 ± 0.44
39.43 ± 1.29
38.93 ± 1.00
36
39.46 ± 1.35b
38.59 ± 1.03
41.96 ± 1.01
39.58 ± 0.98
48
39.83 ± 1.25b
40.08 ± 1.11
40.18 ± 1.06
40.59 ± 1.05
F-value d
8.93
2.83
1.25
1.83
p-value d
0.0007
0.0713
0.323
0.1797
UV
0
40.59 ± 0.36a
41.34 ± 1.13a
43.09 ± 1.01a
42.97 ± 1.02a
24
38.42 ± 1.01b
38.07 ± 0.21b
38.36 ± 0.67b
38.11 ± 0.56b
36
38.53 ± 0.62b
40.41 ± 1.51a
38.99 ± 1.76b
38.66 ± 1.03b
48
38.38 ± 0.73b
40.38 ± 1.25a
42.22 ± 1.54a
43.50 ± 1.29a
F-value
68.84
10.27
19.79
7.78
p-value
0.0035
0.0005
<0.0001
0.0017
Ultrasound
0
43.05 ± 1.15a
40.27 ± 0.65
42.21 ± 1.36a
39.35 ± 1.33
24
37.99 ± 0.72b
38.44 ± 0.24
38.59 ± 1.08bc
38.30 ± 0.47
36
38.62 ± 0.94b
40.46 ± 1.17
38.41 ± 1.46c
39.84 ± 1.78
48
38.62 ± 0.70b
40.75 ± 1.19
40.71 ± 1.17ab
39.66 ± 1.66
F-value
87.29
1.61
5.82
0.72
p-value
<0.0001
0.2218
0.0085
0.5522
a Means were calculated from three replications with duplicate extractions measured for a total
of 6 analyses at each incubation time. When large variation in AOA occurred between samples,
triplicate analysis was conducted. Outliers were removed prior to statistical analysis.
b For each size reduction method, means from the same stress treatment not followed by the
same letter are significantly different at α < 0.05 as determined by Fisher's Least Significant
Difference mean comparison test.
c AOA was the percent inhibition of oxidation of linoleic acid by the peanut sample compared to
control containing methanol (31):
AOA
(
%
)
=
100
[
ln
(
control
abs
0
/
abs
60
)
-
ln
(
sample
abs
0
/
abs
60
)
]
[
ln
(
control
abs
0
/
abs
60
)
]
where AOA is the antioxidant activity, abs is the absorbance of the control or peanut sample
tested at 0 and after 60 mm at 25° C., ambient. Untreated control peanuts had an AOA of
39.34 ± 0.87%.
d The General Linear Model (PROC GLM) was used to determine the F-value and probability.
AOA of untreated peanut kernels was 39.34±0.87%, which is similar to results from stressed peanuts not exposed to post size-reduction stress at 0 h of incubation, 39.93-42.30%, regardless of size-reduction (Table 2). No literature comparison could be made due to the lack of documentation on peanut kernels. However, results are lower than those reported for peanut hulls, ranging from 94.8 to 93.9% in hulls at varied levels of maturity, 74 to 144 d after planting (9), and 99.7% in untreated hulls (24). Peanut hulls contain large concentrations of phenolic compounds (9, 10), such as the three flavoniods 5,7-dihydroxychromone, eriodictyol and luteolin (38), which function as antioxidants (1). Therefore, hulls are expected to have higher levels of AOA than peanut kernels.
AOA of chopped, sliced and whole peanuts not exposed to post size-reduction stress did not change over incubation from 0 to 48 h. However ground peanuts not exposed to post size-reduction stress had a significant decrease (α<0.05) in AOA after 24 h of incubation, then remained stable until 48 h (Table 2).
All peanut samples exposed to UV light had a significant decrease (α<0.05) in AOA after 24 h of incubation (Table 2). At 36 h of incubation AOA remained stable, except for chopped peanut samples, at which time AOA increased to levels not significantly different than 0 h of incubation. After 48 h of incubation, AOA of sliced and whole peanuts increased to the initial level (0 h). AOA of ground and chopped peanuts after 48 h remained at the same level after 36 h of incubation. The decrease in AOA for ground peanuts after 24 h though 48 h in this study are contradictory to results found in the literature (24) for methanolic extracts of peanut hulls, where UV exposure did not significantly (p<0.05) affect AOA.
Ultrasound exposure did not have any effect on AOA of chopped and whole peanuts. However, AOA in sliced peanuts exposed to ultrasound decreased from 0 h of incubation after 24 and 36 h, but increased to levels at 0 to 24 h of incubation after 48 h of incubation (Table 2). AOA in ground peanuts did not significantly change after 24 to 48 h of incubation. No literature comparison can be made on the effect of ultrasound exposure to peanuts.
Total Phenolic Compounds. Results from the analysis of variance of total phenolic compounds are presented in Table 3. Time of incubation was the only significant factor (p<0.01) affecting the total phenolic compound concentration in peanut samples (Table 3). Size-reduction and post harvest size-reduction stress did not significantly affect total phenolic compound concentration. Mean values and significant differences of total phenolic compounds are shown in Table 4.
TABLE 3
Results of analysis of variance on the effect of size
reduction, stress, incubation time, and their interaction
on total phenolic compounds in peanut kernels.
Source of variation
F-value
Prob > F
Size reduction
0.81
0.4901
Post size reduction stress
0.40
0.6744
Incubation time
5.32
0.0019**
Size reduction * incubation time
0.17
0.6804
Size reduction * stress
0.93
0.3361
Incubation time * stress
0.42
0.5192
Size reduction * incubation time * stress
0.39
0.5347
*Significant at α < 0.05
**Significant at α < 0.01
TABLE 4
Mean values for total phenolic compound concentration, measured
spectrophotometrically at 726 nm, in peanut kernels treated with 4 size reduction
methods and 3 stressed then incubated. a, b
Post size
reduction
Incubation
Total Phenolics c (mg/g)
stress
time (h)
Ground
Chopped
Sliced
Whole
None
0
1.07 ± 0.28
0.96 ± 0.43a
1.19 ± 0.21
0.69 ± 0.51c
24
1.24 ± 0.11
1.23 ± 0.36a
0.92 ± 0.33
1.37 ± 0.19a
36
0.95 ± 0.32
0.39 ± 0.21b
1.13 ± 0.24
0.94 ± 0.35b
48
1.34 ± 0.13
1.31 ± 0.28a
0.87 ± 0.46
1.14 ± 0.23b
F-value d
0.97
8.48
0.59
19.22
p-value d
0.4583
0.0099
0.6461
0.0018
UV
0
1.08 ± 0.32
1.16 ± 0.22
2.06 ± 0.14
1.38 ± 0.16
24
1.01 ± 0.24
1.35 ± 0.13
1.32 ± 0.30
1.42 ± 0.15
36
1.18 ± 0.17
1.20 ± 0.27
1.41 ± 0.34
1.08 ± 0.61
48
1.51 ± 0.24
1.41 ± 0.20
1.41 ± 0.21
1.44 ± 0.18
F-value
1.2
0.22
1.96
1.4
p-value
0.4001
0.8758
0.2390
0.3191
Ultrasound
0
1.40 ± 0.16a
0.72 ± 0.43
1.58 ± 0.11
1.45 ± 0.25
24
0.85 ± 0.34b
1.38 ± 0.21
1.09 ± 0.19
1.31 ± 0.12
36
0.38 ± 0.26c
1.09 ± 0.36
1.23 ± 0.32
1.36 ± 0.18
48
0.99 ± 0.16ab
1.30 ± 0.19
1.19 ± 0.27
1.47 ± 0.21
F-value
10.03
1.92
1.12
0.09
p-value
0.0063
0.2150
0.4414
0.9627
a Means were calculated from three replications with duplicate extractions measured for a total of 6 analyses at each incubation time. When large variation in total phenolic compounds occurred between samples, triplicate analysis was conducted.Outliers were removed prior to statistical analysis.
b For each size reduction method, means for a stress not followed by the same letter are significantly different at α < 0.05 as determined by Fisher's Least Significant Difference mean comparison test.
c Total phenolic compound concentration determined in peanut kernels using a regression equation, y = [44.37(AU)x + 0.019(AU/mg/g)] where y is total phenolic compound (mg/g) and x is peak area, are reported above. Untreated control peanutshad 1.35 ± 0.46 mg/g of total phenolic compounds.
d The General Linear Model (PROC GLM) was used to determine the F-value and probability.
Untreated peanut samples contained 1.35±0.46 mg/g of total phenolic compounds. Imbibition of peanuts with water has no bearing on total phenolic compounds. Low concentration of total phenolic compounds in whole peanuts not exposed to post size-reduction stress may be a result of method variability due to interfering compounds, described previously. Results show that the peanut kernels contain lower concentrations of total phenolic compounds than peanut hulls, 7.80 mg/g (24), which is expected as hulls are darker in color, and darker color is associated with increased levels of phenolic compounds (38). Total phenolic compound concentration of ground and sliced peanuts not exposed to post size-reduction stress was not affected over incubation for 0 to 48 h. Total phenolic compound concentration in chopped peanuts not receiving post size-reduction stress significantly decreased (α<0.05) after 36 h of incubation then increased to levels not significantly different than 0 and 24 h after 48 h (Table 4). Concentration of total phenolic compounds in whole peanuts not exposed to post size-reduction stress significantly increased (α<0.05) to a maximum after 24 h of incubation then decreased at 36 h and remained constant after 48 h.
Exposure to UV light had no significant effect on total phenolic compounds, regardless of size reduction or incubation time (Table 4). Results found in the study are contradictory to the literature (24), where a significant (p<0.05) decrease in total phenolic compounds occurred in methanolic extracts of peanut hull powder after exposure to UV light. However hull samples in the literature were exposed to UV light over a longer period of time, 6 d (24), compared to 10 min in the present study.
Ultrasound had no significant effect on total phenolic compound concentration in chopped, sliced and whole peanuts (Table 4). Only ground peanuts exposed to ultrasound had a significant decrease (α<0.05) in total phenolic compounds after 24 and 36 h of incubation (Table 4). However concentration of total phenolic compounds in ground peanuts increased to levels not significantly different (α<0.05) than 0 and 24 h after 48 h (Table 4). A comparison with findings in the literature can not be made due to the lack of reports on this effect.
A large variation occurred in total phenolic compound concentration in chopped and whole peanuts not exposed to post size-reduction stress and ground peanuts exposed to ultrasound (Table 4). Since no trend in total phenolic compound concentration can be identified in these samples, variation could be attributed to method variability.
Trans-resveratrol. Evaluation of the UV spectrum for the peak corresponding to trans-resveratrol in peanut extracts revealed an irregular shape compared to that in standards. However, previous analysis of peanut extracts by GC-MS confirmed that the compound identified was trans-resveratrol. The compound identified had an identical retention time and similar fragmentation pattern to that of trans-resveratrol standard and published data (34, 39).
Results from analysis of variance of trans-resveratrol concentration are presented in Table 5. Size-reduction, post size-reduction stress, incubation time, and the interaction between size-reduction and incubation time were the factors that significantly (p<0.01) affected trans-resveratrol concentration in peanut kernels (Table 5).
TABLE 5
Results of analysis of variance on the effect of size reduction,
stress, incubation time, and their interaction on
trans-resveratrol in peanut kernels.
Source of variation
F-value
Prob > F
Size reduction
27.42
0.0001**
Post size reduction stress
3.49
0.0319*
Incubation time
6.96
0.0002**
Size reduction * incubation time
8.85
0.0032**
Size reduction * stress
0.78
0.3767
Incubation time * stress
1.36
0.245
Size reduction * incubation time * stress
0.26
0.6123
*Significant at α < 0.05
**Significant at α < 0.01
Significant differences in mean values of trans-resveratrol concentrations are shown in Table 6 and FIG. 1 . The highest amount of trans-resveratrol was 3.96±0.96 μg/g, found in sliced peanuts exposed to ultrasound after 36 h of incubation.
TABLE 6
Mean values for trans-resveratrol concentration, measured by reverse-phase
high performance liquid chromatography (HPLC) analysis at 307 nm, in peanut
kernels treated with 4 size reduction methods and 3 stresses then incubated. a,b
Post size
reduction
Incubation
Trans-resveratrol concentration c (μg/g)
stress
time (h)
Ground
Chopped
Sliced
Whole
None
0
0.18 ± 0.21b
0.25 ± 0.87c
0.22 ± 0.26c
0.20 ± 0.08c
24
0.65 ± 0.26a
1.47 ± 0.67a
1.43 ± 0.54ab
0.96 ± 0.22b
36
0.76 ± 0.49a
0.89 ± 0.17b
1.06 ± 0.90bc
1.46 ± 0.51a
48
0.49 ± 0.16a
0.74 ± 0.91b
2.15 ± 0.63a
1.44 ± 0.43a
F-value d
4.93
31.33
8.31
47.97
p-value d
0.0074
0.0001
0.0015
0.0001
UV
0
0.17 ± 0.16c
0.30 ± 0.12c
0.33 ± 0.60c
0.20 ± 0.15c
24
0.49 ± 0.37b
0.76 ± 0.35b
1.31 ± 0.54b
0.97 ± 0.27b
36
0.86 ± 0.14a
1.52 ± 0.46a
1.70 ± 0.54b
1.76 ± 0.72a
48
0.67 ± 0.58ab
1.64 ± 0.70a
3.42 ± 0.95a
0.99 ± 0.58b
F-value
18.98
31.27
63.13
12.74
p-value
0.0001
0.0001
0.0001
0.0001
Ultrasound
0
0.26 ± 0.91c
0.16 ± 0.13c
0.20 ± 0.18b
0.10 ± 0.17c
24
0.75 ± 0.23a
1.30 ± 0.36a
2.54 ± 0.54a
0.76 ± 0.15b
36
0.69 ± 0.20ab
0.93 ± 0.21b
3.96 ± 0.96a
1.47 ± 0.97a
48
0.67 ± 0.28b
0.80 ± 0.37b
2.68 ± 0.98a
1.60 ± 0.42a
F-value
78.52
38.75
8.75
67.53
p-value
0.0001
0.0001
0.0007
0.0001
a Means were calculated from three replications with triplicate extractions measured for a total of 9
analyses at each incubation time. Outliers were removed prior to statistical analysis.
b For each size reduction method, means for a stress not followed by the same letter are significantly
different at α < 0.05 as determined by Fisher's Least Significant Difference mean comparison test.
c Concentration of trans-resveratrol are reported as a relation to phenolphthalein (internal standard)
concentration from the peanut extract (38):
μg
of
i
in
sample
=
[
(
μg
of
i
in
standard
PA
of
i
in
standard
)
×
PA
of
in
sample
(
μg
of
IS
in
standard
PA
of
IS
in
standard
)
×
PA
of
IS
in
sample
]
×
μg
of
IS
in
sample
where i is trans-resveratrol, IS is phenolphthalein and PA is the peak area.
Peanut samples were injected at 0.04 ml into a gradient of actetonitrile in acetic acid/water (0.1/9.9,
v/v) increasing from 5 to 41.8% over 23 mm then increasing to 77% over 5 min and finally returned
to 5% over 1 min and held for an additional 5 min with a flow rate of 1.5 ml/min and column
temperature at 25° C. Untreated control peanuts had 0.48 ± 0.08 μg/g of trans-resveratrol.
d The General Linear Model (PROC GLM) was used to determine the F-value and probability.
Untreated peanut kernels contained 0.48±0.08 μg/g of trans-resveratrol where as approximately half of that amount (0.18±0.21 to 0.25±87 μg/g) was found in stressed peanuts not exposed to post size-reduction stress at 0 h of incubation. Lower concentrations of trans-resveratrol in the stressed peanut kernels may be a result of soaking the peanuts in water for 16 h prior to size reduction treatment. However results for trans-resveratrol concentration of untreated peanuts are similar to those reported in the literature (34), where peanuts in storage for up to 3 months contained 0.02-1.79 μg/g.
Trans-resveratrol concentration in all peanut samples not receiving post size-reduction stress significantly increased (α<0.05) from 0 to 24 h of incubation (Table 6; FIG. 1 ). Findings are consistent with those found by Cooksey et al. (17) where resveratrol concentration increased to a range of 4.3 to 23.8 μg/g in eleven different cultivars of peanuts sliced 2 mm thick and incubated for 24 h. In all size-reduced peanuts, the trans-resveratrol concentration remained constant or decreased in concentration from 24 to 36 h. Trans-resveratrol concentration increased in whole kernels from 0 to 48 h of incubation. After 48 h of incubation, trans-resveratrol concentration increased from levels at 0 h of incubation. However, from 36 to 48 h of incubation the concentration remained equal or decreased, except for sliced kernels which increased in resveratrol content. Peanuts that were exposed to size-reduction increased in trans-resveratrol concentration as particle size increased from ground to sliced ( FIG. 1 ). Slicing with 48 h of incubation produced the largest amount of trans-resveratrol (2.15±0.63 μg/g) in peanuts not exposed to post size reduction stress.
In subsequent work, it has been noted that excellent results are obtained with slicing to about 7 mm. Also, slicing to 5 mm results in a good increase in trans-resveratrol concentration.
Exposure of UV light to peanut kernels resulted in a significant increase (α<0.05) in trans-resveratrol concentration as incubation period increased from 0 to 36 h (Table 6). Trans-resveratrol concentration increased from 0 to 24 h of incubation. Then, from 24 to 36 h concentration increased even further. Results are consistent with other studies where UV light exposure to grapes leaves (16) and grapes (19) increased synthesis of resveratrol after incubation for 24 and 23 h, respectively. Trans-resveratrol remained level or increased significantly (α<0.05) from 36 to 48 h in size reduced kernels, but not in whole kernels (Table 6). As particle size increased trans-resveratrol concentration increased, but not in whole kernels ( FIG. 1 ). The highest trans-resveratrol concentration (3.42±0.95 μg/g) in peanuts exposed to UV light was found in sliced peanuts after 48 h of incubation. Creasy and Coffee (19) also found that UV light exposure to grapes and incubation for 48 h increased trans-resveratrol concentration. Fritzemeier and Kindl (40) found that leaves of Vitaceae exposed to UV light stimulated the production of stilbene synthase and catalyzed the reaction of 4-hydroxycinnamoyl-CoA and malonyl-CoA to produce resveratrol.
Ultrasound exposure caused a significant increase (α<0.05) in trans-resveratrol concentration in all samples after 24 h of incubation (Table 6). From 24 to 36 h of incubation, trans-resveratrol concentration decreased or was not significantly different (Table 6). Trans-resveratrol concentration in peanuts incubated for 36 to 48 h did not change (Table 6). In peanuts exposed to size-reduction, trans-resveratrol concentration increased as particle size increased from ground to sliced ( FIG. 1 ). The highest trans-resveratrol concentration in peanuts exposed to ultrasound occurred in sliced kernels at 24, 36 or 48 h of incubation.
The parameters for using UV light and ultrasound have not yet been optimized. It is expected that UV light at other wavelengths, intensities, distances from the bulb, and durations would result in significant trans-resveratrol production. Similarly, ultrasound at other power densities and durations are also expected to be useful. Additionally, it is expected that a combination of UV light and ultrasound, simultaneously or sequentially in either order, would likely result in higher trans-resveratrol concentration.
Relationship between AOA, total phenolic compounds and trans-resveratrol concentration. Significant Pearson's product correlation coefficients (r) obtained between AOA, total phenolic compounds and trans-resveratrol concentration are shown in Table 7. Significant r was found between trans-resveratrol concentration and AOA. However, the magnitude of correlation was low. Since trans-resveratrol has been shown to provide antioxidant activity (1), correlation between the two factors is expected. None of the other combinations tested had significant correlations. These findings are similar to Kahkonen (41), where no significant correlations could be found between the total phenolic content and AOA of plant extracts, berries, fruits, vegetables, cereals, herbs, plant sprouts, seeds and tree leaves and bark. However these results are contradictory to findings by Emmons (31) where total phenolic content was significantly correlated with AOA in oat fractions. Emmons et al. (31) findings suggest that phenolic compounds in the oat might be responsible for a large proportion of the AOA (31).
TABLE 7
Pearson product correlations coefficients (r) among trans-resveratrol
concentration, total phenolic compounds and antioxidant activity in
chopped, ground, sliced an whole peanut kernels exposed to UV
light, ultrasound and none and incubated for 0 to 48 h at 25° C.
Total
Trans-resveratrol
phenolics
Antioxidant activity
(μg/g)
(mg/g)
(%)
r
p-value
r
p-value
r
p-value
Trans-resveratrol
—
—
NS
0.2086
0.0023
(μg/g)
Total phenolics
NS
—
—
NS
(mg/g)
Antioxidant
0.2086
0.0023
NS
—
—
activity (%)
*NS is not significant
Application of post-harvest stress by size-reduction and post size-reduction stress by UV light or ultrasound exposure were effective for increasing trans-resveratrol concentration.
Example II
Peanut Butter Preparation
Peanuts were soaked in 12 L of 0.075% hydrogen peroxide (H 2 O 2 , 20%, Sigma, St. Louis, Mo., U.S.A.) solution for 1 min (42). Peanuts were transferred into a sterile strainer to remove the hydrogen peroxide solution and rinsed with filtered (0.2 μm nylon filter, Millipore Corporation, Bedford, Mass., U.S.A.) deionized water. The three batches of peanuts were combined and placed into a plastic tub (53.34 L×33.02 W×20.32 D), sterilized with 5% H 2 O 2 , containing 20 L of filtered deionized water and soaked for 16 h (11) for full imbibition. The water was drained from the peanuts and the kernels were divided into 3 batches, containing 3 kg, for each of the 3 stress treatments.
One batch of peanut kernels was manually sliced using a razor blade on a sterile cutting board into 0.7 cm thick pieces using a template. The remaining two batches were left as whole kernels, ranging from 1.5 to 2 cm in length. Sliced peanuts and one batch of whole kernels were exposed to ultrasound (Model FS60120V, 29.5 L×15.5 W×14.5 D cm, 260 W; Fisher Scientific, Fair Lawn, N.J., U.S.A.), with a power density of 39.2 mW/cm 3 , by placing 500 g into a 1 L glass beaker filled with 800 ml of filtered dionized water, for a total of 6 batches per treatment. After sonication for 4 min at 25° C. peanuts were placed into a sterile strainer for approximately 5 min, to remove excess water, then transferred to a sterilized quart glass mason jar (Ball Corporation, Munice, Ina., U.S.A.) with two piece lid (Alltrista Corporation, Muncie, Ind., U.S.A.). Each jar was wrapped with aluminum foil (Reynolds 614C, Reynolds Metals Company, Richmond, Va., U.S.A.) to protect samples from light exposure. The entire sample preparation procedure was conducted under dim light to prevent trans-resveratrol isomerizition (28).
After incubation (Environmental Growth Chamber, Chagrin Falls, Ohio, U.S.A.), 100 g of peanuts were left in the jar and stored at −23° C., approximately 1 week, until trans-resveratrol analysis was conducted. Peanuts used for descriptive analysis were placed onto an aluminum screen (29.21×43.18 cm), not more than 2.54 cm thick, and placed into a mechanical convection oven (645 Freas, Precision Scientific, Winchester, Va., U.S.A.) at 40° C. until moisture was reduced to 10±1% by weight, approximately 24 h.
Peanut butter preparation. Approximately 2.5 kg of the three dried stressed peanut samples and untreated peanuts were roasted separately in a gas roaster (Model L5, Probat In., Memphis, Term., U.S.A.) preheated at 177° C. then maintained at 135° C. while the peanuts roasted. Peanuts were visually inspected for color change every minute. Peanuts were removed from the heated barrel of the roaster, approximately 3 to 4 min, when the color looked similar to a medium roast and cooled a perforated tray in the lower base of the roaster. Once the peanuts were cool, approximately 5 min, the color was determined using a colorimeter (Gardner XL800, Pacific Scientific, Bethesda, Md., U.S.A.) with a circumferential sensor (Gardner XL845, Pacific Scientific, Bethesda, Md., U.S.A.).
The colorimeter was calibrated using a yellow reference standard tile (L=79.56, a=−2.17, b=22.98) prior to sample analysis. Peanut kernels were placed evenly on the bottom of the colorimeter sample cup and four sets of readings were obtained per sample by rotating the cup a quarter of a turn each time (Muego-Gnanasekharan and Resurreccion, 1992) the average of these reading were used in the analysis. Peanuts having a Hunter L-value of 50±1 were not further roasted.
Roasted samples were dry blanched (Model EX, Ashton Food Machinery Co., Inc., Newark, N.J., U.S.A.) to crack and remove the skins and testas. Peanut kernels with remaining testa were put through the blancher an additional time then manually inspected. All peanuts were put through a seed cleaner (Almaco seed cleaner, Allan Machine Company, Ames, Iowa, U.S.A.) to remove remaining testa. It is understood that, while the samples are blanched and testas are removed subsequent to size reduction and incubation, the samples could be blanched and testas could be removed prior to size reduction, or at any other step. Also, depending on the particular embodiment, blanching and removal of the testa may not be necessary.
After roasting, each of the peanut samples were coarsely ground using a colloid mill (Morehouse Industries, Los Angeles, Calif., U.S.A.) set with a stone clearance of 0.25 mm (10 notches). The ground sample was manually mixed in a bowl with a wooden spoon with 1% salt (Morton International Inc., Chicago, Ill., U.S.A.) and 6% corn syrup solids (Star-DRI 42F, A. E. Staley Manufacturing Company, Decatur, Ill., U.S.A.) added by weight (Gills and Resurreccion 2000). The entire contents of the bowl were placed into metal pans (30.48 L×20.32 cm) and placed into a mechanical oven (Model # M01440SC, Lindberg/Blue M, Asheville, N.C., U.S.A.) at 60° C. for 30 min. Samples were removed from the oven and 1.5% stabilizer (Fix-X, Procter & Gamble, Cincinnati, Ohio, U.S.A.) was added, by weight, then the sample was manually mixed with a wooden spoon in the same pan to distribute the stabilizer throughout the peanut butter. Samples were passed through a colloid mill with a stone clearance of 0.1 mm (5 notches), to get a finer grind, and a hot water jacket maintained at 75° C., to disperse the stabilizer. The peanut butter was placed into quart mason jars with two piece lids and stored at 4° C. approximately 1 d until sensory testing was conducted. The mill was cleaned between grinding of each of the different peanut samples.
Sensory evaluation. Subsequent sensory evaluation of the peanut butter revealed that size-reduction and post size-reduction stress exposure do not significantly affect spreadability, texture, and roasted peanut intensity. However, ultrasound exposure did negatively affect overall acceptance, aroma, and flavor. While the addition of flavoring agents and/or dilution with untreated peanut products may be used in any composition herein, the addition of flavoring agents and/or dilution with untreated peanut butter is particularly well suited to improve aroma and flavor for compositions using peanut kernel material that has been exposed to ultrasound as the post size-reduction stress. It has been noted that the effect on flavor is most noticeable when thinner slices were used. Thus, for products where aroma and flavor are more important, such as with peanut butter, size reduction to larger slices (illustratively about 7 to 8.5 mm) may be desirable, whereas for peanut flour or other products for which flavor and aroma are less important, size reduction to smaller sizes (illustratively about 5 mm) to obtain a higher trans-resveratrol concentration may be desirable.
Trans-resveratrol concentration. Evaluation of the UV spectrum, using the PDA, for the peak corresponding to trans-resveratrol in peanut extracts revealed a similar shape to that in the standard solutions and the literature (28). The compound identified in the peanut extracts also had an identical retention time (16 min) to the standard solutions therefore we concluded that the compound identified was trans-resveratrol.
Results from analysis of variance of trans-resveratrol are shown in Table 8. Size-reduction, added moisture and time of incubation were significant factors affecting trans-resveratrol concentration in peanut kernels (Table 9). Replication, ultrasound exposure and skin did not significant affect trans-resveratrol concentration in peanut kernels (Table 8). Means of trans-resveratrol concentration for the peanut samples are presented in FIG. 2 , Table 9.
After incubation all stressed peanuts had significantly higher trans-resveratrol than untreated control peanuts regardless of drying and roasting. Skin did not significantly affect the trans-resveratrol concentration of peanut samples (Table 8). Therefore, removing the skins prior to processing peanut butter would not affect the trans-resveratrol concentration.
TABLE 8
Analysis of variance of trans-resveratrol concentration for
peanut samples stressed by slicing, ultrasound and incubation with
skins on or removed and analyzed before and after drying. 1
Stress treatment
F-ratios 2
df 3
Rep
0.2576
2
Size-reduction
<0.0001***
1
Sonication
0.2783
1
Drying
<0.0001***
1
Skin
0.2222
1
Time of incubation
<0.0001***
1
MSE 4
1.14
134
1 Peanuts were stressed by slicing into 0.7 cm or left whole, 1.0 cm, and exposed to ultrasound for 4 min at 25° C. then incubated for 44 h at 25° C. and analyzed for trans-resveratrol before and after drying approximately 24 h at 40° C.
2 Significant at *α < 0.05; **α < 0.01; ***α < 0.001
3 df is degrees of freedom
4 MSE is mean square error
TABLE 9
Means, standard deviations and significant differences of trans-resveratrol (μg/g) in
peanuts stressed by size reduction, ultrasound exposure and incubating at two levels of
moisture. 1,2,3
Stressed 4
Unstressed 5
Incubation Time (h)
0
44
0
Peanut Size (cm)
0.7
1.0
1.0
0.7
1.0
1.0
1.0
Ultra-sound
Drying 6
Skin
Ultrasound
Ultrasound
None
Ultrasound
Ultrasound
None
None
Before
On
0.40 ± 0.3b
0.57 ± 0.16ab
0.74 ± 0.10a
2.73 ± 0.70a
0.76 ± 0.04c
1.08 ± 0.36b
0.45 ± 0.05d
After
On
NA
NA
NA
7.15 ± 1.27a
2.57 ± 1.02b
2.26 ± 0.53b
0.42 ± 0.04c
Off
NA
NA
NA
6.80 ± 0.37a
1.87 ± 0.88b
1.66 ± 0.10b
0.38 ± 0.15c
1 Means were calculated from 3 replications extracted 3 times for a total of 9 samples.
2 Means in each row, for each incubation time, not followed by the same letter are significantly different as determined by Fisher's Least Significant Difference (LSD) at α < 0.05 mean separation test.
3 Trans-resveratrol concentration was determined in samples by reverse-phase high performance liquid chromatography and reported on a dry weight basis.
4 Peanuts were fully imbibed with water then stressed by slicing (0.7 cm) or left whole (1.0 cm), exposed to ultrasound for 4 min at 25° C. then incubated for 44 h at 25° C.
5 Unstressed control peanuts were not exposed to stress application.
6 After incubation peanut samples were dried approximately 24 h at 40° C. then roasted at 135° C. for 3-4 min.
After 44 h of incubation peanuts that were sliced and exposed to ultrasound had the highest amount of trans-resveratrol concentration, regardless of drying and roasting ( FIG. 8 ). Although trans-resveratrol concentration appears to be higher in peanut samples with skins there was no significant difference between samples with or without skins. Slicing and ultrasound exposure increased trans-resveratrol concentration to 2.73±0.7 μg/g and 6.80±0.37-7.15±1.27 μg/g in peanuts before and after drying, respectively. An unexpected large increase in trans-resveratrol concentration occurred in peanuts with or without skins after the drying period, 24 h at 40° C. The highest increase in trans-resveratrol was found in sliced peanuts treated with ultrasound. Whereas trans-resveratrol concentration was lower in whole stressed peanuts exposed or not exposed to ultrasound and the lowest in untreated control peanuts.
A previous study (17) showed that resveratrol increased from 4.3-23.8 to 21.2-42.2 μg/g, in eleven different peanut cultivars, as time of incubation increased from 24 to 48 h, respectively, at 25° C. Therefore the increase in trans-resveratrol after the drying period maybe a result of increased incubation time at conditions that promote trans-resveratrol synthesis.
Results for sliced peanuts exposed to ultrasound are higher than findings in a previous study (43) where concentrations increased from 0.48±0.08 μg/g, in untreated peanuts, to 3.96 μg/g in peanuts that were sliced (2 mm), exposed to ultrasound (4 min at 25° C.) and incubated for 48 h at 25° C. In addition, concentrations in this example are much higher than the recent study (43) where trans-resveratrol increased from 0.29 μg/g, in untreated peanuts, to 1.38 μg/g in peanuts that were sliced 0.7 cm and incubated for 48 h at 25° C. Increased amount of synthesis of trans-resveratrol in the current example may have been a result of shorter storage conditions of the peanuts, approximately 1 mo compared to 1 yr in the later (43). Arora and Strange (11) reported a decrease in the ability of cotyledons to synthesize phytoalexins, in response to slicing 1-2 mm and incubating 48 h at 25° C., after storage for 9 mo. In addition the peanuts used in the current example were harvested in a geographic area similar to that in the previous study by Rudolf (43). McMurtrey and others (26) also found that harvest location affects the synthesis of resveratrol in grapes and wine.
Whole peanuts not exposed to ultrasound had significantly higher trans-resveratrol concentration than whole peanuts exposed to ultrasound after 44 h of incubation. However after drying and roasting the trans-resveratrol concentration in whole stressed peanuts was not significantly different.
Untreated control peanuts contained 0.45±0.05 μg/g of trans-resveratrol. Results are similar to findings in the previous study by Rudolf (43) for raw peanut kernels, 0.48±0.08 μg/g. After peanuts were fully-imbibed and exposed to stress, but not incubated, the sliced peanuts contained 0.40±0.03 μg/g, whole peanuts exposed to ultrasound contained 0.57±0.16 μg/g and whole peanuts not exposed to ultrasound contained 0.74±0.10 μg/g of trans-resveratrol.
It is understood that the resveratrol-enhanced peanut material may be processed into various forms, including but not limited to sliced or chopped peanuts, peanut butter, and peanut flour, each of which may be used in various product.
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14. Sobolev, V. S.; Cole, R. J.; Dorner, J. W. Isolation, purification, and liquid chromatographic determination of stilbene phytoalexins in peanuts. J. A.O.A.C. International 1995, 78 (5), 1177-1182.
15. Langcake, P.; Pryce, R. J. The production of resveratrol by Vitis vinifera and other members of the Vitaceae as a response to infection or injury. Physiological Plant Pathology 1976, 9, 77-86.
16. Subba Rao, P. V.; Wadia, K. D. R.; Strange, R. N. Biotic and abiotic elicitation of phytoalexins in leaves of groundnut ( Arachis hypogaea L.). Physiological and Molecular Plant Pathology 1996, 49, 343-357.
17. Cooksey, C. J.; Garratt, P. J.; Richards, S. E.; Strange, R. N. A dienyl stilbene phytoalexin from Arachis hypogaea. Phytochemistry 1988, 27 (4), 1015-1016.
18. Wotton, H. R.; Strange, R. N. Circumstantial evidence for phytoalexin involvement in the resistance of peanuts to Aspergillus flavus. J. Gen. Micro. 1985, 131, 487-494.
19. Creasy, L. L.; Coffee, M. Phytoalexin production potential of grape berries. J. Amer. Soc. Hort. Sci. 1988, 113 (2), 230-234.
20. Cantos, E.; Garcia-Viguera, C.; de Pascual-Teresa, S.; Tomas-Barberan, F. A. Effect of postharvest ultraviolet irradiation on resveratrol and other phenolics of cv. Napoleon table grapes. J. Agric. Food Chem. 2000, 48 (10), 4606-4612.
21. Cantos, E.; Espin, J. C.; Tomas-Barberan, F. A. Postharvest induction modeling method using UV irradiation pulses for obtaining resveratrol-enriched table grapes: a new “functional” fruit?. J. Agric. Food Chem. 2001, 49 (10), 5052-5058.
22. Lin, L.; Wu, J.; Ho, K.-P.; Qi, S. Ultrasound-induced physiological effects and secondary metabolite (saponin) production in Panax ginseng cell cultures. Ultrasound in Med & Biol. 2001, 27 (8), 1147-1152.
23. Hwang, J.-Y.; Shue, Y.-S.; Chang, H.-M. Antioxidative activity of roasted and defatted peanut kernels. Food Research International 2001, 34, 639-647.
24. Duh, P.-D.; Yen, G.-C. Changes in antioxidant activity and components of methanolic extracts of peanut hulls irradiated with ultraviolet light. Food Chem. 1995, 54, 127-131.
25. Maga, J. A; Lorenz, K. Gas-liquid chromatography separation of the free phenolic acid fractions in various oilseed protein sources. J. Sci. Food Agric. 1974, 25 (7), 797-802.
26. McMurtrey, K. D.; Minn, J.; Pobanz, K.; Schultz, T. P. Analysis of wines for resveratrol using direct injection high-pressure liquid chromatography with electrochemical detection. J. Agric. Food Chem. 1994, 42 (10), 1997-2000.
27. Sobolev, V. S.; Cole, R. J. Trans-resveratrol content in commercial peanuts and peanut products. J. Agric. Food Chem. 1999, 47 (4), 1435-1439.
28. Trela, B. C.; Waterhouse, A. L. Resveratrol: isomeric molar absorptivities and stability. J. Agric. Food Chem. 1996, 44 (5), 1253-1257.
29. Osawa, T,; Namiki, M. A novel type of antioxidant isolated form leaf wax of Eucalyptus leaves. Agric. Biol. Chem. 1981, 45 (3), 735-739.
30. Nawar, W. W. Lipids. In Food Chemistry, 3rd ed.; Fennema, O. R. Ed; Marcel Dekker, Inc.: New York, N.Y., 1996, 276 pp.
31. Emmons, C. L.; Peterson, D. M.; Paul, G. L. Antioxidant capacity of oat ( Avena sativa L.) extracts. 2. In vitro antioxidant activity and contents of phenolic and tocol antioxidants. J. Agric. Food Chem. 1999, 47 (12), 4894-4898.
32. A.O.A.C. Official Methods of Analysis, 14th ed. Association of Official Analytical Chemists: Washington, D.C., 1984; 187-188.
33. Zielinski, H.; Kozlowska, H. Antioxidant activity and total phenolics in selected cereal grains and their different morphological fractions. J. Agric. Food Sci. 2000, 48 (6), 2008-2016.
34. Sanders, T. H.; McMichael, R. W.; Hendrix, K. W. Occurrence of resveratrol in edible peanuts. J. Agric. Food Chem. 2000, 48 (4), 1243-1246.
35. Rudolf, J. L., Resurreccion, A. V. A., Saalia, F. K., Phillips, R. D., Development of a reversed-phase high-performance liquid chromatography method for analyzing trans-resveratrol in peanut kernels. J. Food Chem. 2005, 89, 623-638.
36. Macrae, R. HPLC in food analysis. 2nd edition; Academic Press Inc.: San Diego, Calif., 1982; pp. 59.
37. SAS. Statistical analysis system user's guide , version 8, 4th ed.; SAS Institute, Inc.: Cary, N.C., 1990.
38. Daigle, D. J.; Conkerton, E. J.; Sanders, T. H.; Mixon, A. C. Peanut hull flavonoids: their relationship with peanut maturity. J. Agric. Food Chem. 1988, 36 (6), 1179-1181.
39. Lamikanra, O., Grimm, C. C., Rodin, J. B., Inyang, I. D. Hydroxylated stilbenes in selected American wines. J. Agric. Food Chem. 1996, 44 (4), 1111-1115.
40. Fritzemeier, K.-H.; Kindl, H. Coordinate induction by UV light of stilbene synthase phenylalanine ammonia-lyase and cinnamate 4-hydroxylase in leaves of Vitaceae. Planta 1981, 151, 48-52.
41. Kahkonen, M. P.; Hopia, A. I.; Vuorela, H. J.; Rauha, J.-P.; Pihlaja, K.; Kujala, T. S.; Heinonen, M. Antioxidant activity of plant extracts containing phenolic compounds. J. Agric. Food Chem. 1999, 47 (10), 3954-3962.
42. Clavero M R S, Hung Y-C, Beuchat L R, Nakayama T. 1994. Flavor, color and texture of peanuts treated with hydrogen peroxide. Peanut Science 21(1):1-4.
43. Rudolf J L. 2003. Development of an HPLC method for resveratrol and optimization of post-harvest stress to induce production in peanuts. [MSc Thesis]. Athens, Ga.: University of Georgia. p. Available from: University of Georgia Library, Athens, Ga.
Although the invention has been described in detail with reference to preferred embodiments, variations and modifications exist within the scope and spirit of the invention as described and defined in the following claims. | Methods for increasing the amount of resveratrol in a peanut material are provided, comprising the steps of providing a peanut kernel, size-reducing the peanut kernel, abiotically stressing the size-reduced peanut kernel, and incubating the abiotically stressed size-reduced peanut kernel under conditions capable of increasing the amount of resveratrol in the size-reduced peanut kernel. Resveratrol-enhanced peanut compositions prepared according to these methods are also provided. | 0 |
BACKGROUND OF THE INVENTION
[0001] The invention relates to a tool for machine working of workpieces, particularly on universal machines by lathe working. The tool has a tool holder, which is provided with a fixing element with a shank section and a gripping head thickened compared therewith, as well as a cutting insert to be fixed thereto and which has at least one blade, usually two blades, an opening for the fixing element and at least one gripping surface cooperating with the gripping head. The tool holder has a gripping device for the fixing element.
[0002] Such tools are known from DE 36 32 296 A and DE 42 14 355 A. In the case of the latter tools the fixing element comprises a clamping screw, which projects through a round hole, having a conical land, in a triangular or trapezoidal cutting insert.
[0003] Particularly in the case of universal or automatic machines for the working of very small, precision mechanical workpieces, such as the spindles of clocks and watches and the like, both the cutting inserts and the tool holders are very small. As such universal machines have linear or turret-like tool changers in which the tools are housed in very closely juxtaposed manner and such machines are normally operated continuously in three shifts and only trained personnel are provided for the monitoring of their otherwise automatic operation, a problem arises if a tool has to be replaced, e.g. because it has been damaged. In this case it is normally necessary to wait for a setter, i.e. a qualified fitter, who replaces the tool.
OBJECTS OF THE INVENTION
[0004] Therefore the object of the invention is to create a tool of the aforementioned type, a cutting insert and a method for fitting the cutting insert, in which a tool change is simplified in that it can be carried out by a less well trained person without impairing the machining or working quality.
SUMMARY OF THE INVENTION
[0005] The invention includes by a tool having a cutting insert, which is provided with a slot linking the opening to an outer edge of the cutting insert and which has a width which is no smaller than the thickness of the shank section of the fixing element.
[0006] In this way following the loosening of the fixing element, it is possible to extract the cutting insert transversely to the longitudinal extension of the tool holder, i.e. usually upwards, without completely separating or unscrewing from the tool holder the fixing element, i.e. in most cases the fixing screw. Specifically in the case of small and difficultly accessible tool holders this constitutes an important advantage. Advantageously the fixing element can be located in captive manner on the tool holder, so that it cannot drop into the chip bin, where it is usually irretrievable. This solution also makes it possible to choose fixing elements other than screws, e.g. a cam-clamp fastener.
[0007] A further important advantage is obtained if the fixing element is operable for clamping and unclamping purposes from the side of the tool holder opposite to the cutting insert and preferably from both sides. It is consequently possible to loosen the cutting insert from the rear, particularly in that e.g. in the screw shank is provided an inner gripping surface (hexagonal recess, hexagonal socket head or the like). These internal key surfaces make it possible to apply a corresponding tool from the rear, because on the side where the cutting insert is fixed to the tool holder accessibility is usually impaired by the machine chuck.
[0008] The gripping head and the associated gripping surface can be substantially conical. As the slot width is preferably smaller than the transverse dimensions of the gripping head, despite the slot there is a self-centring of the cutting insert on tightening the fixing element.
[0009] The cutting insert preferably has at least one leg bounding the gap and which is bevelled towards the gap. If the cutting insert has a symmetrical construction, then the two legs bounding the gap give a wedge-shaped orienting surface, which cooperate with corresponding inclined surfaces on the tool holder to bring about a precise orientation of the cutting insert relative to the tool holder. This construction also ensures that in spite of the gap, even in the case of high forces acting on the cutting insert, the two fork-like legs do not have a widening tendency. They are held together by the corresponding stop faces on the holder in the same way as a clip or clamp. The cutting insert is preferably in the form of a reversing or flip plate and correspondingly has two facing blades, which can be brought into use by reversing the cutting insert on the tool holder. Thus, on both sides of its opening, the cutting insert has corresponding conical surfaces.
[0010] To ensure that the cutting insert is pressed with pretension onto the corresponding stop faces of the tool holder, the centre axis of the fixing element and the associated axis of the opening or the gripping surface provided thereon are so dimensioned in their distances or spacings from the stop or orienting surfaces that the cutting insert produces a force acting in the direction of the stop faces on clamping the fixing element. For this purpose the spacing of the gripping head centre axis from the stop face is somewhat smaller than the spacing between the centre axis of the corresponding gripping surface and the orienting surface. However, these are only fractions of millimetres, but which still ensure an automatic tightening.
[0011] The invention also provides a cutting insert for tools for machine working, in which the cutting insert has a slot connecting the opening to an outer edge of the cutting insert and whose width is no smaller than that of the shaft section. It preferably has a triangular configuration with a substantially central opening and a slot provided in one corner and preferably blades are provided at the two other corners.
[0012] The method for fixing to or removing from a tool holder a cutting insert proposed by the invention provides for the cutting insert in the loosening position of the fixing element to be moved over or removed from the shank section of the fixing element transversely to the extension thereof. The fixing element can be moved by a screwing action between the loosening and the clamping position and the loosening position can be secured against further loosening so as to render the fixing element captive.
[0013] These and further features can be gathered from the claims, description and drawings and the individual features, both singly and in the form of subcombinations, can be implemented in an embodiment of the invention and in other fields and can represent advantageous, independently protectable constructions for which protection is claimed here. The subdivision of the application into individual sections and the subheadings in no way restricts the general validity of the statements made thereunder.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Embodiments of the invention are described in greater detail hereinafter relative to the attached drawings, wherein show:
[0015] FIG. 1A side view of a tool according to the invention with a fixed cutting insert.
[0016] FIG. 2A corresponding side view with the cutting insert released from the tool holder.
[0017] FIG. 3A detail section through the tool holder with fitted, but not clamped cutting insert.
[0018] FIG. 4A representation corresponding to FIG. 3 with a clamped cutting insert.
[0019] FIG. 5A tool holder with a one-sided cutting insert with a significantly projecting blade.
[0020] FIG. 6A perspective view of a cutting insert.
[0021] FIG. 7A plan view.
[0022] FIG. 8A side view.
[0023] FIG. 9A front view of the blade of a cutting insert according to FIG. 6 .
[0024] FIG. 10A part-sectional plan view of a tool with a clamped and and 11 unclamped cutting insert.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0025] FIGS. 1 to 4 show a tool 11 in a greatly enlarged form. It is intended for use in universal machines or automatic lathes, where small and usually precision mechanical parts are to be finished in a single setting. This involves internal and external turning, grooving, threading and other operations, which terminate with the cutting off of the workpiece from a rod guided by the automatic chuck. All these operations are performed in automatically controlled manner on the machine, so that the latter operates completely automatically. For this purpose the machine has a complete register of different cutting tools, which can be provided in the form of a displaceable linear register or as a turret head. Each of these tools has a blade with a specific profile able to engage in a working manner in the workpiece. In accordance with the machine type for which they are intended, these tools are also known as “Swiss Tools”.
[0026] The tool 11 has a tool holder 12 and a cutting insert 13 . The tool holder is made steel, but in its shank 14 for clamping to the machine it is provided with a hole, which is filled by a hard metal bar 15 . In the manner described in the aforementioned DE 42 14 355 A, the latter also acts in a vibration-damping manner, which can be attributed to its material structure and particularly the high modulus of elasticity of hard metal.
[0027] At the opposite end of the tool holder a recess 16 is provided thereon and forms a receptacle for the cutting insert 13 . On said recess are provided two stop faces 17 , which are bevelled in such a way that they open to the centre of the recess. With an axis 18 at right angles to the tool holder a fixing element 19 in the form of a screw projects through there and is screwed into a thread 20 in the tool holder.
[0028] In the area carrying the cutting insert, the tool holder is provided with a laterally projecting projection 21 , in which the screw shank 22 is received in a deep depression 23 , also in the clamped state ( FIG. 4 ).
[0029] The fixing element 19 has a gripping head 24 with a conical gripping head surface 25 and an internal key surface 26 for a tightening key 27 . The key surface can be constructed in the manner of a hexagonal recess or a hexagonal socket head gripping surface. The gripping head is contracted somewhat towards the shank, but its external diameter is larger than the screw shank, including the thread provided thereon.
[0030] At the end of the screw shank 22 a circlip 28 is inserted in a groove and which in the loosening position of the fixing element 19 shown in FIG. 3 secures said element against a complete turning out from the thread 20 in that it strikes against the bottom surface 29 of the depression 23 .
[0031] The cutting insert 13 is in the form of a relatively thick, trapezoidal, small hard metal plate. In its centre is provided an opening 30 , which passes in circular manner about a centre axis 31 . The opening is provided with in each case a conical depression symmetrically towards both sides 32 of the cutting insert and as a result gripping surfaces 33 are formed, which are constructed with matching angle and diameter conditions for the gripping head surface 25 of the fixing element. A narrow, cylindrical opening section 34 is provided between the two conical gripping surfaces 33 .
[0032] A slot 36 passes from the short trapezoidal surface 35 of the cutting insert to the opening and its width is dimensioned in such a way that it fits over the screw shank. Its diameter is only slightly wider than the screw shank, i.e. between a few tenths and one or two millimetres wider. However, it is narrower than the external diameter of the gripping surface 33 to the extent that it cooperates with the gripping head 24 . Consequently it can centre in the conical gripping surface in the clamped state and is not drawn into the slot.
[0033] The cutting insert forms a triangular yoke, whose legs 37 to both sides of the opening have on their outer surface orienting faces 38 , whose angle and dimensions match the stop faces 17 .
[0034] The two outer edges of the trapezoidal yoke form the blades 39 of the cutting insert and which are ground or profiled in accordance with their intended use. As a result of the completely symmetrical construction the cutting insert can be used as a small reversing plate, so that in each case one of the two blades 39 can be engaged in a workpiece 40 .
[0035] The recess 16 in the tool holder has an inner stop face 41 with which the cutting insert 13 engages.
[0036] FIG. 5 shows a tool 11 , which is constructed for a cutting insert 13 having a relatively long and narrow blade 39 , which is e.g. suitable for cutting off a larger diameter tool piece. This cutting insert only has one blade and is consequently not reversed. Otherwise all the features of the previously described tool are provided, except for a somewhat different design of the orienting and stop faces 38 , 17 . The fixing element 19 is shown in section.
[0037] FIGS. 6 and 9 clearly show the design of the cutting insert according to the invention. Reference should be made to these drawings with regards to the precise design. It can be seen that the cutting insert is small, compact, but still very stable. The gripping and fixing surfaces are very large compared with the size and moment arms on which the cutting forces act and are close to the blades. The production thereof from a hard metal sintered profile or sintered part is easy, working by grinding being the only requirement. This is a particular advantage compared with conventional cutting inserts, which are provided with two screws. Apart from the fitting disadvantages in that case the cutting insert is relatively long, not very stable and consequently tends to vibrate.
[0038] FIGS. 10 and 11 show a tool 11 with a tool holder 12 and a cutting insert 13 in much the same way as FIG. 5 and in plan view. It is noteworthy that between the gripping head 24 of the fixing element 19 and the associated conical gripping surface 33 a conical, annular disk 50 is provided, whose shape and width are adapted to the gripping head surface and therefore also the corresponding gripping surface 33 of the cutting insert 13 . It acts as a washer and protects the gripping head surface 25 against damage by the edges of the slot 36 interrupting the gripping surface 33 . It is loose and can, as shown in FIG. 11 , be drawn off together with the gripping head 24 , so that the cutting insert can be removed upwards.
[0039] In the embodiment of the fixing element 19 (cap screw) and tightening key 37 shown in FIGS. 10 and 11 there is no need to provide on the screw shank 22 a circlip 28 in the form shown in FIG. 3 . The tightening key profiling 42 , 43 is a hexagonal socket head profile on the side, which is associated with the internal key surface 44 in the screw shank 22 , at a predetermined distance a from the end of the profiling 43 , is fixed a disk forming a stop 51 and is sufficiently large for it to be able to strike against the back 48 of the tool holder 12 when the screw 19 is loosened. Instead of being in the form of a ring mounted on the tightening key 27 , the stop 51 can also be formed by a sleeve or a corresponding thickening of the tightening key shank, which has the distance a from the end of the key surface 43 .
[0000] Method
[0040] The method for fixing or removing the cutting insert 13 on or from the tool holder can be seen in FIGS. 1 to 4 .
[0041] The fixing element is operated by means of the tightening key 27 . As can be seen in FIG. 3 , the latter has on one side a hexagonal socket head-like profiling 42 , which matches the larger, internal key surface 26 in the gripping head 24 and on the other side of its L-shaped, bent shank it has a key surface 43 of the same type, but with smaller dimensions and which matches the internal key surface 44 in the end face 45 of the screw shank 22 .
[0042] FIG. 3 shows the fixing element 19 in its loosening position where the gripping head 24 projects from the opening 30 and the gripping surfaces 25 , 33 are not in engagement with one another. The fixing element 19 is unscrewed from the tool holder 14 to such an extent that the circlip 28 strikes against the bottom surface 29 and consequently provides security against loss of the screw.
[0043] In the manner shown in FIG. 2 , the cutting insert can be extracted upwards in this position, i.e. transversely to the longitudinal extension of the tool holder 14 , in order to replace it by another screw or, after turning by 180ø, for reinsertion for using the opposite blade 39 .
[0044] Following insertion the fixing element is brought back into the gripping or clamping position by screwing in (considered from the gripping head) and this is shown in FIGS. 1 and 4 . In this position the gripping surface 32 engages on the gripping head surface 25 and presses the cutting insert with its one lateral face 32 against the stop face 41 . As a result of the conical gripping surface 33 the cutting insert is self-centred and, assisted by the axial displacement between the axes 18 and 31 of the fixing element and opening, is pressed with the orienting faces 38 against the stop faces 17 . Therefore the cutting insert is secured on the tool holder in its longitudinal position and orientation, as well as in its transverse orientation.
[0045] Gripping or clamping by the wedge-like orienting faces 38 in the corresponding wedge-shaped receptacle of the stop faces 17 also ensures that the forces exerted by the gripping head 24 and which act on the legs 37 , do not lead to a widening of the slot 36 . A corresponding, precisely ground cutting insert can consequently be reversed or replaced by another, corresponding cutting insert, without impairing the precise positioning of the blade relative to the workpiece 40 . Therefore the cutting insert can be replaced by an untrained person without the need for measuring or setting up activities and in particular without having to disassemble the tool holder 14 from the machine. This is inter alia made possible in that the fixing element 19 is accessible and operable from the back 48 of the tool holder opposite to the gripping head and cutting insert 13 through the insertion of the tightening key 27 in the key surface 44 .
[0046] FIGS. 10 and 11 show the tool with tightening keys applied from both sides. In practice, application only takes place from one side. FIG. 10 shows that the conical annular disk 50 is located between the gripping surface 33 and the gripping head surface 25 and consequently protects the latter against damage by seizing or a certain cutting action on the edges 52 (cf. FIGS. 6 and 8 ) of the cutting insert 13 . The annular disk can be rapidly replaced in that the fixing element 19 is completely unscrewed by means of the tightening key and its hexagonal socket head profiling 42 engaging in the gripping head.
[0047] As has been described hereinbefore, in practice the fixing element 19 is always screwed on and down from the tool holder back 48 . For this purpose the spacing a between the stop face 51 and the end of the tightening key profiling 43 is dimensioned in such a way that it is shorter than the thread 20 in tool holder 12 . Thus and as is shown in FIG. 10 , the tightening key 27 can engage in the corresponding, internal key surface 44 and turn the fixing screw 19 between the clamping position ( FIG. 10 ) and an opening position ( FIG. 11 ). However, before the fixing screw 19 completely drops out of the thread 20 , as a result of the stop 51 on the tool holder back 48 the tightening key 27 draws out of the gripping surface profiling 44 in the screw shank 22 , so that the screw cannot be further unscrewed and consequently does not drop out of the thread 20 . This creates automatic security against the loss of the fixing element 19 . | A tool for the machine working of workpieces is more particularly provided for universal machines, which automatically work very small workpieces by different lathe working operations. A cutting insert ( 13 ) can be fixed in a tool holder ( 14 ) by means of a fixing screw ( 19 ). The cutting insert ( 13 ) is constructed as a reversing plate and has two conical receptacles for the conical gripping head ( 25 ) of the fixing screw ( 19 ). This reversing plate has several use possibilities, such as grooving, plunge and turn, threading, front turn, back turn and cut off. The central opening ( 30 ) in the cutting insert is connected by means of a slot ( 36 ) to the narrower trapezoidal surface ( 35 ) of the cutting insert, the slot ( 36 ) being sufficiently wide to fit over the shank of the fixing screw ( 19 ). Thus, after loosening the fixing screw, the cutting insert can be removed laterally and correspondingly fitted again. The screw ( 19 ) is captive and can also be operated from the back ( 48 ) of the tool holder ( 14 ). | 1 |
DESCRIPTION
1. Technical Field
This invention relates generally to the field of obstetrics and gynecology and more particularly to the noninvasive prenatal diagnosis of a meconium state pregnancy.
2. Background Art
During gestation and prior to birth, the fetus, in a normal state pregnancy is continent. During its prenatal life, mucus, bile and epithelial cells build up in the fetus's colon. This buildup is known as "meconium". Meconium contains a large amount of bilirubin and its metabolites which is derived from the breakdown of fetal blood cells. In the normal pregnancy meconium is not excreted until after parturition; however, ongoing or transient stress can cause the fetus to expel meconium into the surrounding amniotic fluid. The incidence of meconium staining often increases with gestational age. This staining results in a "Meconium state pregnancy". The presence of meconium stained fluid is indicative of a need for more intensive early labor monitoring. Infants born with meconium staining have lower overall infant assessment scores than their peers born without meconium staining. Another danger associated with meconium staining is the risk of the infant inhaling meconium into its lungs at the time of birth. This results in "Meconium Aspiration Syndrome", a very severe form of pneumonia that often kills the infant or renders it a pulmonary cripple for life. Meconium aspiration syndrome is also a significant cause of cerebral palsy. Because of the lower infant assessment scores and the risk of meconium aspiration syndrome, infants born with meconium staining have a higher mortality and morbidity rate than infants born without meconium staining.
Currently meconium staining can be diagnosed only by direct visualization of the amniotic fluid. This would usually occur at the time the placental membranes rupture; an event which may not necessarily occur at an early enough stage of labor to allow the detection of meconium staining by that method to be of any practical value. Meconium can also be detected during an amniocentesis. This is an invasive procedure wherein a needle is inserted into the amniotic sac through the abdominal wall and an aliquot of amniotic fluid is withdrawn. This procedure is most often performed in order to perform certain prenatal genetic tests or protein assays. It is not performed for the sole purpose of meconium detection, and is not performed routinely. A diagnostic process that would allow a non-invasive means of detecting meconium staining in a term pregnancy is therefore needed. It is at least one object of this invention to provide a low risk non-invasive process for the detection of meconium stained amniotic fluid that could be performed at any stage of pregnancy. However, those skilled in the art will recognize that this invention could also be useful in the diagnosis of other prenatal conditions that result in the presence of increased porphyrin breakdown products in amniotic fluid.
Heretofore, various inventions have utilized the various qualities of bilirubin in order to quantify the amount of bilirubin in a fluid or to facilitate the remote gathering of fluorometric data. Known prior art methods are described in the following U.S. Pat No. 3,477,818 issued to Fried et al; U.S. Pat. No. 3,923,459 issued to Ertingshausen et al; U.S. Pat. No. 4,204,839 issued to Wu et al; and U.S. Pat. No. 4,412,005 issued to Wu. However, in light of the need for a noninvasive in vivo procedure, the prior art has the disadvantage that it relies either on wet/dry in vitro chemistry procedures or invasive in vivo processes, i.e. catheterization.
DISCLOSURE OF THE INVENTION
This invention is the first to consider the non-invasive in vivo detection of meconium in amniotic fluid. The invention is non-invasive in that the light is passed transcutaneously, transabdominally, transvaginally, transcervically or transamniotically. Due to the fact that different skin colors absorb light with different degrees of efficiency, the preferred embodiment would be transvaginally.
Because human tissue is capable of passing the excitation as well as the emission wavelengths characteristic of the fluorescent pigments contained in meconium with a minimum of attenuation, the excitation wavelength of bilirubin and other biological pigments can be passed through tissue and into the amniotic fluid. This light is absorbed by the fluorescent pigments of meconium, if present, and emitted at a slightly longer wavelength. This emission fluorescence can be filtered and focused into a receiving device, amplified and then displayed or analyzed. A positive readout would be indicative of the presence of meconium.
The means wherein this process would be accomplished would consist of an excitation light source and a detector. The excitation side would consist of a light source, a transmission device, a means of spectral isolation of the appropriate wavelengths for the excitation of the fluorescent pigment in question and a transparent patient-probe interface.
The above-mentioned detector would consist of a means of spectral isolation that would only allow light in the range of the emission band to pass through and would detect any fluorescence being emitted by the bilirubin pigments in the meconium. The emission side of the probe could also contain a second detector; The second detector would determine how much light is being scattered and reflected by the tissue. The detectors would consist of a means of isolating the appropriate wavelength of light, a photosensor, a means of transmitting a signal away from the sensor, an amplifier coupled with data processing circuitry and a readout device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the molecular structure of unconjugated bilirubin. The unconjugated form is the most prevalent form.
FIG. 2 shows the relative position of the gravid female and the fetus after lightening and during one possible method of examination.
FIG. 3 is an enlarged fragmented view of the encircled area in FIG. 2 designated at 3--3. It shows the placement of the probe in the preferred embodiment of the invention.
FIG. 4 shows the excitation spectra of meconium stained amniotic fluid (1:30 dil.) when the wavelength of emission is 515 nm.
FIG. 5 shows the emission spectra of meconium stained amniotic fluid (1:30 dil.) when the wavelength of excitation is 465 nm.
FIG. 6 is a representation of one possible configuration of the probe and uterine wall utilized by the invention.
FIG. 7 shows a diagrammatic view of the system utilized by the present invention.
BEST MOST FOR CARRYING OUT THE INVENTION
Bilirubin is a nitrogen containing organic compound (see FIG. 1) that is weakly fluorescent, i.e. it absorbs light of a particular wavelength and emits it at a slightly longer wavelength.
The present invention could detect meconium either transcutaneously, transabdominally, or transvaginally. The preferred embodiment would be transvaginally due to the effects different skin colors have on the efficiency with which skin absorbs light and the fact that the transvaginal route of detection reduces the amount of tissue that the light must pass through. A typical arrangement is illustrated at FIGS. 2 and 3. The examining physician's hand 30 introduces the probe 22 into the vagina 16 and places the probe 22 against the uterine wall 12. Light from the probe 22 is then passed through the uterine wall 12 and into the amniotic cavity 14 which is filled with amniotic fluid. As can be seen, by passing the light directly across the uterine wall 12, by directing the probe 22 through the vagina 16, the light does not have to pass through the abdominal muscles 13 and fatty tissues 15 thereby significantly reducing the amount of light attenuation due to tissue interference.
As illustrated at FIG. 6, a fiber optic 23 is used to carry the light beam which is passed through a spectral isolation means 24, which will be recognized by those skilled in the art to include filters, prisms, gratings and monochromatic lasers, used to spectrally isolate the excitation wavelengths; the light then passes through the transparent patient-probe interface 26 and across the tissue layer 12'. The thickness of the layer will vary depending upon which route of transmission the user chooses, i.e. transabdominal or transvaginal. The fluorescence that is emitted by the bilirubin passes through the tissue layer and into the probe where it is detected by photosensors 27 and 27.
As the light leaves fiberoptic 23, some of it will be reflected by the various layers. Most of this reflected light will be blocked by the further spectral isolation means 25, which will be recognized by those skilled in the art to include filters, prisms and gratings, used to isolate the emission wavelength. It is possible that some of this light will leak through the further spectral insulation means. The second detector shown as 29 will detect this reflected light and its wavelength will be electronically "subtracted" out of the amplified and analyzed signal so that the displayed signal is the spectra of the fluorescence.
As illustrated at FIG. 7, the signal generated by the detector(s) within probe 22 is then processed by the signal processing means 42. The output generated by said processing means is then displayed by the display device 44. The light source 40 could be incandescent, fluorescent, arc lamp, laser or any other suitable artificial light source. The beam could be continuous, interrupted, modulated or otherwise variable. The preferred embodiment of this invention would utilize an argon laser. The tissue that the light will be traveling through contains large amounts of hemoglobin. Hemoglobin absorbs light very efficiently. An argon laser emits light in the very narrow excitation range which is very close to the minimum absorption curve of hemoglobin's spectra. By use of an argon laser a minimum of light will be lost to hemoglobin absorption.
The excitation wave length of the bilirubin metabolites and other biological pigments in meconium is in the range of 300 nm to 525 nm. (see FIG. 4). The method of isolating this band of light is best accomplished with an interference filter selected for this range when monochromatic laser light is not used. Other acceptable means would include, but not be limited to, equivalent bandpass filters, prisms, or gratings. The emission wave length of the pigments in meconium is 460 nm to 610 nm as illustrated at FIG. 5. The method of isolating this band of light is best accomplished with an interference filter selected for this wavelength. Other acceptable means would include, but not be limited to, equivalent bandpass filters, prisms, or gratings.
Due to the fact that there may be some leakage of reflected excitation light through the emission detector filter, a second detector, as illustrated at FIG. 6, may be utilized to determine the amount of reflected excitation light. This information will allow the formulation of an index that will allow a determination that the light being received, amplified and displayed is actually emitted fluorescence.
The drawings and descriptions herein are only intended to describe one possible means of practicing this invention. They are not intended in any way to limit this invention. Those skilled in the art will readily recognize the utility of this invention in diagnosing other prenatal conditions that result in the buildup of porphyrin breakdown products within the amniotic fluid. | This invention describes a process for the diagnosis of meconium stained amniotic fluid. Meconium staining is often the result of ongoing or transient fetal distress or prolonged gestation. This process involves the non-invasive illumination of the amnion with light of a specific wavelength and detecting the fluorescence of certain biological pigments contained within the meconium. The process uses a source of light and a means of selecting the desired wavelength of light, directing the light to the target area, retrieving the fluorescence, converting the fluorescent emission to an electrical signal, amplifying the signal and analyzing the signal with a data processing unit. | 0 |
TECHNICAL FIELD
[0001] The present invention relates to a novel zinc complex useful as a catalyst for various reactions including transesterification reaction and the like.
BACKGROUND ART
[0002] A lot of multinuclear metal complexes having multiple metal nuclei in each molecule have been developed as highly active catalysts. Of these catalysts, a catalyst comprising a trifluoroacetate-bridged tetranuclear zinc cluster complex containing four zinc ions in a molecule is an excellent catalyst which promotes various reactions such as transesterification reaction, hydroxy group-selective acylation reaction in the presence of an amino group, acetylation reaction, deacetylation reaction, and amidation reaction in an environmentally friendly manner with less by-products (for example, Japanese Patent Application Publication No. 2009-185033, Domestic Re-publication of PCT International Publication No. 2009-047905, Japanese Patent Application Publication No. 2011-079810, J. Org. Chem. 2008, 73, 5147, J. Am. Chem. Soc. 2008, 130, 2944, Synlett 2009, 10, 1659, and Chem, Eur, J. 2010, 16, 11567).
[0003] The tetranuclear zinc cluster catalyst Zn 4 (OCOCF 3 ) 6 O is an excellent catalyst, but it cannot be said that the activity of the catalyst is sufficient. As described in ACS Catal, 2011, 1, 1178, some reports say that the activity is improved to some degree by adding a nitrogen-containing aromatic compound such as DMAP (4-dimethylaminopyridine) or NMI (N-methylimidazole) to improve the activity; however, there still remains a problem of the need for an excess of the additive relative to the catalyst. Moreover, since the tetranuclear zinc cluster catalyst gradually decomposes and loses its activity with the progress of the reaction, the catalyst is difficult to recover and reuse.
SUMMARY OF INVENTION
[0004] An object of the present invention is to provide a novel zinc complex which is highly active as a catalyst, has stability, and further is easy to recover and reuse.
[0005] The present inventors have conducted intensive study, and consequently found that a zinc complex which achieves the above-described object can be obtained by mixing a zinc carboxylate compound with a bidentate ligand in which two imidazole groups are connected by a suitable linker.
[0006] The present invention relates to the following [1] to [10].
[0000] [1] A zinc complex with an octahedral geometry, comprising a repeating unit represented by the following general formula (I):
[0000]
[0007] wherein L represents a linker moiety, and R 1 represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s).
[0000] [2] A zinc complex obtained by reacting
[0008] a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) with
[0009] a compound represented by general formula (V) in an amount of 2 mole equivalents to zinc atoms of the zinc carboxylate compound:
[0000] Zn(OCOR 1a ) 2 .x H 2 O (III),
[0010] wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
[0000] Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n (IV),
[0011] wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and
[0000]
[0012] wherein L represents a linker moiety.
[0000] [3] The zinc complex according to the above-described [1] or [2], wherein
[0013] the linker L is represented by the following general formula (II):
[0000]
[0014] wherein X represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group, an optionally substituted allyl group, or a substituted amino group.
[0000] [4] A catalyst comprising the zinc complex according to any one of the above-described [1] to [3].
[5] A method for acylating a hydroxy group, comprising
[0015] reacting a carboxylic acid or an ester thereof in the presence of the catalyst according to the above-described [4].
[0016] [6] A method for converting a hydroxy group to a carbonate, comprising
[0017] reacting a carbonate ester in the presence of the catalyst according to the above-described [4].
[0018] [7] A method for deacylating a carboxylate ester, comprising
[0019] deacylating the carboxylate ester in the presence of the catalyst according to the above-described [4].
[0020] [8] A method for acylating a hydroxy group with a carboxylic acid or an ester thereof, comprising
[0021] forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to an acylation reaction system:
[0000] Zn(OCOR 1a ) 2 .X H 2 O (III),
[0022] wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
[0000] Zn 4 O(OCOR 1b ) 6 R 1b COOH) n (IV),
[0023] wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and
[0000]
[0024] wherein L represents a linker moiety.
[0000] [9] A method for converting a hydroxy group to a carbonate with a carbonate ester, comprising
[0025] forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to a carbonate formation reaction system:
[0000] Zn(OCOR 1a ) 2 .x H 2 O (III),
[0026] wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
[0000] Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n (IV),
[0027] wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and
[0000]
[0028] wherein L represents a linker moiety.
[0000] [10] A method for deacylating a carboxylate ester, comprising
[0029] forming a catalyst by adding a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) together with a compound represented by general formula (V) to a deacylation reaction system:
[0000] Zn(OCOR 1a ) 2 .x H 2 O (III),
[0030] wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
[0000] Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n (IV),
[0031] wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and
[0000]
[0032] wherein L represents a linker moiety.
[0000] [11] A method for producing a zinc complex represented by general formula (I), comprising
[0033] reacting a zinc carboxylate compound represented by general formula (III) or a zinc carboxylate compound represented by general formula (IV) with
[0034] a compound represented by general formula (V) in an amount of 2 mole equivalents to zinc atoms of the zinc carboxylate compound:
[0000]
[0035] wherein L represents a linker moiety, and R 1 represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s);
[0000] Zn(OCOR 1a ) 2 .x H 2 O (III),
[0036] wherein R 1a represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater;
[0000] Zn 4 O(OCOR 1b ) 6 (R 1b COOH) n (IV),
[0037] wherein R 1b represents an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1; and
[0000]
[0038] wherein L represents a linker moiety.
[0039] The zinc complex represented by general formula (I) of the present invention is highly active as a catalyst, has stability, and further is easy to recover and reuse. Hence, this zinc complex enables reactions with good environmental friendliness, good handleability, and further good economical efficiency. Moreover, the zinc complex of the present invention is useful as a catalyst for synthesis of intermediates for pharmaceutical and agricultural chemicals, functional materials, and structural materials, and the like.
BRIEF DESCRIPTION OF DRAWINGS
[0040] FIG. 1 shows a result of X-ray crystallography of a zinc complex A with an octahedral geometry of the present invention.
[0041] FIG. 2 shows a result of X-ray crystallography of a zinc complex B with a tetrahedral geometry.
[0042] FIG. 3 shows a result of X-ray crystallography of a zinc complex C with an octahedral geometry of the present invention.
[0043] FIG. 4 shows an MS measurement result of the zinc complex A.
[0044] FIG. 5 shows an MS measurement result of the zinc complex C.
DESCRIPTION OF EMBODIMENTS
[0045] Hereinafter, the present invention will be described specifically.
[0046] A zinc complex of the present invention is a zinc complex with an octahedral geometry comprising a repeating unit represented by the following general formula (I):
[0000]
[0047] In general formula (I), L represents a linker moiety. L represents a divalent group of atoms which bridges nitrogen atoms on one side of two imidazole groups.
[0048] The divalent group of atoms may be linear or branched. The divalent group of atoms may be a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, a linear or branched alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylalkylene group having 8 to 20 carbon atoms, a heteroalkylene group having 1 to 20 carbon atoms, a heteroarylene group having 2 to 20 carbon atoms, a heteroarylalkylene group having 3 to 20 carbon atoms, a phenylenevinylene group, a polyfluorene diyl group, a polythiophene diyl group, a dialkylsilane diyl group, or a diarylsilane diyl group. These divalent groups of atoms optionally have substituents. Moreover, any two or more of these groups of atoms may be employed in combination.
[0049] Of these divalent groups of atoms, preferred are optionally substituted alkylene groups, optionally substituted arylene groups, optionally substituted heteroalkylene groups, optionally substituted arylalkylene groups, and optionally substituted heteroarylalkylene groups which may be linear or branched. More preferred are optionally substituted arylalkylene groups and optionally substituted heteroarylalkylene groups which may be linear or branched, and further preferred are optionally substituted arylalkylene groups which may be linear or branched.
[0050] Examples of the linear or branched alkylene group having 1 to 20 carbon atoms include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, and hexadecamethylene groups; branched alkylene groups such as methylethylene, methylpropylene, ethylethylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 1-ethylpropylene, 2-ethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1-propylpropylene, 2-propylpropylene, 1-methyl-1-ethylpropylene, 1-methyl-2-ethyl-propylene, 1-ethyl-2-methyl-propylene, 2-methyl-2-ethyl-propylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 2-ethylbutylene, methylpentylene, ethylpentylene, methylhexylene, methyiheptylene, methyloctylene, methylnonylene, methyldecylene, methylundecylene, methyldodecylene, methyltetradecylene, and methyloctadecylene groups; and the like. Preferred alkylene groups include pentamethylene, hexamethylene, heptamethylene, octamethylene, and nonamethylene.
[0051] These divalent groups of atoms may have substituents described later.
[0052] Cycloalkylene groups having 3 to 8 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, cyclohexenylene, 1,2-cyclohexylenebis(methylene), 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis, and the like. Preferred cycloalkylene groups include a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclohexenylene, 1,2-cyclohexylenebis(methylene), 1,3-cyclohexylenebis(methylene), and 1,4-cyclohexylenebis.
[0053] These divalent groups of atoms may have substituents described later.
[0054] Examples of the linear or branched alkenylene group having 2 to 20 carbon atoms include vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene groups, and the like. These divalent groups of atoms may have substituents described later.
[0055] Examples of the cycloalkenylene group having 3 to 20 carbon atoms include cyclopropenylene, cyclobutenylene, cyclopentenylene, cyclohexenylene, and cyclooctenylene groups, and the like. These divalent groups of atoms may have substituents described later.
[0056] Examples of the linear or branched alkynylene group having 2 to 20 carbon atoms include ethynylene, propynylene, 3-methyl-1-propynylene, butynylene, 1,3-butadiynylene, 2-pentynylene, 2-pentynylene, 2,4-pentadiynylene, 2-hexynylene, 1,3,5-hexatriynylene, 3-heptynylene, 4-octynylene, 4-nonynylene, 5-decynylene, 6-undecynylene, and 6-dodecynylene groups, and the like. These divalent groups of atoms may have substituents described later.
[0057] Examples of the arylene group having 6 to 20 carbon atoms include phenylenes (o-phenylene, m-phenylene, and p-phenylene), biphenylene, naphthylene, binaphthylene, anthracenylene, and phenanthrylene groups, and the like. These divalent groups of atoms may have substituents described later.
[0058] Arylalkylene groups having 8 to 20 carbon atoms include those having a structure of -alkylene-arylene-alkylene-, and preferred specific examples include those having —CH 2 —Z—CH 2 — (where Z is a divalent group derived from benzene, naphthalene, bisphenyl, or diphenylmethane), for example, phenylenebis(methylenes) (1,2-phenylenebis(methylene), 1,3-phenylenebis(methylene), and 1,4-phenylenebis(methylene)), naphthalenebis(methylene), bisphenylenebis(methylene), and the like. Further preferred is 1,3-phenylenebis(methylene). These divalent groups of atoms may have substituents described later.
[0059] The heteroalkylene group having 1 to 20 carbon atoms means a group which is the same as the above-described alkylene group, except that one or more, preferably one to five of the carbon atoms in the main chain of the alkylene group are substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Examples thereof include oxa (or thia) alkylene, dioxa (or dithia) alkylene, alkyleneoxy, alkylenethio, alkylenedioxy, alkylenedithio, azaalkylene, diazaalkylene, phosphaalkylene, diphosphaalkylene, and the like. These divalent groups of atoms may have substituents described later.
[0060] The heteroarylene group having 2 to 20 carbon atoms means a group which is the same as the above-described arylene group, except that one or more, preferably one to five of the carbon atoms in the arylene group are substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Specific examples of the heteroarylene group include divalent groups derived from phenanthrene, pyrrole, pyrazine, pyridine, pyrimidine, indoline, isoindoline, quinoline, isoquinoline, quinoxaline, carbazole, phenylcarbazole, phenanthridine, acridine, furan, benzofuran, isobenzofuran, dibenzofuran, phenyldibenzofuran, diphenyldibenzofuran, thiophene, phenylthiophene, diphenylthiophene, benzothiophene, dibenzothiophene, phenylbenzothiophene, diphenylbenzothiophene, phenyldibenzothiophene, benzothiazole, and the like. Preferred are divalent groups derived from furan, quinoline, isoquinoline, and phenylcarbazole. These divalent groups of atoms may have substituents described later.
[0061] The heteroarylalkylene group having 3 to 20 carbon atoms means a group which is the same as the above-described arylalkylene group, except that one or more, desirably, one to five of the carbon atoms in the arylalkylene group are substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Preferred examples include those having a structure of —CH 2 —Z—CH 2 — (where Z is a divalent group derived from furan, pyrrole, thiophene, pyridine, pyrazole, or imidazole). These divalent groups of atoms may have substituents described later.
[0062] The divalent groups of atoms including the phenylenevinylene group, the polyfluorene diyl group, the polythiophene diyl group, the dialkylsilane diyl group, and the diarylsilane diyl group may have substituents described later.
[0063] Examples of substituents which may be present in the divalent group of atoms represented by L include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aliphatic heterocyclic groups, aromatic heterocyclic groups, alkoxy groups, alkylenedioxy groups, aryloxy groups, aralkyloxy groups, heteroaryloxy groups, acyl groups, substituted amino groups (for example, alkyl-substituted amino groups, aryl-substituted amino groups, aralkyl-substituted amino groups, acyl-substituted amino groups, alkoxycarbonyl-substituted amino groups, and the like), alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, sulfo groups, cyano groups, nitro groups, halogenated alkyl groups, halogen atoms, and the like.
[0064] The alkyl groups may be linear, branched, or cyclic, and examples thereof include alkyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples thereof include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, 2-butyl groups, isobutyl groups, tert-butyl groups, n-pentyl groups, 2-pentyl groups, tert-pentyl groups, 2-methylbutyl groups, 3-methylbutyl groups, 2,2-dimethylpropyl groups, n-hexyl groups, 2-hexyl groups, 3-hexyl groups, 2-methylpentyl groups, 3-methylpentyl groups, 4-methylpentyl groups, 2-methylpentan-3-yl groups, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, and the like.
[0065] The alkenyl groups may be linear or branched, and examples thereof include alkenyl groups having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. Specific examples thereof include vinyl groups, 1-propenyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, 1-pentenyl groups, 2-pentenyl groups, hexenyl groups, and the like.
[0066] The alkynyl groups may be linear or branched, and examples thereof include alkynyl groups having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. Specific examples thereof include ethynyl groups, 1-propynyl groups, 2-propynyl groups, 1-butynyl groups, 3-butynyl groups, pentynyl groups, hexynyl groups, and the like.
[0067] Examples of the aryl groups include aryl groups having 6 to 14 carbon atoms, and specific examples thereof include phenyl groups, naphthyl groups, anthryl groups, phenanthrenyl groups, biphenyl groups, and the like.
[0068] Examples of the aliphatic heterocyclic groups include 5- to 8-membered, preferably 5- or 6-membered monocyclic aliphatic heterocyclic groups having 2 to 14 carbon atoms and containing at least one, preferably one to three heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms and aliphatic heterocyclic groups obtained by condensation of 5- to 8-membered, preferably 5 to 6-membered monocyclic aliphatic heterocycles. Specific examples of the aliphatic heterocyclic groups include 2-oxopyrrolidino groups, piperidino groups, piperazinyl groups, morpholino groups, tetrahydrofuryl groups, tetrahydropyranyl groups, tetrahydrothienyl groups, perhydronaphthyl groups, and the like.
[0069] Examples of the aromatic heterocyclic groups include 5- to 8-membered, preferably 5- or 6-membered monocyclic aromatic heterocyclic groups having 2 to 15 carbon atoms and containing at least one, preferably one to three heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms, and aromatic heterocyclic groups obtained by condensation of 5- to 8-membered, preferably 5 to 6-membered monocycles. Specific examples thereof include pyrrolyl groups, furyl groups, thienyl groups, pyridyl groups, pyrimidyl groups, pyrazyl groups, pyridazyl groups, pyrazolyl groups, imidazolyl groups, oxazolyl groups, thiazolyl groups, indolyl groups, benzofuryl groups, benzothienyl groups, quinolyl groups, isoquinolyl groups, quinoxalyl groups, phthalazyl groups, quinazolyl groups, naphthyridyl groups, cinnolyl groups, benzoimidazolyl groups, benzoxazolyl groups, benzothiazolyl groups, tetrahydronaphthyl groups, and the like.
[0070] The alkoxy groups may be linear, branched, or cyclic, and examples thereof include alkoxy groups having 1 to 6 carbon atoms. Specific examples thereof include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, 2-butoxy groups, isobutoxy groups, tert-butoxy groups, n-pentyloxy groups, 2-methylbutoxy groups, 3-methylbutoxy groups, 2,2-dimethylpropyloxy groups, n-hexyloxy groups, 2-methylpentyloxy groups, 3-methylpentyloxy groups, 4-methylpentyloxy groups, 5-methylpentyloxy groups, cyclohexyloxy groups, and the like.
[0071] Examples of the alkylenedioxy groups include alkylenedioxy groups having 1 to 3 carbon atoms, and specific examples thereof include methylenedioxy groups, ethylenedioxy groups, propylenedioxy groups, and the like.
[0072] Examples of the aryloxy groups include aryloxy groups having 6 to 14 carbon atoms, and specific examples thereof include phenyloxy groups, naphthyloxy groups, anthryloxy groups, benzyloxy groups, and the like.
[0073] Examples of the aralkyloxy groups include aralkyloxy groups having 7 to 12 carbon atoms, and specific examples thereof include benzyloxy groups, 2-phenylethoxy groups, 1-phenylpropoxy groups, 2-phenylpropoxy groups, 3-phenylpropoxy groups, 1-phenylbutoxy groups, 2-phenylbutoxy groups, 3-phenylbutoxy groups, 4-phenylbutoxy groups, 1-phenylpentyloxy groups, 2-phenylpentyloxy groups, 3-phenylpentyloxy groups, 4-phenylpentyloxy groups, 5-phenylpentyloxy groups, 1-phenylhexyloxy groups, 2-phenylhexyloxy groups, 3-phenylhexyloxy groups, 4-phenylhexyloxy groups, 5-phenylhexyloxy groups, 6-phenylhexyloxy groups, and the like.
[0074] Examples of the heteroaryloxy groups include heteroaryloxy groups having 2 to 14 carbon atoms and containing at least one, preferably one to three heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms. Specific examples thereof include 2-pyridyloxy groups, 2-pyrazyloxy groups, 2-pyrimidyloxy groups, 2-quinolyloxy groups, and the like.
[0075] The acyl groups may be linear, branched, or cyclic, and examples thereof include acyl groups having 2 to 10 carbon atoms. Specific examples thereof include acetyl groups, propanoyl groups, butyryl groups, pivaloyl groups, benzoyl groups, and the like.
[0076] The alkoxycarbonyl groups may be linear, branched, or cyclic, and examples thereof include alkoxycarbonyl groups having 2 to 19 carbon atoms. Specific examples thereof include methoxycarbonyl groups, ethoxycarbonyl groups, n-propoxycarbonyl groups, isopropoxycarbonyl groups, n-butoxycarbonyl groups, tert-butoxycarbonyl groups, pentyloxycarbonyl groups, hexyloxycarbonyl groups, 2-ethylhexyloxycarbonyl groups, lauryloxycarbonyl groups, stearyloxycarbonyl groups, cyclohexyloxycarbonyl groups, and the like.
[0077] Examples of the aryloxycarbonyl groups include aryloxycarbonyl groups having 7 to 20 carbon atoms. Specific examples thereof include phenoxycarbonyl groups, naphthyloxycarbonyl groups, and the like. Examples of the aralkyloxycarbonyl groups include aralkyloxycarbonyl groups having 8 to 15 carbon atoms, and specific examples thereof include benzyloxycarbonyl groups, phenylethoxycarbonyl groups, 9-fluorenylmethyloxycarbonyl, and the like.
[0078] Examples of the aralkyloxycarbonyl groups include aralkyloxycarbonyl groups having 8 to 15 carbon atoms, and specific examples thereof include benzyloxycarbonyl groups, phenylethoxycarbonyl groups, 9-fluorenylmethyloxycarbonyl groups, and the like.
[0079] The substituted amino groups include amino groups in which one or two hydrogen atoms are substituted with substituents such as the above-described alkyl groups, the above-described aryl groups, and protective groups for amino group. As the protective groups, any groups used as amino-protecting groups can be used (see, for example, “PROTECTIVE GROUPS IN ORGANIC SYNTHESIS THIRD EDITION (JOHN WILEY & SONS, INC. (1999))). Specific examples of the amino-protecting groups include aralkyl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, and the like.
[0080] Specific examples of the amino groups substituted by an alkyl group(s) include mono- or di-alkylamino groups such as N-methylamino groups, N,N-dimethylamino groups, N,N-diethylamino groups, N,N-diisopropylamino groups, and N-cyclohexylamino groups.
[0081] Specific examples of the amino groups substituted by an aryl group(s) include mono- or di-arylamino groups such as N-phenylamino groups, N-(3-tolyl)amino groups, N,N-diphenylamino groups, N,N-di(3-tolyl)amino groups, N-naphthylamino groups, and N-naphthyl-N-phenylamino groups.
[0082] Specific examples of the amino groups substituted by an aralkyl group(s), i.e., amino group-substituted by aralkyl groups include mono- or di-aralkylamino groups such as N-benzylamino groups and N,N-dibenzylamino groups.
[0083] Specific examples of the amino groups substituted by an acyl group(s) include formylamino groups, acetylamino groups, propionylamino groups, pivaloylamino groups, pentanoylamino groups, hexanoylamino groups, benzoylamino groups, and the like.
[0084] Specific examples of the amino groups substituted by an alkoxycarbonyl group(s) include methoxycarbonylamino groups, ethoxycarbonylamino groups, n-propoxycarbonylamino groups, n-butoxycarbonylamino groups, tert-butoxycarbonylamino groups, pentyloxycarbonylamino groups, hexyloxycarbonylamino group, and the like.
[0085] Specific examples of the amino groups substituted by an aryloxycarbonyl group(s) include phenoxycarbonylamino groups, naphthyloxycarbonylamino groups, and the like.
[0086] Specific examples of the amino groups substituted by an aralkyloxycarbonyl group(s) include benzyloxycarbonylamino groups and the like.
[0087] The halogenated alkyl groups include alkyl groups having 1 to 4 carbon atoms in which hydrogen atoms are substituted with halogen atoms described later, and examples thereof include fluoromethyl groups, difluoromethyl groups, trifluoromethyl groups, trichloromethyl groups, and the like.
[0088] The halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like.
[0089] L is preferably an optionally substituted 1,3-phenylenebis(methylene) group represented by general formula (II). In the formula, X represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group, an optionally substituted allyl group, or a substituted amino group. These groups are the same as the groups described above. The substituted amino group may be an amino group in which two hydrogen atoms are substituted with substituents such as any ones of the above-described alkyl groups, the above-described aryl groups, protective groups for amino group, and the like. The protective groups are the same as those of the above-described substituted amino groups:
[0000]
[0090] Representative examples of the compound represented by general formula (I) are the following compounds (2-1) to (2-12) shown below.
[0000]
[0091] The zinc complex represented by general formula (I) can be obtained by reacting a compound represented by general formula (V) (ligand):
[0000]
[0092] wherein L represents a linker moiety, with
[0093] the general formula (III):
[0000] Zn(OCOR 1a ) 2 .x H 2 O (III),
[0094] wherein R 1a represents a zinc carboxylate compound represented by an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and x represents any number of 0 or greater, or
[0095] the general formula (IV):
[0000] Zn 4 O(OCOR 1b ) 6 R 1b COOH) n (IV),
[0096] wherein R 1b represents a zinc carboxylate compound represented by an alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s), and n represents 0 to 1.
[0097] Examples of the alkyl group having 1 to 4 carbon atoms and optionally having a halogen atom(s) include a trichloromethyl group; a tribromomethyl group; perfluoroalkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group; and the like. Of these groups, a preferred group is a trifluoromethyl (CF 3 ) group.
[0098] x represents any number of 0 or greater, and is preferably in the range from 0 to 8, and further preferably in the range from 0 to 3.
[0099] By single-crystal X-ray crystallography, the obtained zinc complex was identified as a crystal in the form of an infinite chain in which the bonding extend continuously in a one-dimensional direction or two-dimensional directions with an octahedral geometry in which four nitrogen atoms on one side of imidazole groups serving as the ligand are coordinated to one zinc atom, and two carboxylate groups OCOR 1a or OCOR 1b are coordinated to the zinc atom with trans configuration or cis configuration.
[0100] It should be noted that the complex with an octahedral geometry can be obtained when 2 mole equivalents of the ligand is reacted with zinc atoms of the zinc carboxylate compound serving as the raw material. In contrast, when the ligand is 1 equivalent to zinc atoms of the zinc carboxylate compound, a zinc complex with a tetrahedral geometry is obtained, and the zinc complex with a tetrahedral geometry does not have catalytic activity.
[0101] Regarding solvents used for the production of the zinc complex of the present invention, solvents which do not affect the formation of the zinc complex of the present invention can be used. Solvents capable of dissolving the zinc carboxylate compound and the ligand can be used. For example, tetrahydrofuran (THF), benzene, toluene, xylene, hexane, heptane, octane, or the like can be used. Preferred are solvents such as toluene, xylene, and THF, and THF is more preferable. In addition, the reaction can also be conducted as a solventless reaction.
[0102] The reaction temperature is preferably at or above a temperature at which the zinc carboxylate compound and the ligand can be dissolved, and is 30° C. to 250° C., and more preferably 30° C. to 150° C.
[0103] The reaction time is not particularly limited, and the reaction can be conducted in approximately 1 to 45 hours, in general, and preferably in about 2 to 24 hours.
[0104] In most cases, the zinc complex obtained during the reaction is insoluble in the solvent, and precipitates. For this reason, after completion of the reaction, the zinc complex can be obtained by filtration or the like. In a case where the zinc complex is dissolved in the reaction solution or other cases, the zinc complex may be taken out by evaporation of the solvent followed by drying.
[0105] The zinc complex represented by general formula (I) of the present invention obtained under the above-described conditions is stable in the air, and is more stable than the zinc trifluoroacetate tetranuclear cluster complexes which are described in Japanese Patent Application Publication No. 2009-185033, Domestic Re-publication of PCT International Publication No. 2009-047905, and Japanese Patent Application Publication No. 2011-079810, and which are unstable in the air because of their high hygroscopicity. However, it is preferable to handle the zinc complex of the present invention in the presence of inert gas in which the amount of water is small. The inert gas is, preferably, nitrogen, argon, or the like.
[0106] When the zinc complex of the present invention is used as a catalyst, the zinc complex prepared in the presence of a suitable solvent (for example, THF) in advance as described above may be added as a catalyst to the reaction system, or the reaction may be conducted by adding the raw materials, namely, the zinc carboxylate compound represented by general formula (III) or (IV) and the compound represented by general formula (V) (ligand) as a catalyst to the reaction system (in-situ method).
[0107] The zinc complex of the present invention enables a selective acylation reaction of or a selective carbonate formation reaction from an alcoholic hydroxy group in a case where a nucleophilic functional group such as an amino group and an alcoholic hydroxy group are simultaneously present in a reaction system.
[0108] The case where a nucleophilic functional group such as an amino group and an alcoholic hydroxy group are simultaneously present in a reaction system may be a case of a compound having the amino group and the alcoholic hydroxy group in a single molecule, or may be a case of different compounds. The compound having an amino group and an alcoholic hydroxy group in a single molecule may be an amino alcohol. Meanwhile, the case where the compound having an amino group and the compound having an alcoholic hydroxy group are different may be a case where an amine and an alcohol are simultaneously present in the reaction system.
[0109] The amino group may be a primary amino group or a secondary amino group. Meanwhile, the alcoholic hydroxy group may be any one of a primary hydroxy group, a secondary hydroxy group, or a tertiary hydroxy group. The amino alcohol is not particularly limited, as long as the amino alcohol is a compound having an amino group and an alcoholic hydroxy group. Examples of the amino alcohol include open-chain, branched, cyclic, or condensed-cyclic and aliphatic or aromatic amino alcohols and the like.
[0110] The zinc complex of the present invention enables a carbonate formation reaction from a carbonate ester and a compound having an alcoholic hydroxy group. The carbonate ester used in this reaction is a generic term for compounds obtainable by substituting one or two of the two hydrogen atoms of carbonic acid H 2 CO 3 with alkyl or aryl groups. From the viewpoint of handling, compounds in which two hydrogen atoms are substituted are preferable. As the carbonate ester, a dialkyl carbonate or a diaryl carbonate is used. Preferred specific examples of the carbonate ester used include dimethyl carbonate, diethylmethyl carbonate, methyl ethyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, and diphenyl carbonate. Of these carbonate esters, dimethyl carbonate is preferable.
[0111] Compounds having an alcoholic hydroxy group include compounds which are linear or cyclic aliphatic hydrocarbons having one, two, or multiple hydroxy groups. In addition, as the compounds having two or more hydroxy groups, cyclic carbonates can be obtained by, for example, reacting a diol compound and a carbonate ester by using the present catalyst.
[0112] The zinc complex of the present invention enables a deacylation reaction of a compound having an ester group. The compound having an ester group used in this reaction may be an aliphatic carboxylate ester, an aromatic carboxylate ester, or the like. The ester may be an ester derived from a monocarboxylic acid or a polycarboxylic acid.
[0113] Compounds having an ester group used in this reaction include alkyl esters such as methyl esters, ethyl esters, propyl esters, butyl esters, hexyl esters, and octyl esters; aryl esters such as phenyl esters, biphenyl esters, and naphthyl esters; aralkyl esters such as benzyl esters and 1-phenethyl esters; and the like of carboxylic acids described below. Preferred are methyl esters of the carboxylic acids described below.
[0114] The aliphatic carboxylic acid may be a monocarboxylic or polycarboxylic acid having 2 to 30 carbon atoms. Specific examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, propanedicarboxylic acid, butanedicarboxylic acid, hexanedicarboxylic acid, sebacic acid, acrylic acid, and the like.
[0115] In addition, these aliphatic carboxylic acids may be substituted by substituents. The substituents include alkyl groups, alkoxy groups, halogen atoms, amino groups, aryl groups, heteroaryl groups, aralkyl groups, silyloxy groups, hydroxy groups, and the like.
[0116] The aromatic carboxylic acid may be benzoic acid, naphthalenecarboxylic acid, pyridinecarboxylic acid, quinolinecarboxylic acid, furancarboxylic acid, thiophenecarboxylic acid, or the like.
[0117] In addition, these aromatic carboxylic acids may be substituted by any of the above-described alkyl groups, alkoxy groups, halogen atoms, amino groups, aryl groups, heteroaryl groups, aralkyl groups, hydroxy groups, and the like.
[0118] The amount of the zinc complex used as a catalyst in each reaction of the present invention is not particularly limited, but is generally the ratio of zinc atoms is 0.001 to 0.9 mol, more preferably 0.001 to 0.3 mol, further preferably 0.001 to 0.1 mol relative to 1 mol of a raw material.
[0119] Each reaction is conducted in a solvent, in general. Specific examples of the solvent include, but are not particularly limited to, aromatic solvents such as toluene, xylene, and benzene chloride; aliphatic hydrocarbon solvents such as hexane, heptane, and octane; ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, and 1,4-dioxane; amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); and the like. In addition, when the substrate used is a liquid, and the solubility of the zinc complex in the substrate is high, it is not necessary to use a solvent.
[0120] Various reactions using the zinc complex of the present invention as a catalyst can be conducted in the air or in an inert gas atmosphere of nitrogen gas, argon gas, or the like.
[0121] The reaction time is not particularly limited, and in general, the reaction can be conducted in approximately 1 to 45 hours, and preferably about 6 to 18 hours.
[0122] The reaction temperature is not particularly limited, and the reaction is conducted at room temperature to approximately 180° C., preferably 50 to 150° C., more preferably approximately 80 to 150° C. These conditions may be changed, as appropriate, according to the kinds and the amounts of the raw material used and the like.
[0123] The zinc complex of the present invention is dissolved during a reaction at high temperature. However, when the temperature is cooled to room temperature after completion of the reaction, the zinc complex is precipitated again as a solid. For this reason, the zinc complex can be easily recovered by filtration. It has been found that the recovered zinc complex has the same structure as that before the reaction, and the catalytic activity is not lowered even when the zinc complex is reused repeatedly.
[0124] Another technique for the recovery and reuse other than the filtration is as follows. Specifically, in a case where the substrate and the target product have low-boiling points, the reaction liquid is directly concentrated after completion of the reaction, so that the catalyst (zinc complex) can be easily recovered and reused.
[0125] As described above, the catalyst comprising the zinc complex of the present invention does not decompose or lose its activity with the progress of the reaction as in the case of already reported catalysts, but is extremely stable and further exhibits a high activity.
EXAMPLES
[0126] Hereinafter, the present invention will be described in detail based on Examples. However, the present invention is not limited thereto. Note that analytical instruments were as follows. In addition, all operations in Examples were conducted in an argon atmosphere.
[0127] NMR: Varian Unity (400 MHz), Bruker Advanced III (500 MHz)
Reference Example 1
Synthesis of Ligand (A)
[0128]
[0129] To a solution of imidazole (408.7 mg, 6.0 mmol) in 10 mL of dimethoxyethane (DME), sodium hydride (60% in mineral oil, 309.3 mg, 7.73 mmol) was gradually added at 0° C. Subsequently, dichloro-m-xylene (4.87 mmol) was added, followed by stirring at room temperature for 15 hours. A 20% aqueous sodium hydroxide solution was added, followed by extraction with ethyl acetate. The obtained organic layer was washed with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and then the obtained crude product was purified by flash column chromatography (CH 2 Cl 2 /MeOH=20/1) to obtain the target product as a colorless solid in a yield of 98%.
[0130] 1H NMR (500 MHz, CDCl3) δ 7.53 (s, 2H, NCHN), 7.35 (t, J=2.5 Hz, 1H, Ar), 7.10 (s, 2H, Ar), 7.09 (s, 2H, CH2NCHCH), 6.92 (s, 1H, Ar), 6.88 (s, 2H, CH2NCHCH), 5.10 (s, 4H, NCH2)
Reference Example 2
Synthesis of Ligand (B)
[0131]
(a) Synthesis of (5-(tert-Butyl)-1,3-phenylene)dimethanol
[0132] To tetrahydrofuran (THF) (50 mL), 5-tert-butylisophthalic acid (2.22 g, 10.0 mmol) and sodium borohydride (1.17 g, 30.9 mmol) were added. To this suspension, BF3.OEt 2 (3.70 mL, 30.0 mmol) was gradually added at 0° C., followed by stirring at room temperature for 23 hours. The reaction was quenched by adding water, followed by extraction with ethyl acetate. The obtained organic layer was washed with 1 M aqueous hydrochloric acid and saturated aqueous sodium hydrogen carbonate in this order, and dried over anhydrous sodium sulfate. The solvent was evaporated, and then the obtained crude product was purified by flash column chromatography (CH 2 Cl 2 /MeOH=30/1 to 20/1) to obtain the target product as a colorless solid in a yield of 95%.
[0133] 1H NMR (400 MHz, CDCl3) δ 7.33 (s, 2H, Ar), 7.20 (s, 1H, Ar), 4.70 (s, 4H, CH2), 1.33 (s, 9H, CH3)
(b) Synthesis of 1-(tert-Butyl)-3,5-bis(chloromethyl)benzene
[0134] To dichloromethane (15 mL), (5-(tert-butyl)-1,3-phenylene)dimethanol (5.0 mmol) obtained in (a) described above and triethylamine (15.0 mmol) were added. To this solution, methanesulfonyl chloride (14.9 mmol) was gradually added at −15° C., followed by stirring for 40 minutes, and then by stirring at 50° C. for 14 hours. The reaction liquid was washed with 1 M aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated aqueous sodium chloride in this order, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and then the obtained crude product was purified by flash column chromatography (hexane/AcOEt=30/1) to obtain the target product as a colorless solid in a yield of 84%.
[0135] 1H NMR (400 MHz, CDCl3) 7.35 (s, 2H, Ar), 7.25 (s, 1H, Ar), 4.58 (s, 4H, CH2), 1.33 (s, 9H, CH3)
(c) Synthesis of Ligand (B)
[0136] By using 1-(tert-butyl)-3,5-bis(chloromethyl)benzene obtained in (b) described above and imidazole, the target product was obtained as a colorless solid in a yield of 91% by the same method as in Reference Example 1.
[0137] 1H NMR (400 MHz, CDCl3) δ 7.52 (s, 2H, NCHN), 7.10 (d, J=6.4 Hz, 2H, Ar), 7.10 (d, J=6.4 Hz, 2H, CH2NCHCH), 6.88 (s, 2H, CH2NCHCH), 6.70 (s, 1H, Ar), 5.08 (s, 4H, CH2)
Example 1
Production of Zinc Complex
[0138] Zinc complexes of the present invention were prepared by reacting predetermined amounts of ligands A and B with a tetranuclear zinc cluster complex Zn 4 (OCOCF 3 ) 6 O as shown in the following reaction formulae.
[0000]
[0139] Each of the obtained zinc complexes was subjected to single-crystal X-ray crystallography. Table 1 shows the analysis data.
[0000]
TABLE 1
Crystal Data and Data Colestion Parameters a, b
a
b
c
empirical formula
C 32 H 28 F 6 N 8 O 4 Zn
C 30 H 30 F 3 N 4 O 6 Zn
C 40 H 44 F 6 N 8 O 4 Zn
formula weight
767.99
664.95
880.20
crystal system
triclinic
triclinic
monoclinic
space group
P-1
P-1
P2 1 /n (No. 14)
a, Å
8.815(4)
9.747(2)
14.5768(12)
b, Å
9.287(5)
11.299(2)
8.9341(7)
c, Å
11.376(6)
11.586(2)
15.9047(13)
α, deg.
82.508(5)
99.020(2)
—
β, deg.
67.980(5)
107.884(2)
103.2940(10)
γ, deg.
67.616(5)
113.050(2)
—
V, Å 3
798.2(7)
1059.9(4)
2015.8(3)
Z
1
1
2
D calcd , g/cm −3
1.598
1.042
1.450
μ [Mo-Kα], mm −1
0.71069
0.71073
0.71073
T, K
90
90
90
crystal size, mm
2 θ max , deg.
56.6
56.5
57.1
no. of reflections measured
4204
5940
10987
unique data (R int )
3332 (0.0390)
4547 (0.0163)
4583 (0.0165)
data/restraints/parameters
3332/0/246
4547/0/355
4583/0/271
R1 (I > 2.0 σ (I))
0.0864
0.0272
0.0394
wR2 (I > 2.0 σ (I))
0.2019
0.1001
0.1612
R1 (all data)
0.0282
0.0411
wR2 (all data)
0.1017
0.1672
GOF on F 2
0.995
0.936
1.549
Δ ρ, e Å-3
4.450, −5.140
0.447, −0.480
1.222, −1.053
a R1= (Σ | | Fo| − | Fc| |)/(Σ | Fo|).
b wR2 = [{Σ w(Fo 2 − Fc 2 ) 2 }/{Σ w(Fo 4 )}] 1/2 .
[0140] In addition, FIGS. 1 to 3 show the obtained results of the single crystal X-ray structures.
[0141] The single-crystal X-ray crystallography shows that each of the zinc complex A and the zinc complex C of the present invention has an octahedral geometry in which four nitrogen atoms on one side of the imidazole groups are coordinated to one zinc atom and two groups of atoms CF 3 COO are coordinated to the zinc atom with trans configuration. In addition, it has been found that the zinc complex A is an infinite chain complex in which the bonding extends continuously in a one-dimensional direction, and that the zinc complex C is an infinite chain complex in which the bonding extends continuously in two-dimensional directions. In condtrast, the zinc complex B (control) was an one-dimensional infinite complex with a tetrahedral geometry in which two nitrogen atoms on one side of imidazole groups are coordinated to one zinc atom and two groups of atoms, namely, CF 3 COO groups are coordinated to the zinc atom with trans configuration.
[0142] FIG. 4 shows an MS measurement result of the zinc complex A. In addition, FIG. 5 shows an MS measurement result of the zinc complex C. Each ratio represents the ratio between zinc, trifluoroacetic acid, and the ligand having imidazolyl groups.
[0143] Note that the MS measurement was conducted with the following instrument.
[0000] MS (direct introduction (direct inlet, direct infusion)) Zinc complex A: JMS-T100GCV (JEOL Ltd.), ionization mode: FD Zinc complex C: LC-MS-IT-TOF (Shimadzu Corporation), ionization mode: ESI
Example 2
Transesterification Reaction
[0144]
[0145] By using the zinc complex A prepared in Example 1 at a catalyst ratio of 5 mol % (zinc atom mole ratio (Zn/substrate=Zn/S)), a transesterification reaction between methyl benzoate (1.0 mole equivalents) and benzyl alcohol (1.2 mole equivalents) was conducted. Consequently, benzyl benzoate was obtained in a yield of 92%.
Comparative Example 1
Transesterification Reaction Using Zinc Complex B
[0146] A reaction was conducted in the same manner as in Example 2, except that the catalyst was changed to the zinc complex B prepared in Example 1. Consequently, the transesterification reaction did not proceed.
Example 3
Transesterification Reaction Based on In-Situ Method
[0147] A reaction was conducted in the same manner as in Example 2, except that the same amount of Zn 4 (OCOCF 3 ) 6 O and the ligand (A) (8 equivalents to Zn 4 (OCOCF 3 ) 6 O) were added as a catalyst instead of the zinc complex A. Consequently, benzyl benzoate was obtained in a yield of 91%.
Examples 4 to 10
Transesterification Reactions
[0148] Catalytic reactions were conducted as shown in the following formula in a chlorobenzene (PhCl) solvent by using Zn 4 (OCOCF 3 ) 6 O (1 mole equivalent) and various ligands (8 mole equivalents, the ligand was 2 mole equivalents relative to 1 mole equivalent of zinc atoms) as catalysts, which were added to a transesterification reaction system between methyl benzoate and cyclohexanol (catalyst ratio: 1.25 mol %).
[0000]
[0149] Table 2 below collectively shows the reaction results.
[0000]
TABLE 2
Ligand
Yield (%)
Example 4
89
Example 5
84
Example 6
80
Example 7
87
Example 8
52
Example 9
71
Example 10
92
No ligand
10
15
[0150] In addition, the yield was 10% in the case where no ligand was added, and the yield was 15% in the case where a different nitrogen-containing heterocyclic (N-methylbenzimidazole) compound was added as the ligand, revealing that the activity was lower in these cases than in the cases of the ligands used in the present invention.
[0151] Note that the ligands (C) to (G) were obtained by the methods shown in the following schemes.
Synthesis of Ligand (C)
[0152]
[0153] 1H NMR (400 MHz, CDCl3) δ 7.51 (s, 2H, NCHN), 7.35 (m, 5H, Ar), 7.10 (s, 2H, CH2NCHCH), 6.86 (s, 2H, CH2NCHCH), 6.65 (s, 2H, Ar), 6.52 (s, 1H, CH2CCHCCH2), 5.04 (s, 4H, NCH2), 4.96 (s, 2H, OCH2)
Synthesis of Ligand (D)
[0154]
[0155] 1H NMR (500 MHz, CDCl3) δ 7.52 (s, 2H, NCHN), 7.10 (s, 2H, CH2NCHCH), 6.88 (s, 2H, CH2NCHCH), 6.58 (s, 2H, Ar), 6.50 (s, 1H, Ar), 5.04 (s, 4H, NCH2), 3.84 (t, J=6.5 Hz, 2H, OCH2), 1.73 (tt, J=7.5, 6.5 Hz, 2H, OCH2CH2), 1.41-1.35 (m, 4H, CH2CH2CH3), 0.92 (t, J=7.0 Hz, 3H, CH3)
Synthesis of Ligand (E)
[0156]
[0157] 1H NMR (400 MHz, CDCl3) δ 7.53 (s, 2H, NCHN), 7.23 (s, 2H, CH2NCHCH), 7.12 (s, 2H, CH2NCHCH), 6.87 (s, 2H, Ar), 6.80 (s, 1H, Ar), 5.07 (s, 4H, CH2)
Synthesis of Ligand (F)
[0158]
[0159] 1H NMR (500 MHz, CDCl3) δ 7.44 (s, 2H, NCHN), 7.38 (dd, J=9.0, 2.5 Hz, 2H, Ar), 7.12 (s, 2H, CH2NCHCH), 7.09 (dd, J=9.0, 2.0 Hz, 2H, Ar), 6.79 (s, 2H, CH2NCHCH), 5.03 (s, 4H, NCH2)
Synthesis of Ligand (G)
[0160]
[0161] 1H NMR (400 MHz, CDCl3) δ 7.45 (s, 2H, NCHN), 7.09 (s, 2H, CH2NCHCH), 6.86 (s, 2H, CH2NCHCH), 3.95 (d, J=7.6 Hz, 4H, NCH2), 2.11 (m, 2H, CH2CH2CH), 1.65 (m, 2H, CH2CH2CH), 1.47-1.33 (m, 6H, CH2CH2CH).
Examples 11 to 14
Transesterification Reactions
[0162] Reactions were conducted as shown in the following formula by changing the solvent to toluene and by using Zn 4 (OCOCF 3 ) 6 O (1 mole equivalent) and various ligands (8 mole equivalents, each ligand was 2 mole equivalents relative to 1 mole equivalent of zinc atoms) as catalysts, which were added to a transesterification reaction system between methyl benzoate and benzyl alcohol (catalyst ratio: 1.25 mol %).
[0000]
[0163] Table 3 below collectively shows the reaction results.
[0000]
TABLE 3
Ligand
Yield (%)
Example 11
91
Example 12
92
Example 13
97
Example 14
97
[0164] When the ligand (D) of Example 14 was used as the catalyst, the system remained homogeneous one hour after the start of the reaction, but a solid was precipitated at the end of the reaction. The precipitated solid was recovered. The zinc complex C of the present invention serving as the catalyst was successfully recovered in a yield of 63%. A transesterification reaction was conducted by using the recovered zinc complex C in the same manner. The reaction proceeded in about the same yield (92%). Hence, it is conceivable that the catalyst of the present invention can provide good results, even when recycled.
Example 15
Transesterification Reactions (Recovery and Recycle Use of Catalyst)
[0165] In the following transesterification reaction, recycle use was examined in the case where the ligand (B) was used.
[0000]
[0166] After the reactions (the yields of benzyl benzoate were all 90% or higher), each reaction liquid was allowed to cool to room temperature. Then, a solvent was added, followed by stirring. The solution part was removed, and then the residue was dried in a vacuum to recover the zinc complex. Table 4 shows the results.
[0000]
TABLE 4
Example No.
Solvent
Recovery (%)
15-1
None
63
15-2
Hexane
84
15-3
Ethyl acetate
78
15-4
Diisopropyl ether
69
15-5
THF
52
15-6
Diethyl ether
49
15-7
Dichloromethane
<1
[0167] The conditions were further investigated. Consequently, it has been found that the complex can be recovered almost quantitatively by first removing the reaction solvent toluene by distillation, and then adding hexane. The catalyst was recovered by using this method, and the reaction was conducted again. The catalytic reaction was successfully carried out, without any decrease in the reaction yield from that of the previous reaction. In addition, after completion of the fifth reaction, the recovery was 91%.
Example 16
Transesterification Reaction
[0168] A reaction was conducted as shown in the following formula by adding 2 mole equivalents of the ligand (A) relative to 1 mole equivalent of zinc trifluoroacetate hydrate to the transesterification reaction system. With a zinc atom ratio of 3 mol % relative to methyl benzoate, reflux was conducted in chlorobenzene for 5 hours. Consequently, the conversion was 94%.
[0000]
Example 17
Transesterification Reaction
[0169] A reaction was conducted in the same manner as in Example 16 described above. With a catalyst ratio of 2 mol % relative to methyl 4-cyanobenzoate, reflux was conducted in chlorobenzene for 5 hours. Consequently, the raw material methyl 4-cyanobenzoate disappeared, and the conversion was almost 100%.
[0000]
Example 18
Transesterification Reaction
[0170] A catalytic reaction was conducted as shown in the following formula by adding 2 mole equivalents of the ligand (A) relative to 1 mole equivalent of zinc trifluoroacetate hydrate to a transesterification reaction system. With a catalyst ratio of 3.3 mol % relative to methyl 4-nitrobenzoate, reflux was conducted in benzene chloride for 5 hours. The raw material methyl 4-nitrobenzoate disappeared, and the conversion was 99.9%.
[0000]
Example 19
Transesterification Reactions
[0171] Transesterification reactions between cyclohexylmethanol and methyl 4-nitrobenzoate or methyl 4-cyanobenzoate were conducted as shown in the following formula (solvent: chlorobenzene, 5 hours under reflux). With a catalyst ratio of 2.7 mol % relative to each substrate, the esterification reaction proceeded quantitatively.
[0000]
Example 20
Carbonate Formation Reaction
[0172]
[0173] A carbonate formation reaction from cyclohexylmethanol was conducted by using the zinc complex A at a catalyst ratio of 2.5 mol % and using dimethyl carbonate as the solvent (5 hours under reflux). The raw material cyclohexylmethanol almost disappeared, and the carbonate formation reaction proceeded quantitatively.
[0174] As a recycle experiment, the catalyst was filtered, and then the above-described reaction was conducted again. As in the case of the first time, the raw material cyclohexylmethanol almost disappeared, and the transesterification reaction proceeded quantitatively. From this result, it has been found that the catalyst of the present invention can be used repeatedly.
Example 21
Carbonate Formation Reactions
[0175]
[0176] Carbonate formation reactions from cyclohexanol were conducted in the same manner as in Example 20 described above, by using the zinc complex A or the zinc complex C at a catalyst ratio of 2.5 mol % and by using dimethyl carbonate as the solvent (5 hours under reflux). The conversions were 97% and 91%, respectively.
Example 22
Acetylation Reaction
[0177]
[0178] Acetylation of n-butanol with ethyl acetate was conducted by using the ligand (B) and Zn 4 (OCOCF 3 ) 6 O as a catalyst. n-Butanol was refluxed in an ethyl acetate solvent for 18 hours. The target product was obtained in a yield of 99%.
Example 23
Hydroxy Group-Selective Acylation Reaction (Transesterification Reaction in the Presence of Alcohol and Amine
[0179]
[0180] By using 5 mol % of the zinc complex C, a transesterification reaction of a mixture of cyclohexylamine and cyclohexanol with methyl benzoate was conducted under reflux for 46 hours by using diisopropyl ether (i-Pr 2 O) as a solvent. Consequently, cyclohexyl benzoate was obtained in a yield of 67%, and cyclohexylbenzamide was not formed at all. It has been shown that the zinc complex can also be applied to an alcohol compound-selective acylation reaction in the presence of an amino compound.
Example 24
Hydroxy Group-Selective Acylation Reaction (Transesterification Reaction of Amino Alcohol)
[0181]
[0182] A transesterification reaction between methyl benzoate and trans-4-aminocyclohexanol was conducted by using 2.5 mol % of the zinc complex A (solvent: chlorobenzene (PhCl), 5 hours under reflux). The conversion was 75.9%, and the ratio (selectivity) of the compound produced by the reaction between the hydroxy group and methyl benzoate and the compound produced by the reaction between the amino group and methyl benzoate was 84:16. It has been shown that the complex can be applied to a hydroxy group-selective acylation reaction in the presence of an amino group.
Example 25
Hydroxy Group-Selective Carbonate Formation Reaction (Carbonate Formation in the Presence of Alcohol and Amine)
[0183]
[0184] For carbonate formation from cyclohexanol and cyclohexylamine using dimethyl carbonate as a solvent, reflux was conducted for 3.5 hours by using 5.0 mol % of the zinc complex A as a catalyst. The yield of the carbonate compound was 95%, and the yield of the carbamate compound was 5%. It has been shown that the complex can be applied also to an alcohol compound-selective carbonate formation reaction in the presence of an amino compound.
[0185] For the identification of the products, compounds were prepared by esterification and urethane formation of cyclohexanol and cyclohexylamine with methyl chloroformate separately, and the ratio of the products of this example was checked by a gas chromatography (GC) analysis.
Example 26
Hydroxy Group-Selective Carbonate Formation Reaction (Carbonate Formation from Amino Alcohol)
[0186]
[0187] A carbonate formation reaction between dimethyl carbonate and trans-4-aminocyclohexanol was conducted by using 2.5 mol % of the zinc complex A as a catalyst (5 hours under reflux). The conversion of trans-4-aminocyclohexanol was 86%, with an O-selectivity of 91%, an N-selectivity of 4%, and an O,N-selectivity of 5%. This shows that the zinc complex can be applied to a hydroxy group-selective carbonate formation reaction in the presence of an amino group. For the identification of the products, compounds were prepared by esterification and urethane formation of trans-4-aminocyclohexanol with methyl chloroformate, separately, and the ratio of the products of this example was checked by a gas chromatography (GC) analysis.
Example 27
Transesterification Reaction of Carbamate
[0188]
[0189] A transesterification reaction was conducted in a chlorobenzene solvent for 5 hours with a catalyst ratio of 1.5 mol % by using N-phenyl carbamate and cyclohexylmethanol and by adding 2 mole equivalents of the ligand (A) relative to 1 mole equivalent of zinc trifluoroacetate hydrate. Consequently, the conversion was 92%.
Example 28
Transesterification Reactions
[0190] Transesterification reactions were conducted by using methyl benzoate and L-menthol and using the zinc complex A or the zinc complex C as a catalyst (solvent: chlorobenzene (PhCl), 5 hours, reflux). Consequently, the product was obtained with conversions of 34% and 46%, respectively.
[0000]
Example 29
Transesterification Reactions
[0191] Transesterification reactions were each conducted by using 1 equivalent of methyl benzoate and 1.2 equivalents of (+)-menthol, and adding Zn 4 (OCOCF 3 ) 6 O and a ligand to prepare a catalyst (solvent: toluene, 5 hours, reflux). Table 5 shows the results of the transesterification reactions. When no ligand was added, the reaction did not proceed (Comparative Example 6).
[0000]
[0000]
TABLE 5
Ligand
Yield
Example 29-1
D
66%
Example 29-2
H
64%
Example 29-3
I
75%
Example 29-4
J
52%
Comp. Ex. 6
None
N.D.
[0192] The ligands (H), (I), and (J) were synthesized by using the ligand (E) as a raw material.
[0193] Ligand (H): 1 H NMR (500 MHz, CDCl 3 ) δ 7.53 (s, 2H, NCHN), 7.10 (s, 2H, CH 2 NCHCH), 6.92 (s, 2H, Ar), 6.88 (s, 2H, CH 2 NCHCH), 6.72 (s, 1H, Ar), 5.07 (s, 4H, CH 2 ), 2.47-2.42 (m, 1H, CH), 1.83-1.71 (m, 6H, cyclohexyl), 1.40-1.20 (m, 4H, cyclohexyl); 13 NMR (125 MHz, CDCl 3 ) δ150.1, 137.5, 137.1, 130.0, 125.6, 123.4, 119.2, 50.6, 44.3, 34.3, 26.7, 25.9.
[0194] Ligand (I): 1 H NMR (500 MHz, CDCl 3 ) δ 7.53 (s, 2H, NCHN), 7.10 (s, 2H, CH 2 NCHCH), 6.95 (s, 2H, Ar), 6.88 (s, 2H, CH 2 NCHCH), 6.72 (s, 1H, Ar), 5.07 (s, 4H, CH 2 ), 2.85 (qq, J=7 Hz, 1H, CH), 1.19 (d, J=7 Hz, 6H, CH 3 ); 13 C NMR (125 MHz, CDCl 3 ) δ 150.9, 137.4, 137.2, 130.0, 125.3, 123.5, 119.3, 50.6, 34.0, 23.8. Ligand (J): 1 H NMR (500 MHz, CDCl 3 ) δ 7.53 (s, 2H, NCHN), 7.10 (s, 2H, CH 2 NCHCH), 6.90 (s, 2H, Ar), 6.88 (s, 2H, CH 2 NCHCH), 6.74 (s, 1H, Ar), 5.06 (s, 4H, CH 2 ), 2.52 (t, J=7.5 Hz, 2H, CH 2 ), 1.56 (tq, J=7.5, 7.0 Hz, 2H, CH 2 CH 3 ), 0.90 (t, J=7.0 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ) δ 144.7, 137.4, 137.1, 130.0, 127.2, 123.4, 119.3, 50.5, 37.7, 24.4, 13.7.
Example 30
Carbonate Formation Reactions
[0195] A carbonate formation reaction of each of L-menthol and D-menthol was conducted in a dimethyl carbonate solvent by using the zinc complex A at a catalyst ratio of 5.0 mol % (9 hours, reflux). Consequently, the raw materials menthols disappeared. The zinc catalyst was precipitated by adding hexane, and filtered. After evaporation of the solvent, each target product was octained quantitatively.
[0196] Each optical purity was checked by GC measurement. Consequently, the optical purity before the reaction was confirmed to be retained.
[0000]
Example 31
Cyclic Carbonate Formation Reactions
[0197] In a dimethyl carbonate solvent, 1,2-butanediol was refluxed for 5 hours with the zinc catalyst A (a catalyst ratio of 2 mol %) being used. The conversion of 1,2-butanediol to 4-ethyl-1,3-dioxolan-2-one was 94%. In addition, another reaction was conducted by adding zinc trifluoroacetate hydrate (a catalyst ratio of 2 mol %) and the ligand (A) (a catalyst ratio of 4 mol %) in the same manner. Consequently, the raw material 1,2-butanediol disappeared in 9 hours, and the cyclic carbonate was successfully obtained as in the case where the zinc catalyst A was used.
[0000]
Comparative Example 7
Cyclic Carbonate Formation Reaction
[0198] A reaction was conducted by using Zn 4 (OCOCF 3 ) 6 O as a catalyst instead of the zinc catalyst A at a catalyst ratio of 2 mol % under reflux for 5 hours in the same manner as in Example 30. Consequently, the conversion of 1,2-butanediol was 53%, and the raw material 1,2-butanediol did not disappear even after reflux for 9 hours, and the reaction was not completed.
Example 32
Transesterification Reaction
[0199] A transesterification reaction between methyl acetoacetate and 1-adamantanol was conducted by using the zinc complex C (a catalyst ratio of 2.8 mol %) as a catalyst (solvent: chlorobenzene (PhCl), 5 hours under reflux). Consequently, the transesterification product was obtained with a conversion of 46%.
[0000]
Examples 33 to 44
Transesterification Reactions
[0200] By the method of the present invention, transesterification reactions were conducted by using various ester compounds and alcohol compounds. The results are shown below.
[0000]
[0000]
Ex.
R 1
R 2
Ligand
Solvent
Time
Yield
33
CH2═CH—
cyclohexyl
D
i-Pr 2 O
18
78%
hr
34
CH 2 ═C(Me)—
benzyl
D
iPr 2 O
18
76%
hr
35
MeCH(Cl)—
benzyl
B
PhMe
5 hr
96%
36
H
benzyl
D
HCO 2 Et
24
82%
hr
37
2-tolyl
benzyl
D
PhMe
5 hr
85%
38
n-butyl
D
i-Pr 2 O
18 hr
93%
39
Ph
D
PhMe
5 hr
85%
40
Ph
D
PhMe
18 hr
>99%
41
Ph
Me3Si—CH2CH2—
D
PhMe
8 hr
94%
42
Ph
D
PhMe
8 hr
93%
43
PhCH 2 CH 2 —
1-adamantyl
D
xylene
72
92%
hr
44
D
xylene
38 hr
82%
Example 45
Deacylation Reaction
[0201]
[0202] A deacetylation reaction of benzyl acetate was conducted in a methanol solvent by using the zinc complex C. Regarding the amount of the catalyst, 5 mol % of the catalyst was used in terms of the mole ratio of zinc atoms to benzyl acetate. The reaction yield was 93%. | A zinc complex characterized in exhibiting an octahedral structure and being configured from repeating units represented by general formula (I):
wherein L represents a linker region, and R 1 represents a C1-4 alkyl group, which can have a halogen atom. | 1 |
This application is a CIP of 86,605 filed 10/19/79, abandoned, and a CIP of 164,708 filed 6/30/80, abandoned.
BACKGROUND OF THE INVENTION
Trauma to the brain or spinal chord caused by physical forces acting on the skull or spinal column, by ischemic stroke or by hydrocephalus results in edema and swelling of the affected tissues. This is followed by ischemia, temporary or permanent brain and/or spinal chord injury and may result in death. The tissues mainly affected are classified as grey matter, more specifically astroglial cells.
The specific therapy currently used for the treatment of the medical problems described is limited to steroids, such as, the sodium salt of 6-α-methylprednisolone succinate. Although these agents are effective in situations involving white matter edema, they comprise relative ineffective therapy for grey matter edema. Thus, the compounds of this invention comprise a novel and specific treatment for a medical problem where no specific therapy is available.
The compounds of the invention have the added advantage of being devoid of the toxic side effects of the steroids and of having little or no renal effects.
DESCRIPTION OF THE INVENTION
The compounds of the instant invention are best characterized by reference to the following structural formula: ##STR1## wherein R is H, lower alkyl, branched or unbranched, such as methyl, ethyl, propyl, isopropyl, butyl, sec. butyl, isobutyl and the like; lower alkenyl, such as vinyl and allyl; lower alkynyl, such as propargyl; aryl, such as phenyl; aryl lower alkyl, such as benzyl; lower cycloalkyl, such as cyclopropyl and cyclobutyl, lower cycloalkyl lower alkyl, such as cyclopropylmethyl and the like;
R 1 is H, lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like; lower alkenyl, such as, allyl, 2-butenyl, and the like; lower alkynyl, such as, propargyl, butynyl and the like; lower cycloalkyl, such as cyclobutyl, cyclopentyl and the like; substituted lower alkyl, where the substituent is carboxy, lower alkoxycarbonyl, oxo, hydroxy, lower alkoxy, halo, lower acyloxy, lower dialkylamino, sulfamoyl, pyridyl, furyl, tetrahydrofuryl, aryl, 1-methylpiperidyl, morpholinyl, pyrrolidinyl, 1-methylpiperazinyl, thienyl, and the like; substituted cycloalkyl, such as carboxycycloalkyl; and the like; heterocyclic, such as, imidazolyl, pyridyl, thiazolyl, pyrazinyl, furyl, and the like; aryl, such as phenyl, carboxyphenyl, hydroxymethylphenyl and the like;
Y 1 and Y 2 are Cl and CH 3 ##STR2## where R 2 is H, methyl or ethyl, R 3 is H, F or methyl and R 2 and R 3 may be joined together to form a ring which can be represented by>C(CH 2 ) n where n=2, 3, or 4.
Since the 9a carbon atom in the molecule is asymmetric, the compounds of the invention are racemic; however, these compounds can be resolved, so that the invention includes the pure enantiomers. In addition, in some instances, the group represented by A and by R 1 includes an asymmetric carbon atom. Thus, these molecules may contain two or three asymmetric carbon atoms and now can consist of two or four diastereomers, each of which consists of two enantiomers. The invention includes each diastereomer and their enantiomers whenever they exist.
Although the invention involves novel [(5,6,9a-substituted-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-alkanoic and cycloalkanoic acids, it also includes the obvious analogs, the corresponding esters, salts and their derivatives such as anhydrides, amides, hydrazides, guanidides and the like.
PREFERRED EMBODIMENTS OF THE INVENTION
The preferred embodiments of the instant invention are realized in structural formula IA wherein:
R is lower alkyl, alkenyl, alkynyl, cyclopropyl, cyclopropylmethyl, or aralkyl ##STR3##
R 2 is hydrogen, lower alkyl, substituted alkyl, such as carboxyalkyl, hydroxyalkyl, dihydroxyalkyl, trihydroxyalkyl, oxoalkyl, dilower alkylaminoalkyl, and heterocyclic-alkyl.
Y 1 and Y 2 are chloro
Also included are the enantiomers of each racemic compound.
A preferred compound is [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid.
Another preferred compound is [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-3-oxo-9a-isopropyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid.
Another preferred compound is [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid.
Another preferred compound is [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid and its enantiomers.
Another preferred compound is [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid and its enantiomers.
Another preferred compound is [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Another preferred compound is 1-carboxy-1-methylethyl [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 1-carboxy-1-methylethyl [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 3-pyridylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 2-oxopropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 2-(dimethylamino)-ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is 3-carboxypropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and its enantiomers.
Another preferred compound is carboxymethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Another preferred compound is 3-hydroxypropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Another preferred compound is [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid hydrazide.
Especially preferred are the (+)R enantiomers of the racemic modification of each compound; thus, the most preferred compounds are the (+)R enantiomers of the compounds tested supra.
Included within the scope of this invention are the analogs and derivatives of the parent carboxylic acids, their salts, their esters and their amides and other derivatives which may be prepared by conventional methods well known to those skilled in the art.
Thus, the acid addition salts can be prepared by the reaction of the carboxylic acids of the invention with an appropriate amine, guanidine, ammonium hydroxide, alkali metal hydroxide, alkali metal bicarbonate or alkali metal carbonate and the like. The salts are selected from among the non-toxic, pharmaceutically acceptable bases.
The synthesis of the carboxylic acid compounds of Formula II is generally carried out by the hydrolysis of the corresponding ester (III): ##STR4##
The process can be effected by heating the ester in a solution of acetic and aqueous inorganic acid, such as hydrochloric acid, sulfuric acid and the like. The hydrolysis also can be effected in aqueous alcoholic base such as sodium hydroxide or potassium hydroxide in aqueous methanol or ethanol. The product is recovered by acidification with an acid, such as, hydrochloric acid. The reaction can be carried out at temperatures of 30° C. to 100° C. for periods of about 20 minutes to 6 hours, depending on the specific ester used and the other reaction conditions. In the instances, such as where A is --CHF--, it is advantageous to carry out the hydrolysis using a weak base, such as aqueous sodium bicarbonate. A solvent, such as aqueous ethanol, methanol or isopropyl alcohol is used and the mixture heated at 45° C. to 100° C. for periods of 15 minutes to 4 hours. Acidification of the reaction mixture with strong aqueous acids, such as hydrochloric acid, hydrobromic acid or sulfuric acid produces the desired compound of Formula II.
A second method for the preparation of compounds of the type illustrated by Formula II involve the reaction of a haloalkanoic or halocycloalkanoic acid (X-A-COOH) with the appropriate phenol (IV). ##STR5## Using a haloalkanoic or halocycloalkanoic acid X-A-COOH, where X=iodo, bromo or chloro and A is as defined above, for example, iodoacetic acid or bromofluoroacetic acid, as the etherification agent, the reaction is conducted in the presence of a base. The base is selected from among the alkaline earth or alkali metal bases such as sodium or potassium carbonate, calcium hydroxide and the like. The reaction is carried out in a liquid reaction milieu, the choice being based on the nature of the reactants; however, solvents which are reasonably inert to the reactants and are fairly good solvents for the compounds of Formula IV and the X-A-COOH reagent, can be used. Highly preferable are dimethylformamide, ethanol, acetone, and N-methylpyrrolidine-2-one, and the like.
A third method for preparing compounds of Formula II involves the pyrolysis of the corresponding tert.-butyl ester (IB): ##STR6##
This method involves heating a tert.-butyl ester of the type illustrated by formula IB at from about 80° C. to 120° C. in a suitable nonaqueous solvent in the presence of catalytic amount of a strong acid. The solvents are generally selected from among the type benzene, toluene, xylene, etc. and the acid catalyst may be a strong organic or inorganic acid, such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, sulfuric etc. The acid, being a catalyst, is generally used in relatively small quantities as compared to the tert.-butyl ester (IB). It is to be noted that this reaction is a pyrolysis and not a hydrolysis, since water is excluded from the reaction and the products are a carboxylic acid (Formula II) and isobutylene and no alcohol is produced.
Another method of converting compounds of Type IB to those of Type II is by heating compounds of type IB with trifluoroacetic acid is a solvent like dichloromethane.
A fourth method is limited to the instances wherein compounds of Formula IIA are produced, i.e., where A is ethylene: ##STR7##
This synthesis involves the reaction of the appropriate phenol (IV) with propiolactone in the presence of a base and a solvent, preferably while heating and stirring the reaction mixture. Solvents, such as a mixture of water and an alcohol, such as methanol, ethanol or propanol are used. The base is selected from among the alkali metal hydroxides or carbonates, such as sodium hydroxide, potassium hydroxide, potassium carbonate and the like. The temperature is generally at the boiling point of the solvent mixtures but it may be at 50° C.-110° C. depending on the reactants involved. The product is isolated by acidification of the reaction mixture with a strong acid such as hydrochloric or sulfuric acid.
Special methods are used to synthesize compounds of Formula II where R is vinyl (Formula IIB) or cyclopropyl (Formula IIC). ##STR8##
An alkyl [(2-ethylidene-1-oxo-2,3-dihydro-1H-indene-5-yl)oxy]alkanoate is treated with methyl vinyl ketone (MVK) in the presence of a base, such as, potassium tert.-butoxide, in 1,2-dimethoxyethane at 0° C. or lithium dimethylamide at -70° C. in tetrahydrofuran. The reaction is conducted in an atmosphere of dry nitrogen.
The alkyl [[1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy]alkanoate produced is cyclized to an alkyl [(3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]alkanoate by heating in the presence of a reagent like pyrrolidine acetate and the like in benzene or toluene. Heating with a base, such as, potassium tert.-butoxide in tert.-butyl alcohol is also effective.
Finally, the compound of Formula IIB is produced by saponification of the alkyl [(3-oxo-9a-vinyl, 1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]alkanoate by heating with a base, such as, sodium or potassium hydroxide in a solvent, such as water or a mixture of methanol or ethanol and water. The product is generated upon acidification with an acid, such as, hydrochloric or sulfuric acid.
Alternatively, compounds of Formula IIB can be generated directly from an alkyl [[1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy]alkanoate by dissolving in a mixture of an alcohol, such as, methanol or ethanol and aqueous sodium hydroxide or potassium hydroxide. After standing at ambient temperature for 24 to 48 hours, the product is isolated by acidification with an acid, such as, hydrochloric or sulfuric acid.
The preparation of compounds of Formula IIC is carried out by treating an alkyl [(3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]alkanoate with a zinc-copper couple and methylene iodide in a solvent, such as, ethyl ether, tetrahydrofuran or 1,2-dimethoxyethane at ambient temperature for an hour according to the conditions of the Simmons-Smith reaction. The alkyl [(3-oxo-9a-cyclopropyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is then hydrolyzed to a compound of Formula IIC by heating with an aqueous-alcoholic solution of a base, such as, potassium hydroxide or sodium hydroxide followed by acidification with an acid, such as, hydrochloric or sulfuric acid.
Alternatively, a compound of Formula IIC can be produced by treating an alkyl [[1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy]alkanoate with zinc-copper couple and methylene iodide in tetrahydrofuran to give an alkyl [[1-oxo-2-(3-oxobutyl)-2-cyclopropyl-2,3-dihydro-1H-inden-5-yl]oxy]alkanoate which is then cyclized and finally hydrolyzed by the methods just described. Likewise, the alkyl [[1-oxo-2-(3-oxobutyl)-2-cyclopropyl-2,3-dihydro-1H-inden-5-yl]oxy]alkanoate may be converted directly to IIC by treatment with aqueous methanolic sodium hydroxide followed by acidification with hydrochloric acid.
The preparation of compound IV can be carried out by one or the other of two methods. The first method involves the following three-step process: ##STR9##
Compounds of the type represented by Formula V which are used to produce the compounds of this invention have generally been described in the scientific and/or patent literature. For those that have not been previously disclosed or must be prepared by new methods, a description of their synthesis will be described later.
The first step (Step A) in the synthesis involves the reaction of a compound of Formula V with methyl vinyl ketone to produce a compound of Formula VI. The reaction is catalyzed by a base, such as triton B (benzyltrimethylammonium hydroxide) in methanol but other bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or sodium methoxide are effective catalysts. Solvents which are inert to the reaction and are effective in dissolving the reactants and product are normally used. Tetrahydrofuran is an especially preferred solvent but others, like p-dioxane or 1,2-dimethoxyethane can be used. The reaction is generally conducted at ambient temperatures but temperatures in the range of 10° C. to 45° C. or somewhat above or below these values can be used.
The second step (Step B) in the synthesis is the cyclization of a compound of Formula VI to give a compound of Formula VII. The reaction is generally conducted in the presence of a solvent such as benzene, toluene, xylene, anisole and the like but many other solvents which are inert to the reactants and to the catalyst are useful. A catalyst is necessary for increasing the rate of reaction. Salts of weak organic acids and weak inorganic or organic bases are preferred; for example, pyrrolidine acetate, piperidine acetate, pyrrolidine propionate and the like. The reaction is preferably conducted at the temperature of the boiling solvent but temperature of 30° C.-120° C. can be used. It is advantageous to carry out the reaction under conditions in which the water produced in the reaction is constantly removed. This is effected by various means, such as using a Dean-Stark constant water separator or co-distilling the solvent and the water. Another device for removing the water is to add molecular sieves designed for removing water, for example, Davison Molecular Sieves of 3A size M-564 (Cation: potassium, base:alumina-silicate).
In some instances, bases, such as potassium tert.-butoxide in tert.-butyl alcohol or potassium hydroxide or sodium hydroxide in aqueous methanol or ethanol may be used to effect cyclization.
The last step (Step C) involves the ether cleavage of a compound of Formula VII to produce a compound of Formula IV. This can be accomplished by many of the agents known to cleave ethers, especially useful are hydrohalide salts of weak bases, such as pyridine hydrochloride or pyridine hydrobromide, but other agents, such as aqueous hydrobromic acid or aluminum bromide can be used. When pyridine hydrohalides are used, the temperatures above that which these substances melt are generally employed. This usually involves temperatures in the range of 150° C. to 215° C., but temperatures somewhat lower or higher can be used. The period of heating varies depending on the specific compound but periods of from 15 minutes to 2 hours may be used.
The second method for preparing compounds of Formula IV is shown by the five-step reaction illustrated below. It should be mentioned that this is not simply a cyclical method whereby a compound of the invention (Formula II) is converted to one of its precursors (Formula IV) simply to be reconverted to the product again (Formula II).
In this instance, a readily accessible compound of Formula VIII, for example, where the A moiety is CH 2 , is converted to a compound of Formula II which, in turn, is converted to a compound of Formula IV which now can be used to synthesize a compound of Formula II which is difficultly accessible, i.e., wherein A is --CHF--, >C(CH 3 ) 2 , or >C(CH 2 ) 3 . ##STR10##
The first step (Step A) involves the esterification of compound of Formula VIII to produce the ester of Formula IX. The starting material, Formula VIII, is generally known; however, the synthesis of those which are not known or are accessible only by new methods will be discussed later. The esterification can be effected by many of the known methods. Especially useful is the procedure whereby compound of Formula VIII is reacted with an alkyl halide, such as methyl iodide, in the presence of an alkaline earth or alkali metal carbonate, such as potassium carbonate or sodium carbonate in the presence of a solvent such as dimethylformamide, 1-methylpyrrolidin-2-one, and the like to produce a compound of Formula IX. The reaction is generally conducted at a temperature of 30° C.-60° C. for from 3 to 20 hours. Alternatively, the esterification may be effected by the reaction of a compound of Formula VIII with an alkanol, such as methanol, ethanol or isopropyl alcohol in the presence of an acid catalyst. The acid catalyst may be a strong organic or inorganic acid, such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like.
The second step (Step B) involves the reaction of a compound of Formula IX with methyl vinyl ketone to form a compound of Formula X. The conditions for this reaction are similar to those described above for the conversion of a compound of Formula V to one of Formula VI.
The third step (Step C) is the cyclization of compounds of Formula X to form those of Formula IC. The conditions for this reaction are similar to those described for the conversion of compounds of Formula VI to those of Formula VII.
The fourth step (Step D) is the hydrolysis of compounds of Formula IC to those of Formula II. The conditions of this reaction have been described earlier.
The final step (Step E) is the ether cleavage of a compound of Formula II to produce a compound of Formula IV. The conditions for this reaction are similar to those described for the conversion of a compound of Formula VII to those of Formula IV.
As indicated earlier, those compounds of Formula V and Formula VIII which are not known or are accessible only by new synthetic routes, may be prepared by methods disclosed in this invention which are illustrated below. ##STR11##
The first step is the etherification of a compound of Formula XI to produce a compound of Formula XII. This is accomplished by a reaction involving a compound of Formula XI in any one of a number of chemical processes; especially useful is dimethyl sulfate in the presence of potassium carbonate using a solvent, such as dimethylformamide.
The second step (Step B) is the conversion of a compound of Formula XII to one of Formula XIII. This can be accomplished by one or another of many methods; especially useful is the reaction of a compound of Formula XII with malonic acid in the presence of a solvent such as pyridine and a weak organic base, such as piperidine or pyrrolidine. The reaction is effected by heating for 1 to 6 hours at a temperature of 75° C. to 120° C., preferably at about 95° C. to 100° C. Quenching the reaction mixture in ice and acidification with a strong acid, such as hydrochloric acid yields the desired compound of Formula XIII.
The third step (Step C) involves the catalytic hydrogenation of a compound of Formula XIII to produce a compound of Formula XIV. The reduction is conducted in an atmosphere of hydrogen at an initial pressure of 10 to 100 psi and at temperatures of from 15° C. to 45° C. A solvent in which the starting material and product are reasonably soluble and which is inert to the reactants, product and catalyst is employed. Solvents such as tetrahydrofuran, dioxane, and the like are especially useful. The catalyst is usually a finely divided noble metal (which may be on an inert support) i.e., palladium on charcoal or it may be a noble metal derivative which upon exposure to hydrogen is reduced to the free metal, i.e., platinum oxide.
The fourth step (Step D) consists of the cyclization of a compound of Formula XIV to produce a compound of Formula XV. This is accomplished by first converting a compound of Formula XIV to the corresponding acid chloride using a reagent like thionyl chloride or phosphorus oxychloride. A solvent, such as benzene is advantageous. The acid chloride is subjected to the conditions of the Friedel-Crafts reaction which results in the cyclization of the acid chloride to form a compound of Formula XV. A reagent such as aluminum chloride, stannic chloride and the like are used to effect the cyclization. The reaction is conducted in a typical Friedel-Crafts solvent, such as methylene chloride or carbon disulfide. The reaction time is generally 1 to 6 hours.
The fifth step (Step E) involves the reduction of a compound of Formula XV to one of Formula XVI. This reaction is accomplished by using zinc amalgam and hydrochloric acid. The reaction is generally conducted in a solvent such as a mixture of water and an alkanol, such as ethanol or 1-propanol. The reaction time is generally between 3 and 10 hours and is generally conducted at temperatures of 60° C. to 110° C. The time and temperature are interdependent so that when the temperature is lower, the time is longer.
The sixth step (Step F) involves the oxidation of a compound of formula XVI to produce one of Formula XVII. The oxidation is best accomplished using a reagent such as chromium trioxide in a mixture of acetic acid and water. The reaction is advantageously conducted at ambient temperatures but temperatures somewhat higher or lower may be used.
The seventh step (Step G) consists of the alkylation of a compound of Formula XVII to produce one of Formula V. This first involves formation of the anion of a compound of Formula XVII by treatment with a base, such as an alkali metal alkoxide, for example, potassium tert.-butoxide in tert.-butyl alcohol. An alkali metal hydride, such as sodium hydride and the like, or an alkali metal amide, such as sodium amide, lithium amide and the like, also may be used. The anion is then treated with an alkylating agent, Alkyl-X. Solvents which are inert to the reactants may be employed. Suitable solvents are 1,2-dimethoxyethane, tert.-butyl alcohol, dimethylformamide, benzene and the like. The reaction is conducted at a temperature in the range from about 25° C. to about 150° C.
The eighth step (Step H) consists of the ether cleavage of a compound of Formula V to produce one of Formula XVIII. This reaction is carried out under conditions similar to those described earlier for the conversion of compounds of Formula VII to those of Formula IV.
The ninth step (Step I) consists of the etherification of a compound of Formula XVIII to one of Formula IX. This reaction is carried out under conditions described for the conversion of compounds of Formula IV to those of Formula IC.
Compound VIII may be prepared by one of two methods. The first method (Step J) involves the hydrolysis or pyrolysis of a compound of Formula IX to produce one of Formula VIII. This reaction is carried out by the methods described for the conversion of compounds of Formula IC or ID to those of Formula II.
The second method for the preparation of compounds of Formula VIII is the etherification of compounds of Formula XVIII. This reaction is carried out by the methods described for the conversion of compounds of Formula IV to those of Formula II.
As mentioned earlier, the compounds of this invention possess one and sometimes two or three asymmetric carbon atoms. In the instances where they possess two or three asymmetric carbon atoms, the reaction whereby these chiral centers are established can produce two or four diastereomers. These may be separated to obtain each pure diastereomer by methods well known to those skilled in the art, such as by fractional crystallization, column chromatography, high pressure liquid chromatography and the like.
Those compounds possessing only one asymmetric carbon atom, as well as each pure diastereomer from compounds possessing two or three asymmetric carbon atoms, consist of a racemate composed of two enantiomers. The resolution of the two enantiomers may be accomplished by forming a salt of the racemic mixture with an optically active base such as (+) or (-) amphetamine, (-) cinchonidine, dehydroabietylamine, (+) or (-)-α-methylbenzylamine, (+) or (-)-α-(1-naphthyl)ethylamine, (+) cinchonine, brucine, or strychnine and the like in a suitable solvent such as methanol, ethanol, 2-propanol, benzene, acetonitrile, nitromethane, acetone and the like. There is formed in the solution two diastereomeric salts one of which is usually less soluble in the solvent than the other. Repetitive recrystallization of the crystalline salt generally affords a pure diasteriomeric salt from which is obtained the desired pure enantiomer. The optically pure enantiomer of the [5,6,9-a-substituted-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]alkanoic cycloalkanoic acid is obtained by acidification of the salt with a mineral acid, isolation by filtration and recrystallization of the optically pure antipode.
The other optically pure antipode may generally be obtained by using a different base to form the diastereomeric salt. It is of advantage to isolate the partially resolved acid from the filtrates of the purification of the first diastereomeric salt and to further purify this substance through the use of another optically active base. It is especially advantageous to use an optically active base for the isolation of the second enantiomer which is the antipode of the base used for the isolation of the first enantiomer. For example, if (+)-α-methylbenzylamine was used first, then (-)-α-methylbenzylamine is used for the isolation of the second (remaining) enantiomer.
The compounds of Formula I which are esters (i.e. compounds of Formula IC, where R 3 is lower alkyl, alkenyl, alkynyl, cycloalkyl, substituted alkyl, such as carboxyalkyl, alkoxycarbonylalkyl, hydroxyalkyl, carboxycycloalkyl, dihydroxyalkyl, trihydroxyalkyl, oxoalkyl, diloweralkylaminoalkyl, heterocyclic-alkyl, aralkyl and aryl) can be prepared by a variety of methods including one or more of the following seven methods.
The first method involves the etherification of compounds of Formula IV with a haloalkanoic acid ester or halocycloalkanoic acid ester such as, X--A--COOR 3 , where X is halo and A is defined previously to produce compounds of Formula IC. The reaction is illustrated graphically below: ##STR12##
In general, the reaction is conducted in the presence of a base, such as an alkali metal carbonate, hydroxide or alkoxide such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium ethoxide and the like. Solvents which are essentially inert to the reactants and product and in which the reactants and product are reasonably soluble are usually employed. Dimethylformamide, ethanol and acetone, for example, have been found to be especially advantageous to use as solvents. The reaction may be conducted at a temperature in the range from about 25° C. to the boiling point temperature of the particular solvent employed. The reaction is generally complete in about 15 to 60 minutes; but, if lower temperatures are employed or if the particular halo ester is not very reactive, the reaction time may be much longer.
The second method for the synthesis of compounds of Formula IC involves the cyclization of compounds of Formula X to produce those of Formula IC. This method will be discussed later.
The third method for the preparation of compounds of Formula IC involves the esterification of compounds of Formula II. This may be accomplished by well known esterification methods such as those described for the conversion of compounds of Formula VIII to those of Formula IX (vide infra).
A fourth method involves a transesterification process as shown below. ##STR13## This involves heating an ester of Formula ID (where R 4 is selected from the same group as R 3 except it cannot be identical to R 3 in this reaction). The reaction proceeds successfully with a variety of alcohols (R 3 OH) and is generally carried out in the presence of a catalytic amount of R 3 OM where M is a sodium or potassium ion. The reaction is carried out in the presence of an ion-exchange resin, such as, amberlite and the like. Solvents, such as, methylene chloride, chloroform, carbon tetrachloride, are employed and the reaction is conducted at temperatures ranging from 30° C. to the boiling point of the solvent employed. The reaction time varies from 2 hours to one day.
A fifth method consists of the esterification of a salt of the corresponding carboxylic acid (II) with the appropriate alkyl or aralkyl halide (R 3 X) where X represents halogen. ##STR14##
The reaction is carried out in the presence of a base, such as, potassium carbonate, sodium carbonate and the like which generates the corresponding salt of the compound of Formula II. The reaction is generally carried out in the presence of a solvent such as, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, and the like at temperatures usually in the range of 50° to 120° C. The reaction time varies from one to 24 hours depending on the temperature and the nature of the reactants.
A sixth method consists of the reaction of a mixed anhydride of Formula XIX with an appropriate alcohol R 3 OH. ##STR15##
The mixed anhydride is generally generated in situ from the corresponding carboxylic acid (Formula II) and ethyl chloroformate in tetrahydrofuran (or similar solvent) at a low temperature (such as, -10° C. to +10° C.) in the presence of an appropriate base (such as triethylamine and the like). The alcohol, R 3 OH, is added and the reaction mixture gradually increased to ambient temperature over a period of one to 5 hours and finally heated at 50° C. to the boiling point of the solvent for one to 6 hours.
The seventh method involves the reaction of a 1-acylimidazole derivative of Formula XX with an alcohol of Formula R 3 OH. ##STR16##
The acylimidazole (XX) is generally prepared in situ by the reaction of a Compound II with 1,1'-carbonyldiimidazole in a solvent (such as tetrahydrofuran, 1,4-dioxane and the like) at a temperature of -10° to +10° C. Reaction of the alcohol (R 3 OH) with XX is generally conducted in the presence of a catalytic amount of a base (such as sodium hydride), KOC(CH 3 ) 3 and the like). The reaction is generally carried out at temperatures between 0° C. and ambient temperature and requires from one to 24 hours for completion.
It should be pointed out that the R 3 moiety of the esters of Formula IC may possess a chemically reactive function which requires the presence of a chemical protective group during one or another of the seven synthetic methods described. These protective groups may be removed by one of several processes, such as selective hydrolysis, hydrogenolysis and the like.
The preparation of derivatives of the carboxylic acids (Formula II) of the invention are accomplished by methods well known by those skilled in the art. For example, an anhydride of Formula XXI is prepared from a compound of Formula II by reaction with a carbodiimide in an organic solvent. ##STR17## For example a compound of Formula II can be reacted with a carbodiimide, such as N,N'-dicyclohexylcarbodiimide or N,N'-di-p-tolylcarbodiimide in a solvent such as benzene, chlorobenzene, methylene choride or dimethylformamide to produce a compound of Formula XXI.
The amide, hydrazide, guanidide and the like derivatives (Formula XXII) of compounds of the invention are prepared by methods well known to those skilled in the art. For example, a compound of Formula II is converted to the acylimidazole (XX) (described above) which, in turn, is treated ##STR18## with the appropriate base (R 4 R 5 NH) to obtain the desired derivative (Formula XXII). Thus, if R 4 R 5 NH represents ammonia or an amine, i.e., where R 4 and R 5 are hydrogen or lower alkyl, and the like, the product is an amide. If R 4 R 5 NH represents a hydrazide, i.e., R 4 is amino or dilower-alkylamino and R 5 is hydrogen or lower alkyl, the product is a hydrazide. If R 4 is ##STR19## and R 5 is hydrogen the product is guanidide.
The reactions described may be conducted in an excess of the reactant base as a solvent or one may use a conventional solvent, such as dimethylformamide, 1-methylpyrrolidin-2-one and the like.
The acid addition salts of Formula XXIII (where B + represents a cation from a pharmaceutically acceptable base) are prepared by reacting a carboxylic acid of Formula II with an appropriate alkali metal or alkaline earth bicarbonate, carbonate or alkoxide, an amine, ammonia, an organic quaternary ammonium hydroxide, guanidine and the like. The reaction is illustrated below: ##STR20##
The reaction is generally conducted in water but when alkali metal hydroxides and alkoxides and the organic bases are used, the reaction can be conducted in an organic solvent, such as ethanol, dimethylformamide and the like.
The preferred salts are the sodium, ammonium, diethanolamine, 1-methylpiperazine, piperazine and the like salts.
Inasmuch as there is a wide variety of symptoms and severity associated with grey matter edema, particularly when it is caused by blows to the head or spinal chord, the precise treatment protocol is left to the practitioner. It is up to the practitioner to determine the patient's response to treatment and to vary the dosages accordingly. A recommended dosage range is from 1 μg. to 10 mg./kg of body weight as a primary dose and a sustaining dose of half to equal the primary dose, every 4 to 24 hours.
The compounds of this invention can be administered by a variety of established methods, including intravenously, intramuscularly, subcutaneously, and orally. As with dosage, the precise mode of administration is left to the discretion of the practitioner.
Recent studies in experimental head injury by R. S. Bourke et al. (R. S. Bourke, M. A. Daze and H. K. Kimelberg, Monograph of the International Glial Cell Symposium, Leige, Belgium, August 29-31, 1977 and references cited therein) and experimental stroke by J. H. Garcia et al. (J. H. Garcia, H. Kalimo, Y. Kamijyo and B. F. Trump, Virchows Archiv. [Zellopath.], 25, 191 (1977), indicate that astroglial swelling, a secondary and spotentially inhibitable process, is a fundamental pathophysiological response to ischemic/traumatic brain insult in both pathological disorders. Furthermore, astroglial swelling is believed to reduce oxygen available to neurons by prolongation of the oxygen diffusion pathaway. Thus, the damage to cerebral grey matter may be far more extensive as a result of pathological events secondary to astroglial swelling than as a result of damage inflicted by the initial ischemic/traumatic insult. Consequently, it is of prime importance than the treatment commence as soon as possible after the initial trauma in order to minimize the brain cell damage and the possibility of death or permanent paralysis.
One aspect of this invention is the treatment of persons with grey matter edema by concomitant administration of a compound of formula I, IC or II or a pharmaceutically acceptable salt, or amide thereof and an antiinflammatory steroid. These steroids are of some, albeit limited, use in control of white matter edema associated with ischemic stroke and head injury. Steroid therapy is given according to established practice as a supplement to the compound of formula I, IC or II as taught elsewhere herein.
The compounds of formula I, IC, or II are utilized by formulating them in a composition such as tablet, capsule or elixir for oral administration. Sterile solutions or suspensions can be used for parenteral administration. About 70 μg to 750 mg. of a compound or mixture of compounds of formulae I, IC, or II or a physiologically acceptable salt, or amide is compounded with a physiologically acceptable vehicle, carrier, excipient, binder, preservative, stabilizer, flavor, etc. in a unit dosage form as called for by accepted pharmaceutical practice. The amount of active substance in the composition is such that dosage in the range indicated is obtained.
Illustrative of the adjuvants which may be incorporated in tablets, capsules and the like are the following: a binder such as gum tragacanth, acacia, corn starch or gelatin; an excipient such as dicalcium phosphate; a disintegrating agent such as corn starch, potato starch, alginic acid and the like; a lubricant such as magnesium stearate; a sweetening agent such as sucrose, lactose, or saccharin; a flavoring agent such as peppermint, oil or wintergreen or cherry. When the dosage unit form is a capsule, it may contain in addition to materials of the above type a liquid carrier such as a fatty oil. Various other materials may be present as coatings or to otherwise enhance the pharmaceutical elegance of the preparation. For instance, tablets may be coated with shellac, sugar or the like. A syrup or elixir may contain the active compound, sucrose as a sweetening agent, methyl and propyl parabens as preservatives, a dye and a flavoring such as cherry or orange flavor.
Sterile compositions for injection can be formulated according to conventional pharmaceutical practice by dissolving or suspending the active substance in a conventional vehicle such as water for injection, a naturally occurring vegetable oil like sesame oil, coconut oil, peanut oil, cottonseed oil, etc., or a synthetic fatty vehicle like ethyl oleate or the like. Buffers, preservatives, antioxidants and the like can be incorporated as required.
The following examples are included to illustrate the preparation of representative dosage forms.
EXAMPLE 1
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-Fluoren-7-yl)oxy]acetic Acid
Steps A and B. 5,6-Dichloro-9a-ethyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one
6,7-Dichloro-2-ethyl-5-methoxy-2,3-dihydro-1H-inden-1-one (32.4 gm., 0.125 mole) is dissolved in tetrahydrofuran (300 ml.) and 40% triton-B in methanol (3 ml.) is added. Methyl vinyl ketone (12.3 gm., 0.175 moles) is added dropwise to the stirring reaction mixture over a period of 10 minutes. The temperature rises from 26° C. to 35° C. The mixture is stirred for an additional hour and most of the volatile material is removed by evaporation in vacuo using a rotary evaporator.
Water (200 ml.) is added and the mixture extracted with ether (three 100 ml. portions). The combined ether extracts are dried over Na 2 SO 4 and then evaporated in vacuo to give a residual oil which is 6,7-dichloro-2-ethyl-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one. The material is dissolved in dry benzene (200 ml.), placed in a constant water separator (Dean-Stark), treated with acetic acid (1.5 ml.) and pyrrolidine (1.5 ml.). The mixture is refluxed for two hours after which time water ceases to separate. Then the solvent is distilled until only 50 ml. remains and then methanol (100 ml.) is added. Upon chilling in an ice bath, 5,6-dichloro-9a-ethyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (16.2 gm.) separates, m.p. 159°-165° C. This material is satisfactory for use in the next step.
Step C. 5,6-Dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one
5,6-Dichloro-9a-ethyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (15 gm., 0.048 mole) is mixed with pyridine hydrochloride (120 gm.) in a reaction vessel and heated in a metal bath at 195°-200° C. for 30 minutes. The mixture is cooled somewhat and poured with stirring into cold water (800 ml.). The solid that separates is removed by filtration and washed with water. After drying, the product is triturated with acetonitrile (80 ml.) at 60°, cooled, filtered and dried. The yield of crude 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is 12.2 gm., m.p. 260°-265° C. This material is pure enough for use in the next step.
Step D. Ethyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (6.0 gm., 0.02 mole), ethyl bromoacetate (4.0 gm., 0.025 mole) and potassium carbonate (8.3 gm., 0.06 mole) in dimethylformamide (35 ml.) is heated at 50° C. and stirred for one hour. The mixture is cooled and poured into water (300 ml.). The solid product that separates is removed by filtration, then washed with water followed by benzene (10 ml.).
The yield of ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate after drying, is 6.9 gm. After two recrystallizations from acetonitrile 4.8 gm. remains, m.p. 164°-166° C.
Step E. [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic Acid
Ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.8 gm., 0.012 mole) is dissolved in acetic acid (30 ml.) containing 5% aqueous hydrochloride acid (10 ml.). The mixture is heated and stirred on a steam bath for an hour. The solution is diluted with water (8 ml.) and cooled. The product that separates is recrystallized twice from a 1:6 (v/v) mixture of water and acetic acid. The yield of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid is 2.6 gm., m.p. 237°-238° C.
Anal. Calcd. for C 17 H 16 Cl 2 O 4 : C, 57.48; H, 4.54. Found: C, 57.97; H, 4.43. C, 57.21; H, 4.29.
Using a procedure similar to that described in Example 1, except in Step A there is substituted for the 6,7-dichloro-2-ethyl-5-methoxy-2,3-dihydro-1H-inden-1-one an equimolar amount of:
EXAMPLE 2
Step A. 6,7-Dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 3
Step A. 6,7-Dichloro-5-methoxy-2-methyl-2,3-dihydro-1H-inden-1-one.
EXAMPLE 4
Step A. 6,7-Dichloro-5-methoxy-2-propyl-2,3-dihydro-1H-inden-1-one.
EXAMPLE 5
Step A. 6,7-Dichloro-2-isopropyl-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 6
Step A. 2-Butyl-6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 7
Step A. 6,7-Dichloro-2-isobutyl-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 8
Step A. 6,7-Dichloro-2-cyclopetyl-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 9
Step A. 2-Benzyl-6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one.
EXAMPLE 10
Step A. 6,7-Dichloro-5-methoxy-2-phenyl-2,3-dihydro-1H-inden-1-one.
In Examples 2, Step A through Example 10, Step A, the reaction is carried out as described in Example 1, Step A, then by using each product and conducting the reaction as in Example 1, Step B, there is obtained:
EXAMPLE 2
Steps A and B: 6,7-Dichloro-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 3
Steps A and B. 6,7-Dichloro-5-methoxy-2-methyl-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-7-methoxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 4
Steps A and B. 6,7-Dichloro-5-methoxy-2-(3-oxobutyl)-2-propyl-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-7-methoxy-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 5
Steps A and B. 6,7-Dichloro-2-isopropyl-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-9a-isopropyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 6
Steps A and B. 2-Butyl-6,7-dichloro-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 9a-butyl-5,6-dichloro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-one.
EXAMPLE 7
Steps A and B. 6,7-Dichloro-2-isobutyl-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-9a-isobutyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 8
Steps A and B. 6,7-Dichloro-2-cyclopentyl-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-9a-cyclopentyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 9
Steps A and B. 2-Benzyl-6,7-dichloro-5-methoxy-2-(3-oxobutyl)-2,3-dihydro-1H-inden-1-one and then 9a-benzyl-5,6-dichloro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 10
Steps A and B. 6,7-Dichloro-5-methoxy-2-(3-oxobutyl)-2-phenyl-2,3-dihydro-1H-inden-1-one and then 5,6-dichloro-7-methoxy-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
Carrying out the reaction as described in Example 1, Step C, except that the 5,6-dichloro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one of Example 1, Step C is substituted by an equimolar quantity of the product of Example 2, Step B, Example 3, Step B, Example 4, Step B, Example 5, Step B, Example 6, Step B, Example 7, Step B, Example 8, Step B, Example 9, Step B, and Example 10, Step B to obtain:
EXAMPLE 2
Step C. 5,6-Dichloro-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 3
Step C. 5,6-Dichloro-7hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 4
Step C. 5,6-Dichloro-7-hydroxy-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 5
Step C. 5,6-Dichloro-7-hydroxy-9a-isopropyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 6
Step C. 9a-Butyl-5,6-dichloro-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 7
Step C. 5,6-Dichloro-9a-isobutyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 8
Step C. 5,6-Dichloro-9a-cyclopentyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 9
Step C. 9a-Benzyl-5,6-dichloro-7hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 10
Step C. 5,6-Dichloro-7-hydroxy-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
Carrying out the reaction as described in Example 1, Step D, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a -tetrahydro-3H-fluoren-3-one of Example 1, Step D, is substituted by an equimolar quantity of the product of Example 2, Step C, Example 3, Step C, Example 4, Step C, Example 5, Step C, Example 6, Step C, Example 7, Step C, Example 8, Step C, Example 9, Step C or Example 10, Step C to obtain:
EXAMPLE 2
Step D. Ethyl [(5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 3
Step D. Ethyl [(5,6-dichlor-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 4
Step D. Ethyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 5
Step D. Ethyl [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H -fluoren-7-yl)oxy]acetate.
EXAMPLE 6
Step D. Ethyl [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 7
Step D. Ethyl [(5,6-dichloro-9a-isobutyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 8
Step D. Ethyl [(5,6-dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 9
Step D. Ethyl [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 10
Step D. Ethyl [(5,6-dichloro-3-oxo-9a-phenyl1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Carrying out the reaction as described in Example 1, Step E. except that the ethyl [(5,6-di-chloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate of Example 1, Step E is substituted by an equimolar quantity of the product of Example 2, Step D, Example 3, Step D, Example 4, Step D, Example 5, Step D, Example 6, Step D, Example 7, Step D, Example 8, Step D, Example 9, Step D or Example 10, Step D, there is obtained:
EXAMPLE 2
Step E. [(5,6-Dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 3
Step E. [(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 4
Step E. [(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 5
Step E. [(5,6-Dichloro-3-oxo-9a-isopropyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 6
Step E. [(9a-Butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H fluoren-7-yl)oxy]acetic acid.
EXAMPLE 7
Step E. [(5,6-Dichloro-9a-isobutyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 8
Step E. [(5,6-Dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 9
Step E. [(9a-Benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 10
Step E. [(5,6-Dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
By carrying out the reaction as described in Example 1, Step D, except that the ethyl bromoacetate is substituted by an equimolar quantity of:
EXAMPLE 11
Step A. Ethyl 2-bromopropanoate.
EXAMPLE 12
Step A. Ethyl 2-bromobutyrate.
EXAMPLE 13
Step A. Ethyl 2-bromo-2-methylpropanoate.
EXAMPLE 14
Step A. Ethyl 1-bromocyclobutane-1-carboxylate.
There is obtained:
EXAMPLE 11
Step A. Ethyl 2-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-propanoate.
EXAMPLE 12
Step A. Ethyl 2-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]butyrate.
EXAMPLE 13
Step A. Ethyl 2-methyl-2-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-propanoate.
EXAMPLE 14
Step A. Ethyl 1-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclobutane-1-carboxylate.
By carrying out the reaction as described in Example 1, Step D, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is substituted by 5,6-dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (Example 3, Step C) and the ethyl bromoacetate substituted by Example 15, Step A: ethyl 2-bromo-2-methylpropanoate Example 16, Step A: ethyl 1-bromocyclobutane-1-carboxylate. There is obtained:
EXAMPLE 15
Step A. Ethyl 2-methyl-2-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]propanoate.
EXAMPLE 16
Step A. Ethyl 1-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclobutane-1-carboxylate.
By carrying out the reaction as described in Example 1, Step E, except that the ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is substituted by the product of Example 11, Step A, Example 12, Step A, Example 13, Step A, Example 14, Step A, Example 15, Step A, or Example 16, Step A, whereby there is obtained:
EXAMPLE 11
Step B. 2-[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]propanoic acid.
EXAMPLE 12
Step B. 2-[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]butyric acid.
EXAMPLE 13
Step B. 2-Methyl-2-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-propanoic acid.
EXAMPLE 14
Step B. 1-[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclobutane-1-carboxylic acid.
EXAMPLE 15
Step B. 2-Methyl-2-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]propanoic acid.
EXAMPLE 16
Step B. 1-[(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclobutane-1-carboxylic acid.
EXAMPLE 17
3-[(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]propanoic acid
5,6-Dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (9.0 gm., 0.03 mole) is dissolved in 10% aqueous sodium hydroxide solution (35 ml.). The solution is heated to boiling with stirring, the heat source is removed and β-propiolactone (23.8 gm., 0.33 mole) is added at such a rate to keep the solution boiling. During the reaction, 10% aqueous sodium hydroxide is added as necessary to keep the reaction mixture alkaline to litmus paper.
When the reaction is complete, the solution is cooled and made acid to Congo red paper with 6 normal hydrochloric acid. The product that separates is removed by filtration and dissolved by treatment with a 5% solution of sodium hydroxide (three 50 ml. portions). The combined aqueous extracts are acidified to Congo red paper with 6 normal hydrochloric acid. The product is removed by filtration, washed with water and dried. Recrystallization from a mixture of acetic acid and water gives pure 3-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a -tetrahydro-3H-fluoren-7-yl)oxy]propanoic acid.
Carrying out the reaction as described in Example 17 except that the 5,6-dichloro-9a-methyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is substituted by an equimolar quantity of:
EXAMPLE 18
5,6-Dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
EXAMPLE 19
5,6-Dichloro-7-hydroxy-9a-isopropyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one. There is obtained:
EXAMPLE 18
3-[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]propanoic acid.
EXAMPLE 19
3-[(5,6-Dichloro-9a-isopropyl -3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]propanoic acid.
EXAMPLE 20
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. Methyl [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate
[(6,7-Dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid (31.7 gm. 0.1 mole) is dissolved in dimethylformamide (300 ml.) and potassium carbonate (20.7 gm., 0.15 mole) is added. The mixture is stirred and heated at 60° C. for 10 minutes in a vessel protected from atmospheric moisture. Methyl iodide (12.6 ml., 28.4 gm., 0.2 mole) is added and heating and stirring continued for 3 hours. The mixture is cooled, added, with stirring to water (3 liters) and the solid that separated removed by filtration and dried. Recrystallization from methanol gives 27 gm. of methyl [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
Step B. Methyl {[6,7-dichloro-2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}-acetate
Methyl [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate (15.8 gm., 0.05 mole) is suspended in dry tetrahydrofuran (100 ml.) containing trition-B (1 ml.). The suspension is stirred at ambient temperature and methyl vinyl ketone (5.02 gm., 0.072 mole) is added. The solution which becomes warm initially, is stirred at ambient temperature for 4 hours. Then, the stirring solution is treated with methyl vinyl ketone (0.3 ml.) and triton-B (0.6 ml.) every 4 hours for the next twenty hours.
The reaction mixture is evaporated in vacuo at 50° C. and the residual material dissolved in ether (100 ml.). The ether solution is washed with water (two 20 ml. portions), dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated in vacuo and the residue triturated with ether (10 ml.), filtered and dried. The yield of methyl {[6,7-dichloro-2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}actetate is 12.3 gm., m.p. 78°-79° C. This material is adequate for use in the next step.
Step C. Methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of methyl {[6,7-dichloro-2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate (9.0 gm., 0.024 mole), pyrrolidine (1.70 gm., 0.024 mole) and acetic acid (1.42 gm., 0.024 mole) in toluene (100 ml.) is heated at 85° C. for one hour. The solution is concentrated in vacuo at 50° C. to obtain the crude product.
The product is subjected to column chromatography on silica gel (300 gm.) using a mixture of dichloromethane and tetrahydrofuran (100/4 v./v.) as the eluent. The yield of pure methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetate is 5.05 gm., m.p. 182°-183° C.
Step D. [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.0 gm., 0.011 mole) is added to a solution composed of 20% aqueous sodium hydroxide solution (4.32 ml., 0.022 mole) and methanol (45 ml.). The mixture is stirred and heated at reflux for two hours and then concentrated in vacuo at 50° C. The residue is dissolved in water (50 ml.) and made acid to Congo red paper with 6 normal hydrochloric acid. The solid that separates is removed by filtration, washed with water, then with a little methanol and finally with a little ether. After drying, the product weighs 3.14 gm., m.p. 235° C. After recrystallization from acetic acid, the yield of pure [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is 2.61 gm., m.p. 237°-239° C.
Anal. Calcd. for C 17 H 16 Cl 2 O 4 : C, 57.48; H, 4.54. Found: C, 57.35; H, 4.62.
Carrying out the reaction as described in Example 20, Step A, except that the [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid is substituted by an equimolar quantity of:
EXAMPLE 21
Step A. [(6,7-Dichloro-1-oxo-2-propyl-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
EXAMPLE 22
Step A. [(2-Butyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
EXAMPLE 23
Step A. [(2-Ethyl-6,7-dimethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
EXAMPLE 24
Step A. [(2-Ethyl-1-oxo-2,3-dihydro-1H-benz[e]inden-5-yl)oxy]acetic acid. There is obtained:
EXAMPLE 21
Step A. Methyl [(6,7-dichloro-1-oxo-2-propyl-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
EXAMPLE 22
Step A. Methyl [(2-Butyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
EXAMPLE 23
Step A. Methyl [(2-ethyl-6,7-dimethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
EXAMPLE 24
Step A. Methyl [(2-ethyl-1-oxo-2,3-dihydro-1H-benz[e]inden-5-yl)oxy]acetate.
Carrying out the reaction as described in Example 20, Step B, except that the methyl [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate is substituted by an equimolar quantity of the product of Example 21, Step A, Example 22, Step A, Example 23, Step A or Example 24, Step A. There is obtained:
EXAMPLE 21
Step B. Methyl {[6,7-dichloro-2-propyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate, m.p. 91°-93° C.
EXAMPLE 22
Step B. Methyl {[6,7-dichloro-2-butyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate, m.p. 92°-93° C.
EXAMPLE 23
Step B. Methyl {[2-ethyl-6,7-dimethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate.
EXAMPLE 24
Step B. Methyl {[2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-benz[e]inden-5-yl]oxy}acetate.
Carrying out the reaction as described in Example 20, Step C, except that the methyl{[6,7-dichloro-2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate is substituted by an equimolar quantity of the product of Example 21, Step B, Example 22, Step B, Example 23, Step B, or Example 24, Step B, there is obtained:
EXAMPLE 21
Step C. Methyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, m.p. 158°-159° C.
EXAMPLE 22
Step C. Methyl [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, 153.5°-154° C.
EXAMPLE 23
Step C. Methyl [(9a-ethyl-5,6-dimethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetate.
EXAMPLE 24
Step C. Methyl [(7a-ethyl-10-oxo-7,7a,8,9-tetrahydro-10H-benzo[c]fluoren-5-yl)oxy]acetate.
Carrying out the reaction as described in Example 20, Step D, except that the methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is substituted by an equimolar quantity of the product of Example 21, Step C, Example 22, Step C, Example 23, Step C or Example 24, Step C. There is obtained:
EXAMPLE 21
Step D. [(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 22
Step D. [(9a-Butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 23
Step D. [(9a-Ethyl-5,6-dimethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 24
Step D. [(7a-Ethyl-10-oxo-7,7a,8,9-tetrahydro-10H-benzo[c]fluoren-5yl)oxy]acetic acid.
EXAMPLE 25
[(5,6-Dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. Methyl [(6,7-dichloro-2-isopropyl-1-oxo-2,3-dihydro-1H-inden-5yl)oxy]acetate
[(6,7-Dichloro-2-isopropyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid 33.4 gm. 0.1 mole) is dissolved in dimethylformamide (300 ml.) and potassium carbonate (20.7 gm., 0.15 mole) is added. The mixture is stirred and heated at 60° C. for 10 minutes in a vessel protected from atmosphere moisture. Methyl iodide (12.6 ml., 28.4 gm., 0.2 mole) is added and heating and stirring continued for 3 hours. The mixture is cooled, added, with stirring to water (3 liters) and the solid that separated removed by filtration and dried. Recrystallization from methanol gives methyl [(6,7-dichloro-2-isopropyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
Step B. Methyl {[6,7-dichloro-2-isopropyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate
Methyl [(6,7-dichloro-2-isopropyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate (16.5 gm., 0.05 mole) is suspended in dry tetrahydrofuran (100 ml.) containing triton-B (1 ml.). The suspension is stirred at ambient temperature and methyl vinyl ketone (5.02 gm., 0.072 mole) is added. The solution which becomes warm initially, is stirred at ambient temperature for 4 hours. Then, the stirring solution is treated with methyl vinyl ketone (0.3 ml.) and triton-B (0.6 ml.) every 4 hours for the next twenty hours.
The reaction mixture is evaporated in vacuo at 50° C. and the residual material dissolved in ether (100 ml.). The ether solution is washed with (two 20 ml. portions), dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated in vacuo and the residue triturated with ether (10 ml.), filtered and dried. The product is methyl [6,7-dichloro-2-isopropyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy acetate.
Step C. Methyl [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-floren-7-yl)oxy]acetate
A mixture of methyl [(6,7-dichloro-2-isopropyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl)oxy]acetate (9.3 gm., 0.024 mole), potassium tert.-butoxide (2.70 gm., 0.024 mole) and tert.-butyl alcohol (100 ml.) is heated at 85° C. for three hours. The solution is concentrated in vacuo at 50° C. to obtain the crude product.
The product is subjected to column chromatography on silica gel (300 gm.) using a mixture of dichloromethane and tetrahydrofuran (100/4 v./v.) as the eluent. The product is pure methyl [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetate.
Step D. [(5,6-Dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Methyl [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.2 gm., 0.011 mole) is added to a solution composed of 20% aqueous sodium hydroxide solution (4.32 ml., 0.022 mole) and methanol (45 ml.). The mixture is stirred and heated at reflux for two hours and then concentrated in vacuo at 50° C. The residue is dissolved in water (50 ml.) and made acid to Congo red paper with 6 normal hydrochloric acid. The solid that separates is removed by filtration, washed with water, then with a little methanol and finally with a little ether. After drying, the product is recrystallized from acetic acid to give pure [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid. Using a procedure similar to that described in Example 25, except that in Step A there is substituted for the [(6,7-dichloro-2-isopropyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid, an equimolar amount of:
EXAMPLE 26
Step A. [(6,7-Dichloro-2-cyclopentyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
EXAMPLE 27
Step A. [(6,7-Dichloro-1-oxo-2-phenyl-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
EXAMPLE 28
Step A. [(2-Benzyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid.
In Examples 26, Step A through 28, Step A, the reaction is carried out as described in Example 25, Step A, there is obtained:
EXAMPLE 26
Step A. Metyl [(6,7-dichloro-2-cyclopentyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
EXAMPLE 27
Step A. Methyl [(6,7-dichloro-1-oxo-2-phenyl-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
EXAMPLE 28
Step A. Methyl [(2-benzyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
In Example 25, Step B, the starting material is the product from Step A. Using the products from step A of Example 26, 27 and 28 as starting materials but conducting the reaction as in Example 25, Step B, there is obtained:
EXAMPLE 26
Step B. Methyl {[[6,7-dichloro-2-cyclopentyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy]}acetate
EXAMPLE 27
Step B. Methyl {[6,7-dichloro-1-oxo-2-(3-oxobutyl)-2-phenyl-2,3-dihydro-1H-inden-5-yl]oxy}acetate.
EXAMPLE 28
Step B. Methyl {[2-benzyl-6,7-dichloro-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}acetate.
Using the products from Step B of Example 26, 27, 28 as starting material in place for the Example 25, Step B, and conducting the reaction as in Example 25, Step C there is obtained:
EXAMPLE 26
Step C. Methyl [(5,6-dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 27
Step C. Methyl [(5,6-dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetate.
EXAMPLE 28
Step C. Methyl [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 28
Step C. Methyl [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Using the products from Step C of Examples 26, 27 and 28 as starting materials in place of the product from Example 25, Step C and conducting the reaction as in Example 25, Step D, there is obtained:
EXAMPLE 26
Step D. [(5,6-Dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 27
Step D. [(5,6-Dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 28
Step D. [(9a-Benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 29
[(5,6-Dichloro-3-oxo-2-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid.
Step A. Methyl [(6,7-dichloro-2-ethylidene-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate
[(6,7-Dichloro-2-ethylidene-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetic acid (U.S. Pat. No. 3,704,314) (30.1 gm., 0.1 mole) is dissolved in methanol (150 ml.) and conc. sulfuric acid (0.5 ml.) added. The mixture is stirred and refluxed for 2 hours. The solvent is removed in vacuo by evaporation on a rotary evaporator and the residue dissolved in ethyl ether, washed with water and dried over sodium sulfate. The ether is removed by evaporation in vacuo in a rotary evaporator to give methyl[(6,7-dichloro-2-ethylidene-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
Step B. Methyl [6,7-dichloro-1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy acetate.
Methyl (6,7-dichloro-2-ethylidene-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate (25.4 gm., 0.08 mole) is dissolved in 1,2-dimethoxyethane (350 ml.) which had been boiled and cooled under dry nitrogen. Maintaining an atmosphere of dry nitrogen, the solution is cooled to 0° C. and potassium tert.-butoxide (900 mg., 0.008 mole) is added. Keeping the temperature at 0°, methyl vinyl ketone (11.2 gm., 0.16 mole) is added with stirring over 30 minutes. After stirring 2 hours at 0° C., the reaction mixture is allowed to warm to ambient temperature overnight. The solvent is removed in vacuo in a rotary evaporator, and the residue dissolved in ether, washed with water and dried over anhydrous magnesium sulfate. Evaporation of the ether in vacuo gave methyl [6,7-dichloro-1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy acetate.
Step C. Methyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of methyl {[[6,7-dichloro-1-oxo-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5yl)oxy}acetate (9.0 gm., 0.024 mole), pyrrolidine (1.70 gm., 0.024 mole) and acetic acid (1.42 gm., 0.024 mole) in toluene (100 ml.) is heated at 85° C. for one hour. The solution is concentrated in vacuo at 50° C. to obtain the crude product.
The product is subjected to column chromatography on silica gel (300 gm.) using a mixture of dichloromethane and tetrahydrofuran (100/4 v./v.) as the eluent. The product is methyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step D. [(5,6-Dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Methyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.0 gm., 0.011 mole) is added to a solution composed of 20% aqueous sodium hydroxide solution (4.32 ml., 0.022 mole) and methanol (45 ml.). The mixture is stirred and heated at reflux for two hours and then concentrated in vacuo at 50° C. The residue is dissolved in water (50 ml.) and made acid to Congo red paper with 6 normal hydrochloric acid. The solid that separates is removed by filtration, washed with water, then with a little methanol and finally with a little ether. After recrystallization from acetic acid, there is obtained pure [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Alternatively, [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetic acid may be produced by the following process.
Methyl{[6,7-dichloro-1-oxo-2-(3-oxobutyl)-2-vinyl-2,3-dihydro-1H-inden-5-yl]oxy}acetate (7.3 gm., 0.02 mole) is dissolved in a solution of methanol (100 ml) and water (50 ml.) containing sodium hydroxide (9.43 gm., 0.236 mole), taking care to keep the temperature below 25° C. The solution is kept at ambient temperature for 48 hours. The solution is concentrated in vacuo to 100 ml. in a rotary evaporator at room temperature and poured into water (250 ml.) containing concentrated hydrochloric acid (26 ml.) with cooling. The product is separated by filtration, washed with water, dried and recrystallized from a mixture of acetic acid and water to obtain [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 30
[(5,6-Dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. Ethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
A solution of [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl-oxy]acetic acid (Example 29, Step D) (8.82 g., 0.025 mole) absolute ethanol (300 ml.) and 12 N HCl (5 ml.) in ethanol (20 ml.) is heated under reflux on the steam bath with stirring for an hour. The excess solvent is removed under reduced pressure. Ice and water are added to the oily residue and the product extracted into methylene chloride. After drying over MgSO 4 , the solution is concentrated to yield the product.
Recrystallization from tetrahydrofuran-etherpetroleum ether (1:1:2) gives ethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step B. Ethyl [(5,6-Dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
To a hot, rapidly stirred solution of cupric acetate monohydrate (7.0 gm., 0.02 mole) in glacial acetic acid is added zinc dust (70 gm., 1.08 gm. atom). After about 30 seconds, all the copper has deposited on the zinc. The couple is allowed to settle for 0.5 to 1 minute, then as much as possible of the acetic acid is decanted, care being taken not to lose the silt-like couple. The dark reddish-gray couple is then washed with one 100 ml. portion of acetic acid followed by three 200 ml. portions of tetrahydrofuran.
A mixture of the zinc-copper couple, prepared as described above, (48 gm.) and methylene iodide (37.5 gm.) in tetrahydrofuran (300 ml.) is heated under reflux in a nitrogen atmosphere for an hour. Ethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (8.2 gm., 0.02 mole) is added to the cooled mixture and stirring continued at 25° C. for 24 hours. The mixture is diluted with toluene (200 ml.), filtered and the filtrate is washed successively with saturated aqueous solutions of ammonium chloride and sodium bicarbonate and then with water. The organic layer is dried over anhydrous magnesium sulfate and the solvent removed using a rotary evaporator at reduced pressure. The residue is purified by column chromatography using a silica-gel column to give ethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step C. [(5,6-Dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Ethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.2 gm., 0.011 mole) is added to a solution composed of 20% aqueous sodium hydroxide solution (4.32 ml., 0.022 mole) and methanol (45ml.). The mixture is stirred and heated at reflux for two hours and then concentrated in vacuo at 50° C. The residue is dissolved in water (50 ml.) and made acid to Congo red paper with 6 normal hydrochloric acid. The solid that separates is removed by filtration, washed with water, then with a little methanol and finally with a little ether. After drying, the product is recrystallized from acetic acid to give pure [(5,6-dichloro-3-oxo-9a-cyclopropyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 31
Resolution of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. A mixture of racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid (7.1 gm., 0.02 mole) and dextro(+)cinchonine (5.89 gm., 0.02 mole) is dissolved in the minimum volume of boiling acetonitrile, is cooled to 5° C. and aged for 48 hours. The crystalline product is removed by filtration and recrystallized twice from the minimum volume of acetonitrile. (The mother liquors from each recrystallization are combined and saved).
The pure salt is suspended in water (40 ml.) treated with 6 normal hydrochloric acid (5 ml.) and the precipitate that forms is removed by filtration and dried. This pure (+) enantiomer of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic is then recrystallized from a mixture of tetrahydrofuran and ethyl ether, m.p. 238°-240° C.;
α 23 ° 589 (C=1.1), +151.2.
Step B. The combined acetonitrile mother liquors from Step A are evaporated at reduced pressure and the residue treated with water (50 ml.) and 6 normal hydrochloric acid (7.5 ml.). The resulting precipitate is removed by filtration and dried.
This residual partially resolved [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (2.86 gm., 0.0118 mole) is treated with 1(-)cinchonidine (3.47 gm., 0.0118 mole) and the mixture dissolved in the minimum quantity of acetonitrile. After cooling for 48 hours, the salt that separates is removed by filtration and recrystallized twice from the minimum volume of acetonitrile. The pure salt is suspended in water (50 ml.), treated with 6 normal hydrochloric acid (5 ml.) and the precipitate that separates is removed by filtration and dried. This solid is recrystallized from a mixture of tetrahydrofuran and ethyl ether to give the (-) enantiomer of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid, m.p. 239°-241° C.,
α 23 ° 589 (C=1.1)=-151.2°.
EXAMPLE 32
Steps A and B. The Two Enantiomers of [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31 except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 1, Step E) is substituted by an equimolar quantity of racemic [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 6, Step E), there is obtained the two enantiomers of [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 33
Steps A and B. The Two Enantiomers of [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of racemic [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 47, Step L) there is obtained the two enantiomers of [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxo]acetic acid.
EXAMPLE 34
Steps A and B. The Two Enantiomers of [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 48, Step L), there is obtained the two enantiomers of [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 35
Steps A and B. The Two Enantiomers of [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3-fluoren-7-yl)oxy]acetic acid (Example 1, Step E) is substituted by an equimolar quantity of racemic [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 50, Step L), there is obtained the two enantiomers of [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 36
Steps A and B. The two enantiomers of [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Carrying out a reaction as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 1, Step E) is substituted by an equimolar quantity of racemic [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 9, Step E), there is obtained the two enantiomers of [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 37
Steps A and B. The two enantiomers of [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3-H-fluoren-7-yl)oxy]acetic acid is substituted by an equimolar quantity of [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 4, Step E) there is obtained the two enantiomers of [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 38
Steps A and B. The two enantiomers of [(5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid (Example 2, Step E), there is obtained the two enantiomers of [(5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 39
Steps A and B. The two enantiomers of [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as descrived in Example 31, except that the reacemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-b 7-yl)oxy-acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 3, Step E), there is obtained the two enantiomers of [(5,6-dichlor-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 40
Steps A and B. The two Enantiomers of [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 25, Step D), there is obtained the two enantiomers of [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid.
EXAMPLE 41
Steps A and B. The two enantimoers of [(5,6-dichloro-9a-cyclopentyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 26, Step D), there is obtained the two enantiomers of [(5,6-dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 42
Steps A and B. The two enantiomers of [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxyl]acetic acid (Example 29, Step D), there is obtained the two enantiomers of [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid.
EXAMPLE 43
Steps A and B. The two enantiomers of [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid is replaced by an equimolar quanitity of racemic [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 30, Step D), there is obtained the two enantimoers of [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 44
Steps A and B. The two enantiomers of [(5,6-dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out the resolution as described in Example 31, except that the racemic [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetic acid is replaced by an equimolar quantity of racemic [(5,6-dichloro-3-oxo-9-a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 27, Step D), there is obtained the two enantiomers of [(5,6-dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetic acid.
EXAMPLE 45
1-[(5,6-Dichloro-9a-methyl--3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylic acid
Step A. 5,6-Dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
Carrying out a reaction as described in example 1, Step C, except that the 5,6-dichloro-9a-ethyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is replaced by an equimolar quantity of [(5,6-dichloro-oxy]acetic acid (Example 3, Step E), there is obtained 5,6-dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
Step B. Ethyl 1-[(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylate.
Carrying out a reaction as described in Example 1, Step D, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one and ethyl bromoacetate are replaced by equimolar quantities of 5,6-dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one and ethyl 1-bromocyclopentane-1-carboxylate, there is obtained ethyl 1-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylate.
Step C. 1-[(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylic acid.
Carrying out a reaction as described in Example 1, Step E, except that the ethyl [(5,6-dichloro-9a-ethyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is replaced by an equimolar quantity of ethyl 1-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylate, to give 1-[(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]cyclopentane-1-carboxylic acid.
EXAMPLE 46
Fluoro [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. 5,6-Dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one.
Carrying out a reaction as described in Example 1, Step C, except that the 5,6-dichloro-9a-ethyl-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is replaced by an equimolar quantity of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D), there is obtained 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3one.
Step B. Ethyl fluoro[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Carrying out a reaction as described in Example 1, Step D, except that the ethyl bromoacetate is replaced by an equimolar quantity of ethyl bromofluoroacetate, there is obtained ethyl fluoro [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step C. Fluoro[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Ethyl fluoro [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (4.01 gm., 0.02 mole) is dissolved in ethanol (75 ml.) and treated with a solution of sodium bicarbonate (3.36
gm., 0.04 mole) in water (150 ml.). The mixture is heated and stirred on a steam bath for 15 minutes and then concentrated in vacuo to a volume of 50 ml. The residual solution is diluted with water (50 ml.) and acidified to Congo red test paper with 6 normal hydrochloric acid. The precipitate that forms is removed by filtration, washed with water and dried. The product is sufficiently pure for use but it may be further purified by recrystallization from a mixture of acetic acid and water to produce pure fluoro[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 47
[(9a-Allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. 2,3-dichloro-4hydroxybenzaldehyde
A mixture of 2,3dichloro-4-hydroxybenzaldehyde (19.1 gm., 0.1 mole) and potassium carbonate (34.4 gm., 0.25 mole) in dimethylformamide (50 ml.) is stirred and treated dropwise over 15 minutes with dimethyl sulfate (14.1 gm., 0.11 mole). The reaction is exothermic; after 45 minutes the mixture is poured with stirring into water (300 ml.). The solid product that separates is removed by filtration, washed with water and then washed with a little methanol. After drying the yield of 2,3-dichloro-4-methoxybenzaldehyde is 16 gm., m.p., 117°-118° C.
Step B. 2,3-Dichloro-4-methoxycinnamic acid
A mixture of 2,3-dichloro-4-methoxybenzaldehyde (158 gm., 0.77 mole), malonic acid (146 gm., 1.4 mole), pyridine (450 ml.) and piperidine (15 ml.) is heated and stirred on a steam bath for 23/4 hours. The hot reaction mixture is poured, with stirring into a mixture of concentrated hydrochloric acid (770 ml.) and crushed ice (3.1 kg.).
The solid that separates is removed by filtration, then washed, first with water and then with a little methanol. After drying, the solid is dissolved in a solution containing sodium hydroxide (61.6 gm.) and water (7.7 liters). The insoluble material is removed by filtration and the filtrate acidified with concentrated hydrochloric acid.
The solid 2,3-dichloro-4-methoxycinnamic acid that separates is removed by filtration, washed with water and dried. The yield is 179 gm. (96%), m.p. 246°-249° C. This crude material is adequate for use in the next step.
Step C. 3-(2,3-Dichloro-4-methoxyphenyl)-propanoic acid.
2,3-Dichloro-4-methoxycinnamic acid (200.8 g., 0.813 mole) is dissolved in tetrahydrofuran (1600 ml.) and 5% platinum on charcoal (16.3 gm.) is added. The mixture is divided into 8 separate units and each is placed in a Parr hydrogenation apparatus in an atmosphere of hydrogen at an initial pressure of 50 p.s.i. Upon shaking, the time required for the reduction of each batch is 35 to 60 minutes.
The combined reaction mixtures are filtered and the solvent removed by distillation at reduced pressure to give crude 3-(2,3-dichloro-4-methoxyphenyl(propanoic acid, 176.3 gm., m.p. 141°-143° C. The material is adequate for use in the next step.
Step D. 4,5-Dichloro-6-methoxy-2,3-dihydro-1H-inden-1-one.
3-(2,3-Dichloro-4-methoxyphenyl)propanoic acid (176.3 g., 0.708 mole) is placed in benzene (500 ml.) and thionyl chloride (101.8 ml., 1.42 mole) is added. The mixture is refluxed for 11/2 hours and the volatile materials removed by distillation at reduced pressure. The residual oil is dissolved in benzene (50 ml.) and the solvent again removed at reduced pressure. This process is repeated and the residue is dissolved in dry methylene chloride (500 ml.).
The solution is placed in a flask protected from atmospheric moisture by a calcium chloride drying tube and cooled via an ice bath. Then aluminum chloride (94.4 gm., 0.708 mole) is added portionwise via a vessel attached to the reaction flask by Gooch rubber tubing. After the addition is complete, the cooling bath is removed and stirring at ambient temperature is continued for 3 hours.
The reaction mixture is poured, with stirring into ice water (1635 ml.) containing concentrated hydrochloric acid (218 ml.). The solid that separates is collected by filtration, washed with water and dried. The yield is 160 gm. This material is recrystallized (while treating with decolorizing charcoal) from acetonitrile to give 4,5-dichloro-6-methoxy-2,3-dihydro-1H-inden-1-one, 129.1 gm., m.p. 163°-165°.
Step E. 4,5-Dichloro-6-methoxy-2,3-dihydro-1H-indene.
An amalgam of zinc, prepared from zinc (65 gm.) and mercuric chloride (3.5 gm.), is stirred with a mixture of water (20 ml.), ethanol (20 ml.) and concentrated hydrochloric acid (50 ml.). The mixture is heated to boiling and a slurry of 4,5-dichloro-6-methyl-2,3-dihydro-1-H-inden-1-one (23.1 gm., 0.1 mole) in a mixture of hot ethanol (150 ml.), water (20 ml.) and concentrated hydrochloric acid (50 ml.) is added over 15 minutes. Then the boiling mixture is treated with concentrated hydrochloric acid (50 ml.) over an hour. Boiling and stirring is continued for 5 hours longer and then the stirring is terminated and the mixture is cooled. The liquid portion is separated by decantation and concentrated to half its volume in vacuo. The solid portion of the reaction mixture is extracted with ether (four 50 ml. portions). The combined ether extracts and liquid portion of the reaction mixture are united in a separatory funnel and water (250 ml.) is added. The mixture is thoroughly shaken and the ether layer separated, washed with water, then with brine and finally dried over anhydrous magnesium sulfate. Evaporation of the ether gives 15.2 g. of crude 4,5-dichloro-6-methyoxy-2,3-dihydro-1H-indene, m.p. 78°-82° C. This material is adequate for use in the next step.
Step F. 6,7-Dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one.
4,5-Dichloro-6-methoxy-2,3-dihydro-1H-indene (21 gm., 0.097 mole) is dissolved in acetic acid (280 ml.) and chromium, trioxide (14 gm., 0.14 mole) in a mixture of water (15 ml.) and acetic acid (40 ml.) is added dropwise with stirring over a period of one hour. The mixture is poured, with stirring into cold water (1200 ml.) and the solid that separates is removed by filtration, washed with water and dried. The product, which consists of a mixture of the desired material and the isomer described in Step D, is subjected to column chromatographic separation using 225 gm. of silica gel and chloroform is used for elution. Evaporation of the solvent gives 6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one, 5.2 gm., m.p. 154°-156° C.
Step G. 2-Allyl-6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one.
6.7 -Dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one(63.5 gm., 0.274 mole) is dissolved in a mixture of dry tert.-butyl alcohol (500 ml.) and dry benzene (1.5 liters). The solution is refluxed and potassium tert.-butoxide (46 gm., 0.301 mole) in dry tert.-butyl alcohol (1 liter) is added as rapidly as possible. The solution is refluxed for another 1/2 hour, cooled to 20° C., stirred and treated with allyl bromide (36 gm., 0.301 mole). The mixture is stirred and refluxed for 4 hours, cooled and treated with water (250 ml.). The crude 2-allyl-6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one is separated by filtration, washed with water, dried and recrystallized from a mixture of benzene and hexane.
Step H. 2-Allyl-6,7-dichloro-5-hydroxy-2,3-dihydro-1H-inden-1-one.
Dry pyridine hydrochloride (500 gm.) is melted and heated to 195° C. and 2-allyl-6,7-dichloro-5-methoxy-2,3-dihydro-1H-inden-1-one (45.4 gm., 0.167 mole) is added with stirring. The reaction mixture is kept at 195° C. for 45 minutes and then poured with vigorous stirring into crushed ice (2 kg.). The crude produce is collected by filtration, washed with water and dried. The 2-allyl-6,7-dichloro-5-hydroxy-2,3-dihydro-1H-inden-1-one is recrystallized from a mixture of ethanol andwater.
Step I. Ethyl [(2-allyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
Carrying out a reaction as described in Example 1, Step D, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is replaced by an equimolar quantity of 2-allyl-6,7-dichloro-5-hydroxy-2,3-dihydro-1H-inden-1-one, there is obtained ethyl [(2-allyl-6,7-dichloro-1-oxo-2,3-dihydro-1-H-inden-5-yl)oxy]acetate.
Step J. Ethyl {[2-allyl-6,7-dichloro-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy}-acetate.
Carrying out a reaction as described in Example 20, Step B, except that the methyl [(6,7-dichloro-2-ethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)-oxy]acetate is replaced by an equimolar quantity of ethyl [(2-allyl-6,7-dichloro-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate, there is obtained ethyl [2-allyl-6,7-dichloro-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy acetate.
Step K. Ethyl [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate.
Carrying out a reaction as described in Example 20, Step C, except that the methyl [6,7-dichloro-2-ethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy acetate is replaced by an equimolar quantity of ethyl (2-allyl-6,7-dichloro-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl)oxy)acetate, there is obtained ethyl [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step L. [9a-Allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Carrying out a reaction as described in Example 20, Step D, except that the methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is replaced by an equimolar quantity of ethyl [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3-H-fluoren-7-yl)oxy]acetate, there is obtained [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 48
[(5,6-Dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetra-3H-fluoren-7-yl)oxy]acetic acid
By carrying out a series of reactions as described in Example 47, except that in Step G, the allyl bromide is replaced by an equimolar quantity of propargyl bromide and using the produce from each step in the subsequent step, there is obtained:
Step G. 6,7-Dichloro-5-methoxy-2-propargyl-2,3-dihydro-1H-inden-1-one.
Step H. 6,7-Dichloro-5-hydroxy-2-propargyl-2,3-dihydro-1-H-inden-1-one.
Step I. Ethyl [(6,7-dichloro-1-oxo-2-propargyl-2,3-dihydro-1H-inden-5yl)oxy]acetate.
Step J. Ethyl [6,7-dichloro-1-oxo-2-(3-oxobutyl)-2-propargyl-2,3-dihydro-1H-inden-5yl]-oxy acetate.
Step K. [5,6-Dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate.
Step L. [(5,6-Dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 49
[(5,6-Dichloro-9a-(2-methylpropyl)-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out a series of reactions as described in Example 47, except that in step G, the allyl bromide is replaced by and equimolar quantity of 2-methylpropyl bromide, and using the produce from each step in the subsequent one, there is obtained:
Step G. 6,7-Dichloro-2-(2-methylpropyl)-5-methyoxy-2,3-dihydro-1H-inden-1-one.
Step H. 6,7-Dichloro-2-(2-methylpropyl)-5-hydroxy-2,3-dihydro-1H-inden-1-one.
Step I. Ethyl {[6,7-dichloro-2-(2-methylpropyl)-1-oxo-2,3-dihydro-1H-inden-5-yl]oxy]}acetate.
Step J. Ethyl [6,7-dichloro-2-(2-methylpropyl)-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1H-inden-5-yl]oxy acetate.
Step K. Ethyl [5,6-dichloro-9a-(2-methylpropyl)-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl]oxy acetate.
Step L. [5,6-Dichloro-9a-(2-methylpropyl)-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl]oxy acetic acid.
EXAMPLE 50
[(5,6-Dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3-H-fluoren-7-yl)oxy]acetic acid
Carrying out a series of reactions as described in Example 47, except that in Step G, the allyl bromide is replaced by an equimolar quantity of (bromomethyl)cyclopropane, and using the product from each step in the subsequent step, there is obtained:
Step G. 6,7-Dichloro-2-cyclopropylmethyl-5-methoxy-2,3-dihydro-1H-inden-1-one.
Step H. 6,7-Dichloro-2-cyclopropylmetnyl-5-hydroxy-2,3-dihydro-1H-inden-1-one.
Step I. Ethyl [(6,7-dichloro-2-cyclopropylmethyl-1-oxo-2,3-dihydro-1H-inden-5-yl)oxy]acetate.
Step J. Ethyl {8 6,7-dichloro-2-cyclopropylmethyl-1-oxo-2-(3-oxobutyl)-2,3-dihydro-1-H-inden-5-yl]oxy}acetate.
Step K. Ethyl [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step L. [(5,6-Dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 51
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
5,6-Dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (Example 1, Step C) (15 gm., 0.048 mole), potassium carbonate (13.3 gm., 0.096 mole), dimethylformamide (100 ml.) and iodoacetic acid (10.6 gm., 0.057 mole) is stirred at room temperature for 24 hours. The reaction mixture is poured into water (150 ml.), stirred, warmed to 50° C., filtered and the filtrate acidified with 6N hydrochloric acid to obtain [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid, which after recrystallization from acetic acid, melts at 237° C.-238° C.
EXAMPLE 52
[(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Carrying out a reaction as described in Example 51, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3-H-fluoren-3-one is replaced by an equivalent quantity of 5,6-dichloro-7-hydroxy-9a-methyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (Example 3, Step C), and there is obtained [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 53
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. tert.-Butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
A mixture of 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (Example 1, Step C) (15 gm., 0.048 mole), tert.-butyl bromoacetate (10.3 gm., 0.0528 mole), potassium carbonate (13.3 gm., 0.096 mole) and dimethylformamide (100 ml.) is stirred at 35° C. for an hour and then cooled and poured into water (100 ml.). The solid that separates is tert.-butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, which is separated by filtration, washed with water and dried. This material is adequate for use in the next step.
Step B. [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Tert.-butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (8.22 gm., 0.02 mole) in benzene (100 ml.) containing p-toluenesulfonic acid (0.6 gm.) is refluxed for 20 minutes. The solid that separates upon cooling is [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid, m.p. 237° C.-238° C.
EXAMPLE 54
[(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid
Step A. Tert.-butyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Carrying out a reaction as described in Example 53, Step A, except that the 5,6-dichloro-9a-ethyl-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one is replaced by an equimolar quantity of 5,6-dichloro-7-hydroxy-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-3-one (Example 4, Step C), thereby is obtained tert.-butyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetate.
Step B. [(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
Carrying out a reaction as described in Example 53, Step B, except that the tert.-butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)acetate is replaced by an equimolar amount of tert.-butyl [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate, thereby is obtained [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
EXAMPLE 55
Benzyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 20, Step C) (5.8 g., 0.016 mole) is dissolved in a mixture of dry benzyl alcohol (50 ml) and methylene chloride (40 ml.) containing amberlite IRA 400 (ethoxide) (5-6 g.). The mixture is stirred magnetically at reflux for four hours and then filtered. The filtrate is concentrated in vacuo to give a yellow solid (5.3 g.) which upon trituration with ethanol and washing with ether yields the product.
EXAMPLE 56
Ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A solution of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D) (0.15 g. 0.004 mole) absolute ethanol (60 ml) and 12 N HCl (5 ml.) in ethanol (20 ml.) is heated under reflux on the steam bath with stirring for an hour. The excess solvent is removed under reduced pressure. Ice and water are added to the oily residue and the product extracted into ether. After drying over MgSO 4 , the solution is concentrated to yield 1.6 g. of product, m.p. 160°-162° C.
Recrystallization from tetrahydrofuran-ether-petroleum ether (1:1:2) gives 1.15 g. of ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, m.p. 164°-166° C.
By carrying out the reaction as described in Example 56, except that the ethanol is replaced by an equal amount of:
EXAMPLE 57
1-Propanol
EXAMPLE 58
Isopropyl alcohol
EXAMPLE 59
1-Butanol
EXAMPLE 60
Cyclobutanol
EXAMPLE 61
Allyl alcohol
EXAMPLE 62
Propargyl alcohol
There is obtained:
EXAMPLE 57
Propyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 58
Isopropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 59
Butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 60
Cyclobutyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 61
Allyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 62
Propargyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
By carrying out the reaction as described in Example 56 except that the [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar amount of:
EXAMPLE 63
(+) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31, Step A).
EXAMPLE 64
(-) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31, Step B).
There is obtained:
EXAMPLE 63
Ethy (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, m.p. 94°-97° C.
EXAMPLE 64
Ethyl (-) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate, m.p. 94°-97° C.
EXAMPLE 65
Carboxymethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Step A. Benzyloxycarbonylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture containing [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D) (1.07 g, 0.003 mole), potassium carbonate (0.41 g, 0.003 mole) and benzyl bromoacetate (0.69 g, 0.003 mole) in dimethylformamide (35 ml) is heated at 80° C. for two hours. Then this mixture is filtered and the filtrate is concentrated in vacuo. The residue is dissolved in methylene chloride, washed with aqueous sodium bicarbonate and than water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give a viscous oil which is triturated with ether to give 1.06 g. of product.
Step B. Carboxymethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Benzyloxycarbonylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate (1.0 g, 0.002 mole) (Step A) is dissolved in tetrahydrofuran (35 ml) and hydrogenated at ambient temperatures and atmospheric pressure employing 10% Pd/C (0.05 g.) as the catalyst in 2 hours. The catalyst is filtered through super-cel in an atmosphere of nitrogen. Then the filtrate is concentrated in vacuo at 50° C. to give the product (0.74 g) which is purified by recrystallization from methanol (9 ml) to yield 0.50 g of product, m.p. 179°-181° C.
By carrying out the reaction as described in Example 65, Step A, except that the benzyl bromoacetate is replaced by an equimolar quantity of:
EXAMPLE 66
Step A. Benzyl 5-bromopentanoate
EXAMPLE 67
Step A. Benzyl 2-bromopropanoate
EXAMPLE 68
Step A. Benzyl 4-bromobutanoate
There is obtained:
EXAMPLE 66
Step A. 4-(Benzyloxycarbonyl)butyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 67
Step A. 1-(Benzyloxycarbonyl)ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluorenyl)oxy]acetate.
EXAMPLE 68
Step A. 3-(Benzyloxycarbonyl)propyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
By carrying out the reaction as described in Example 65, Step B, except that the benzyloxycarbonylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is replaced separately by the compounds produced in Example 66, Step A, Example 67, Step A, and in Example 68, Step A, there is produced:
EXAMPLE 66
Step B. 4-Carboxybutyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 67
Step B. 1-Carboxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 68
Step B. 3-Carboxypropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
By carrying out the reaction as described in Example 65, Step A, except that the [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar quantity of:
EXAMPLE 69
Step A. (+) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31), there is obtained:
EXAMPLE 69
Step A. Benzyloxycarbonylmethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
By carrying out the reaction as described in Example 65, Step B, except that the benzyloxycarbonylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate is replaced by the product of Example 69, Step A, there is obtained:
EXAMPLE 69
Step B. Carboxymethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 70
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Step A. (+) 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole.
(+) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31, Step A) (0.71 g., 0.002 mole) is suspended in dry tetrahydrofuran (20 ml) and cooled to 0° C. A solution of 1,1'-carbonyldiimidazole (0.32 g, 0.002 mole) in tetrahydrofuran (5 ml) is added. The solution of 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole that is formed is used in the next step without isolation.
Step B. 1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
To the solution of (+) 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole (0.002 mole) prepared in Step A at 0° C. is added with stirring 2-hydroxyisobutyric acid (0.21 g., 0.002 mole). After stirring overnight at the ambient temperature, the colorless reaction mixture is concentrated in vacuo at 50° C. The resultant yellow liquid is chromatographed using a silica-gel (60 gm) column and eluted with a mixture of methylene chloride and isopropyl alcohol (100/5 v.v.). The product is obtained by evaporation of the solvent in vacuo.
By carrying out the reaction as described in Example 70, Steps A and B, except that the (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid is replaced by an equimolar amount of:
EXAMPLE 71
(+) [(5,6-Dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 38, Step A). k
EXAMPLE 72
(+) [(5,6-Dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 39, Step A).
EXAMPLE 73
(+) [(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 37, Step A).
EXAMPLE 74
(+) [(5,6-Dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 40, Step A).
EXAMPLE 75
(+) [(9a-Butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 32, Step A).
EXAMPLE 76
(+) [(5,6-Dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 43, Step A).
EXAMPLE 77
(+) [(5,6-Dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 35, Step A).
EXAMPLE 78
(+) [(5,6-Dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 41, Step A).
EXAMPLE 79 (+) [(5,6-Dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 42, Step A).
EXAMPLE 80
(+) [(9a-Allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 33, Step A).
EXAMPLE 81
(+) [(5,6-Dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 34, Step A).
EXAMPLE 82
(+) [(9a-Benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 36, Step A).
EXAMPLE 83
(+) [(5,6-Dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 44, Step A).
there is obtained:
EXAMPLE 71
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 72
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-methyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 73
1-Carboxy-1-methylethyl (+) [(dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 74
1-Carboxy-1-methylethyl (+) [(dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 75
1-Carboxy-1-methylethyl (+) [(9a-butyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 76
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 77
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-cyclopropylmethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 78
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-cyclopentyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 79
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 80
1-Carboxy-1-methylethyl (+) [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 81
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 82
1-Carboxy-1-methylethyl (+) [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 83
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-9a-phenyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 84
2-(4-Morpholinyl)ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Step A. 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole.
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D) (0.71 g., 0.002 mole) is suspended in dry tetrahydrofuran (20 ml) and cooled to 0° C. A solution of 1,1'-carbonyldiimidazole (0.32 g, 0.002 mole) in tetrahydrofuran (5 ml) is added. The solution of 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole that is formed is used in the next step without isolation.
Step B. 2-(4-Morpholinyl)ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
To the solution of 1-{[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole (0.002 mole) prepared in Step A at 0° C. is added with stirring 4-(2-hydroxyethyl)morpholine (0.26 g., 0.002 mole) and a catalytic amount of sodium hydride (10 mg). After stirring overnight at the ambient temperature, the colorless reaction mixture is concentrated in vacuo at 50° C. The resultant yellow liquid is chromatographed using a silica-gel (60 gm) column and eluted with a mixture of methylene chloride and isopropyl alcohol (100/5 v.v.). The product is triturated with ether to give analytically pure product, 0.58 g, m.p. 133°-133.5° C.
By carrying out the reaction as described in Example 84, Step B, except that the 4-(2-hydroxyethyl)morpholine is replaced by an equimolar amount of:
EXAMPLE 85:
2-Dimethylaminoethanol
EXAMPLE 86:
3-Diethylaminopropanol
EXAMPLE 87:
1-(2-Hydroxyethyl)pyrrolidine
EXAMPLE 88:
1-Methyl-3-hydroxypiperidine
EXAMPLE 89: 1-Methyl-4-hydroxypiperidine
there is obtained:
EXAMPLE 85
2-Dimethylaminoethyl [(5,6-dichloro-9a-ethyl-3- oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 86
3-Diethylaminopropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 87
2(1-pyrrolidinyl)ethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 88
1-Methyl-e-piperidyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 89
1-Methyl-4-piperidyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 90
(5-Hydroxymethyl-2-furyl)methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetra-hydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D) (1.43 g, 0.004 mole) is suspended in dry tetrahydrofuran (10 ml) and then triethylamine (0.401 g., 0.004 mole) is added. The resulting solution is cooled at 0° C. followed by the addition of ethyl chloroformate (0.438 g, 0.004 mole) in tetrahydrofuran (5 ml) to form the mixed anhydride and triethylamine hydrochloride which precipitates. To this mixture is added 3,5-di(hydroxymethyl)furan (1.03 g, 0.008 mole) in tetrahydrofuran (5 ml). The reaction mixture is then allowed to rise to ambient temperature before refluxing for one hour. The triethylamine hydrochloride that separates (0.55 g) is filtered and the filtrate is concentrated in vacuo to give a brown solid (2.71 g) which is purified by column chromatography over silica gel (100 g) by elution with a mixture of methylene chloride-tetrahydrofuran (100/4 v.v.) followed by a mixture of methylenechloride-isopropanol (100/5 v.v.) to give 0.55 g. of product which is recrystallized first from isopropanol and then from acetonitrile to give an impure material which melts at 135.5°-137° C. This material is further purified by high pressure liquid chromatography using a Whatman Partisil M9 10/25 PAC column and methylene chloride-isopropyl alcohol (100/2 v.v.) at a flow rate of 5 ml./min. The yield of analytically pure product is 280 mg., m.p. 142°-143° C.
By carrying out the reaction as described in Example 90, except that the 2,5-di(hydroxymethyl)furan is replaced by an equimolar amount of:
EXAMPLE 91:
Dihydroxyacetone
EXAMPLE 92:
2-Methoxyethanol
EXAMPLE 93:
Tetrahydrofurfuryl alcohol
EXAMPLE 94:
1,1,1-Tris(hydroxymethyl)ethane
there is obtained:
EXAMPLE 91
3-Hydroxy-2-oxopropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 92
2-Methoxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 93
Tetrahydrofurfuryl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 94
2,2-Bis(hydroxymethyl)propyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 95
2-Oxopropyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Potassium carbonate (0.2 g) is suspended in a solution of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 20, Step D) (0.4 g, 0.0011 mole) in dimethylformamide (3 ml). After warming the suspension on a steam bath for 15 minutes, chloroacetone (0.5 g, 0.005 mole) is added and the mixture heated for an additional 15 minutes. The reaction mixture is cooled, poured into water (50 ml) and the product extracted into ether (three 15 ml portions). The extract is dried over Na 2 SO 4 . After filtration, the extract is concentrated to give a yellow oil. Trituration with cold ether causes crystallization to occur. The crystalline product weighs 0.1 g and melts at 153°-155° C.
EXAMPLE 96
3-Hydroxypropyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
By substitution of an equimolar amount of 3-bromo-1-propanol for the chloroacetone in Example 95, there is obtained a crude product which is column chromatographed on silica gel and eluted with a mixture of acetic acid, acetone and toluene (5/5/90 v.v.v.). The product weighs 100 mg and melts at 114°-117° C.
By carrying out the reaction as described in Example 95, except that the chloroacetone is replaced by an equimolar amount of:
EXAMPLE 97:
2-Bromoethanol
EXAMPLE 98:
2-Bromo-1,3-propanediol
EXAMPLE 99:
2-Bromoethanesulfonamide
EXAMPLE 100:
1-Bromo-2,3-propanediol
there is obtained:
EXAMPLE 97
2-Hydroxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 98
1-(Hydroxymethyl)-2-hydroxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 99
2-Sulfamoylethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 100
2,3-Dihydroxypropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 101
3-Pyridylmethyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 20, Step C) (0.74 g, 0.002 mole), 3A molecular sieves (10 g) and 3-hydroxymethylpyridine (0.65 g, 0.006 mole) in methylene chloride (40 ml) is stirred at ambient temperature overnight.
The reaction mixture is then filtered through super-cel and washed with methylene chloride. The filtrate is concentrated in vacuo at 50° C. This residue is chromatographed over silica gel (30 g) by elution with a methylene chloride-isopropanol mixture (100/3 v.v.) to give 0.36 g of product which is recrystallized from isopropanol (7 ml) to yield 0.23 g of product containing isopropanol. This sample is dried at 83° C. for 13 hours in vacuo to remove the solvent. The yield of product is 0.20 g., m.p. 120°-121° C.
By carrying out the reaction as described in Example 101 except that the 3-hydroxymethylpyridine is replaced by an equimolar quantity of:
EXAMPLE 102:
2-Hydroxymethylpyridine
EXAMPLE 103:
4-Hydroxymethylpyridine
EXAMPLE 104:
3-Hydroxymethylpyridine-N-oxide
there is obtained:
EXAMPLE 102
2-Pyridylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 103
4-Pyridylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 104
3-Pyridylmethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate-N-oxide.
EXAMPLE 105
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic Acid Anhydride
A stirred suspension of 5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)-oxy]acetic acid (14.2 gm., 0.04 mole) in methylene chloride (1.5 liters) is treated with a solution of N,N-dicyclohexylcarbodiimide (4.33 gm., 0.021 mole) in methylene chloride (100 ml.). After an hour, the solvent is removed by distillation and the residue treated with dry ether (150 ml.). The dicyclohexylurea is removed by filtration and the ether removed by evaporation at reduced pressure to give [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid anhydride.
EXAMPLE 106
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide
1-{[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetyl}imidazole (Example 84, Step A) (0.81 gm, 0.002 mole) in tetrahydrofuran (20 ml) is treated with 25% aqueous ammonium hydroxide (5 ml). After warming for an hour at 35° C., the solvent is removed in vacuo whereby the product remains which is washed with water and recrystallized from acetic acid.
By carrying out the reaction as described in Example 106, except that the 25% aqueous ammonium hydroxide is replaced by:
EXAMPLE 107A:
(t-Butoxycarbonyl)methylamine
EXAMPLE 108A:
2-(t-Butyoxycarbonyl)ethylamine
there is obtained:
EXAMPLE 107
Step A. N-(t-Butoxycarbonylmethyl)-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide
EXAMPLE 108
Step A. N-[2-(t-Butoxycarbonyl)ethyl]-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide.
EXAMPLE 107
Step B. N-Carboxymethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide.
N-(t-Butoxycarbonylmethyl)-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide (Example 107, Step A) (600 mg) is dissolved in toluene (100 ml), treated with p-toluenesulfonic acid (50 mg) and the mixture refluxed for 2 hours. The solvent is removed and the product dissolved in an aqueous sodium bicarbonate solution, filtered and acidified to Congo-red paper with dilute hydrochloric acid. The solid that separates is removed by filtration, washed with water and dried. The yield is 300 mg.
EXAMPLE 108
Step B. N-(2-Carboxyethyl)-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide
By carrying out the reaction as described in Example 107, Step B, except that the N-(t-butoxycarbonylmethyl)-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide is replaced by an equimolar amount of N-[2-(t-butoxycarbonyl)ethyl]-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide. There is obtained N-(2-carboxyethyl)-[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetamide.
EXAMPLE 109
2,3-Dihydroxypropyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Step A. (2,2-Dimethyl-1,3-dioxolan-4-yl)methyl[(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of 2 gm. of [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid, 3 ml. of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane and 0.5 g. of p-toluenesulfonic acid hydrate are heated on the steam bath for 3 hours. The dark reaction mixture then is chromatographed on 300 g of silica, and eluted with acetic acid-acetone-toluene (5:5:90). Fractions containing a single component (Rf˜0.4) are pooled and concentrated to a yellow oil. On standing overnight, a mixture of crystalline solid and yellow oil resulted. The mixture is filtered and the solid recrystallized from tetrahydrofuran-ether-petroleum ether (5:15:25). The yield of pure product is 0.3 g., m.p. 143°-145° C.
Step B. 2,3-Dihydroxypropyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
A mixture of 165 mg of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate from Example 109, Step A is dissolved in 100 ml. of 0.075 N hydrochloric acid and 20 ml. of acetone and heated, with stirring at 50°-55° C. for 2 hours. The mixture is cooled and neutralized with a solution of sodium bicarbonate. The solution is saturated with sodium chloride and extracted two times with 100 ml. portions of 20% tetrahydrofuran in ether. The extract is dried over Na 2 SO 4 . After filtration, the filtrate was concentrated to a yellow oil that solidified on standing. After recrystallization from tetrahydrofuran-ether-petroleum ether, there is obtained 110 mg. of product, m.p. 135°-138° C.
EXAMPLE 110
1-(Hydroxymethyl)-2-hydroxyethyl [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
Step A. (2-Phenyl-1,3-dioxan-5-yl) [(5,6-dichloro-9a-ethyl-3 -oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
By substituting the 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane used in Example 109, Step A, with an equimolar quantity of 5-hydroxy-2-phenyl-1,3-dioxane and conducting the reaction, as described in Example 109, Step A, there is obtained (2-phenyl-1,3-dioxan-5-yl) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
Step B. 1-(Hydroxymethyl)-2-hydroxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
By substituting the (2,2-dimethyl-1,3-dioxolan-4-yl)methyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate used in Example 109, Step B by an equimolar amount of (1-phenyl-1,3-dioxan-5-yl) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate and conducting the reaction as described in Example 109, Step B, there is obtained 1-(hydroxymethyl)-2-hydroxyethyl [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 111
[(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid hydrazide
By conducting a reaction as described in Example 106, except that an equimolar quantity of anhydrous hydrazine is used in place of the ammonium hydroxide, there is obtained [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid hydrazide.
By carrying out a reaction as described in Example 70, Step B, except the 2-hydroxyisobutyric acid is replaced by an equimolar amount of:
EXAMPLE 112:
2-Ethyl-2-hydroxybutyric acid
EXAMPLE 113:
L(+)-lactic acid
EXAMPLE 114:
5-Hydroxypentanoic acid
EXAMPLE 115:
1-Hydroxycyclobutanecarboxylic acid
EXAMPLE 116:
1-Hydroxycyclopentanecarboxylic acid
There is obtained:
EXAMPLE 112:
1-Carboxy-1-ethylpropyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 113:
L(+)1-Carboxyethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
EXAMPLE 114:
4-Carboxybutyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 115:
1-Carboxycyclobutyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 116:
1-Carboxycyclopentyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate.
EXAMPLE 117
Parenteral Solution of the Sodium Salt of (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31, Step A) (100 mg) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml. and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 118
Parenteral Solution of the Sodium Salt of (+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 37, Step A) (100 mg) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml. and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 119
Parenteral Solution of the Sodium Salt of (+) [(5,6-dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(5,6-Dichloro-3-oxo-9a-propargyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 34, Step A) (100 mg) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml. and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 120
Parenteral solution of the Sodium Salt of (+) [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(5,6-Dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 43, Step A) (100 mg) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml. and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 121
Parenteral Solution of the Sodium Salt of (+) [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 33, Step A) (100 mg.) is dissolved in 0.05 N sodium bicarbonate solution (6 ml.) by warming and stirring. The solution is then diluted to 10 ml with water and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 122
Parenteral Solution of the 1-Methylpiperazinium Salt of (+) [(9a-benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid.
(+) [(9a-Benzyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (100 mg.) Example 36, Step A) is dissolved by warming and stirring in a solution of 0.05 N 1-methylpiperazine (6 ml). The solution is then diluted to 10 ml with water and sterilized by filtration. All the water used in the preparation is pyrogen-free.
Similar parenteral solutions can be prepared by replacing the active ingredient of the above example by any of the other carboxylic acid compounds of this invention.
EXAMPLE 123
Parenteral Solution of the Sodium Salt of 1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
1-Carboxy-1-methylethyl (+) [(5,6-Dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 70, Step B) (100 mg.) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml and sterilized. All the water used in the preparation is pyrogen-free.
EXAMPLE 124
Parenteral Solution of the Sodium Salt of 1-Carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
1-Carboxy-1-methylethyl (+) [(5,6-Dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 73) (100 mg.) is dissolved by stirring and warming in a solution of 0.05 N sodium bicarbonate (6 ml). The solution is then diluted to 10 ml and sterilized. All the water used in the preparation is pyrogen-free.
EXAMPLE 125
Parenteral Solution of the Sodium Salt of 1-Carboxy-1-methylethyl (+) [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
1-Carboxy-1-methylethyl (+) [(9a-allyl-5,6-dichloro-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 80) (100 mg.) is dissolved in 0.05N sodium bicarbonate solution (6 ml.) by warming and stirring. The solution is then diluted to 10 ml with water and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 126
Parenteral Solution of the Ammonium Salt of 1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a -isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate
1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-isopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (100 mg.) (Example 74) is dissolved by warming and stirring in a solution of 0.05N ammonium hydroxide (6ml). The solution is then diluted to 10 ml with water and sterilized by filtration. All the water used in the preparation is pyrogen-free.
EXAMPLE 127
Dry-filled capsules containing 50 mg. of active ingredient per capsule
______________________________________ Per Capsule______________________________________(+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetra-hydro-3H-fluoren-7-yl)oxy]-acetic acid 50 mg.Lactose 149 mg.Magnesium Stearate 1 mg.Capsule (Size No. 1) 200 mg.______________________________________
The (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 31, Step A) is reduced to a No. 60 powder and then lactose and magnesium stearate are passed through a No. 60 bolting cloth onto the powder and the combined ingredients admixed for 10 minutes and then filled into a No. 1 dry gelatin capsule.
EXAMPLE 128
Dry-filled capsules containing 50 mg. of active ingredient per capsule
______________________________________ Per Capsule______________________________________(+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetra-hydro-3H-fluoren-7-yl)oxy]-,acetic acid 50 mg.Lactose 149 mg.Magnesium Stearate 1 mg.Capsule (Size No. 1) 200 mg.______________________________________
The (+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetic acid (Example 37, Step A) is reduced to a No. 60 powder and then lactose and magnesium stearate are passed through a No. 60 bolting cloth onto the powder and the combined ingredients admixed for 10 minutes and then filled into a No. 1 dry gelatin capsule.
EXAMPLE 129
Dry-Filled Capsules Containing 50 mg. of Active Ingredient Per Capsule
______________________________________ Per Capsule______________________________________1-Carboxy-1-methylethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetra-hydro-3H-fluoren-7-yl)oxy]acetate 50 mg.Lactose 49 mg.Magnesium Stearate 1 mg.Capsule (Size No. 1) 100 mg.______________________________________
The 1-carboxy-1-methylethyl (+) [(5,6-dichloro-9a-ethyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7yl)oxy]acetate (Example 70, Step B) is reduced to a No. 60 powder and then lactose and magnesium stearate are passed through a No. 60 bolting cloth onto the powder and the combined ingredients admixed for 10 minutes and then filled into a No. 2 dry gelatin capsule.
EXAMPLE 130
Dry-Filled Capsules Containing 50 mg. of Active Ingredient Per Capsule
______________________________________ Per Capsule______________________________________1-Carboxy-1-methylethyl(+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate 50 mg.Lactose 49 mg.Magnesium Stearate 1 mg.Capsule (Size No. 1) 100 mg.______________________________________
The 1-carboxy-1-methylethyl (+) [(5,6-dichloro-3-oxo-9a-propyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate (Example 73) is reduced to a No. 60 powder and then lactose and magnesium stearate are passed through a No. 60 bolting coth onto the powder and the combined ingredients admixed for 10 minutes and then filled into a No. 2 dry gelatin capsule.
Similar dry-filled capsules can be prepared by replacing the active ingredient of the above example by any of the other compounds of this invention. | The invention relates to novel [(5,6,9a-substituted-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]alkanoic and cycloalkanoic acid and their analogs, esters, salts and derivatives. These compounds are synthesized by methods selected from a number of synthetic routes depending on the particular structure, choice of intermediate or preferred reaction sequence. The compounds are useful in the treatment and prevention of injury to the brain and spinal chord due to accidents, ischemic stroke and hydrocephalus; compositions for such uses are also disclosed. | 2 |
This is a continuation of application Ser. No. 620,007 filed Sept. 30, 1975 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to deployable solar cell arrays, and more particularly to a semi-rigid solar cell panel whose width when deployed is in excess of the width of the spacecraft which stores the panels during launch.
2. Description of the Prior Art
There have been a variety of mechanical configurations proposed for deployable solar arrays. The various configurations fall into two general classes; rigid substrate and flexible substrate. The substrate is the structural element to which the rather fragile solar cells are affixed. In the case of the rigid substrate type of solar arrays, the structural element is usually formed of honeycombed material, and it is necessarily designed to be sufficiently rigid so that it is self-supporting between restraints during the launch phase. The conventional approach employs honeycomb material on the order of one inch in thickness for large arrays. No supplemental structure except for the deployment mechanism is required after deployment in orbit.
In order that an array with a large surface area may be stored within the confines of the launch vehicle shroud, multiple hinging of separate substrate panels is frequently employed. In such a concept, the several substrate panels with hinges between each panel are folded in accordion pleated fashion with the panels stacked one on top of the other with the stack extending radially outward of the spacecraft axis corresponding to the launch vehicle. Obviously, the height or radial extent of the stack of these panels becomes an important limitation because of the thickness of the substrate. Either the spacecraft volume is reduced to permit the necessary stack height, or the maximum power available is limited by the spacecraft volume requirements. Further, the panel width must decrease as the panels are stacked radially outward of the spacecraft axis, since the launch vehicle shroud being cylindrical in form must encompass the spacecraft and the separate rigid substrate panels of the solar cell array. Thus, the outermost panels must have a different width than the innermost if the deployment area is to be maximized, while shroud volume consumption is minimized. This not only introduces great complexity in the deployment mechanism, but requires a coordinated deployment sequence involving in most cases a scissors linkage attached to the edges of the substrates. Further, latching devices are required at the hinges between substrate panels and/or the linkage mechanism to rigidize the array, particularly subsequent to deployment.
The nature of any stacked panel solar cell array limits the maximum solar cell area presented for power generation prior to deployment, to one-half of the total area when two panels are used, one-third when three are used, etc.
Further, attempts have been made to place various hinged panel sections about the various sides or faces of the spacecraft body while maintaining the panel sections within the cylindrical volume limits of the launch vehicle shroud and while, at the same time, exposing the complete surface area of the panels prior to deployment. This keeps the deployment mechanism simplified, but these requirements require at least two hinged sub-panels affixed to primary panels if large solar cell surface areas are to be achieved.
Regardless of the nature of mounting the solar cell panel sections to the periphery of the spacecraft body, the rigid substrates, being relatively thick, constrains the maximum area by the fact that each panel element of the array lies on a chord of the circular shroud envelope. In addition, the chordal nature of the panel elements prohibits maximum spacecraft volume from being achieved. The deployed solar cells of the rigid class thus described suffer the inherent inefficiencies because of the discontinuous nature of the substrate. Each of the several separate panels or sections must have a portion of the substrate clear of solar cells around its periphery, about the points of hinge mechanization, and in the regions of the launch support interfaces. This, of course, requires more substrate area and weight than is necessary for the power function alone. In addition every discontinuity in the substrate surface imposes design limitations upon the electrical configuration of the solar cell layout, thus leading to additional inefficiencies. Further, at every hinge line, it is necessary to strap wire across the joint to provide electrical continuity and the system suffers the attendant reliability reduction. The nature of the rigid solar cell panels of the past design require that the necessary power area be achieved in finite increments with each increment the area of one sub-panel or section. For example; if 30 square feet of array is required and a design using two sub-panels is optimized, then each panel must necessarily be 15 square feet in area. Any growth in the requirements may only then be accomplished by adding a third panel having a similar 15 square foot surface area, not likely to be an optimum, or by major redesign of the sub-panels and launch restraint. Similar difficulties exist but perhaps to a more limited degree with the second of the above described type of fixed rigid solar cell panel array.
With respect to the second class of deployable solar cell arrays using the principle of a flexible substrate, the flexible substrate solar cell arrays are characterized by a "paper thin" substrate to which the solar cells are mechanically affixed. The negligible stiffness of this assembly requires special packaging to survive launch vibrations in a mechanized structure, to which the solar array is attached, for deployment and to provide sufficient structural stiffness in the deployed state. Solar cell arrays of this class are preferred over rigid substrate arrays, at higher power levels where they become weight competitive or superior and/or where the absolute power requirement (deployed area) exceeds that which can be realistically achieved with the simpler rigid substrate array. The substantial mechanical complexity of these arrays and the more severe transient temperatures (due to low thermal mass) suffered in orbit is generally believed to make them less reliable and more expensive than rigid arrays.
The present invention is directed to the solving of the problems inherent to conventional rigid substrate solar cell and flexible substrate solar cell arrays.
SUMMARY OF THE INVENTION
The present invention is directed to a deployable solar cell array which employs a continuous, elastically deformable, semi-rigid panel which is nominally flat when deployed and elastically deformed and wrapped about the spacecraft body during vehicle launch.
Specifically, at least one solar cell panel is curved into arcuate form to conform the panel to the spacecraft body and/or launch vehicle envelope and is coupled to the body by releasable restraint means. The spacecraft includes deployment means for each panel in the form of a deployment arm hinged at its ends respectively to the spacecraft body and to the panel. Spring biased hinges couple the deployment arm at one end to the center of the body and at the other end to an edge of its panel to automatically deploy the panel radially outward of the body and at some distance therefrom in response to release of the restraint means. A motor mounted on the spacecraft body and coupled to the inboard end of each deployment arm is preferably employed to rotate each deployed panel about the axis of the deployment arm to align the solar cells with the solar radiation. Preferably, a pair of semi-rigid solar cell panels are wrapped about opposite sides of the spacecraft body with edges of respective panels in confronting position and commonly latched at their opposed edges under elastically deformed restraint, each panel being mounted on its deployment arm.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a spacecraft incorporating the self-deployable, elastically deformable, semi-rigid multiple panel solar cell array of the present invention, with the panels elastically deformed and wrapped about the exterior of the spacecraft.
FIG. 2 is a perspective view of the spacecraft, similar to that of FIG. 1, with the ends of the panels released from the spacecraft and tangent thereto prior to full panel deployment.
FIG. 3 is a perspective view of the spacecraft, similar to that of FIGS. 1 and 2, with the paired semi-rigid panels in fully deployed position.
FIG. 4 is a side elevational view of a portion of the spacecraft of FIG. 2 corresponding to conditions of FIG. 2.
FIG. 5 is a side elevational view of a portion of the spacecraft similar to that of FIG. 4 with a panel in fully deployed position.
FIG. 6 is an end view of a portion of the spacecraft showing the deployment mechanism under conditions corresponding to those of FIGS. 3 and 5.
FIG. 7 is an enlarged end view, partially in section, of the portion of the spacecraft of FIG. 6.
FIG. 8 is an enlarged side view, partially in section, of that portion of the spacecraft of FIG. 7.
FIG. 9 is an enlarged side view, partially in section, of the hinge construction of a deployment arm of FIG. 4 to its panel.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The illustrated embodiment of the invention involves the utilization of a spacecraft indicated generally at 10 in which the spacecraft body 12 is of modified cylindrical configuration conforming partially to the circular configuration of the launch vehicle shroud (not shown) and having a diameter generally corresponding thereto. In this respect, the spacecraft body 12 is provided with opposed flattened outer walls nominally identified as an upper wall 14 and a lower wall 16 when the spacecraft is oriented as shown in FIG. 1. Alternatively, the spacecraft 12 may be a true cylinder. However, in this case, upper and lower arcuate lattice supports or frameworks 18 are provided on walls 14 and 16 for physically supporting opposed solar cell panels indicated generally at 20 and 22, the panels 20 and 22 constituting the major elements of the present invention. Arcuate sidewalls 24 of the spacecraft body 12 form an enclosure along with opposed end walls 26 and upper and lower walls 14 and 16 respectively. The lattice supports or frameworks 18 have a radius of curvature conforming to that of the sidewalls 24 and act essentially as extensions thereof, these members 18 being formed of tubular metal material and mounted to the top and bottom walls 14 and 16 by suitable mounting pins 28. The purpose of the lattice supports or framework 18 is to provide a curved surface acting as a continuation of the sidewalls 24 about which panels 20 and 22 are wrapped and constrained during vehicle launch. The solar panels 20 and 22 are made up of a continuous semi-rigid elastically deformable substrate 30 of conventional light weight metal honeycomb construction; being rectangular in configuration and having a length L on the order of the axial length of the spacecraft 12 and a width W in excess of the diameter or width of the spacecraft 12. The substrate may, for example, be formed of an aluminum sandwich having a thickness approximately 0.25 inches as example (3 mil skins; three-sixteenths cell 2.0 pounds per cubic foot density core) based on a spacecraft configuration requiring a storage radius of curvature of approximately 50 inches for each panel 20 and 22. Thin solar cells 32 form an array mounted to the radially outer surface of each panel; the make up of the solar cells being quite conventional and forming a very thin outer layer for panels 20 and 22. The electrical connections and the like between individual cells and between the panels 20 and 22 and the interior of the spacecraft body 12 are purposely not shown, as they are quite conventional.
In the illustrated embodiment, the pair of panels 20 and 22 are mounted to opposite faces of the spacecraft opposing in this case the upper and lower walls 14 and 16 of the spacecraft body 12. Alternatively, a single panel could be employed which could be wrapped completely about the periphery of the spacecraft body 12 with the ends of the panel facing each other, however, in the illustrated embodiment, edges 34-36 of the upper panel 20 face edges 38 and 40, respectively, of the lower panel 22 when the panels are elastically deformed and circularly wrapped about the spacecraft body 12. In order to maintain the panels, by way of the elastically deformed substrates 30, wrapped about the spacecraft body 12, the illustrated embodiment of the invention incorporates a plurality of simple, rotatable T latches 42 mounted in line with each other and the axis of the spacecraft on the arcuate end walls 24 of the spacecraft body. The latches 42 include elongated heads 44 rotatable 90° such that the opposite ends of the heads 44 of the latches overlie the confronting edges of the respective panels as seen in contrasting FIGS. 1 and 2. The manner of restraining the panels under elastically deformed conditions is illustrative only of one approach. For instance, it is contemplated that panel tie-down and release may be accomplished by a continuously extending tie-down element integral with a zip cord release, or that the rotatable latches 42 may be replaced by a series of longitudinally spaced pyrotechnic bolts. In any case, subsequent to preloading, that is, elastically deforming the naturally flat panels 20 and 22 into curved configuration from the position shown in FIG. 2 to the position in FIG. 1 by manual or mechanical means, the latches 42 in this instance are rotated such that the elongated heads 44 have their ends overlying the edges of respective panels to maintain the panels in position conforming to the circular configuration of the launch vehicle shroud (not shown) and with the stored energy due to elastic deformation effecting self-return to the flat position at the time of deployment after launch and the reaching by the launch vehicle spacecraft at the appropriate altitude.
Each lattice support 18 as seen in FIG. 3 is formed to include a slot 46 extending longitudinally inwardly from one end of the spacecraft 12 and past the center thereof. A deployment arm indicated generally at 50 is pivotably mounted at one end 68 to the spacecraft body 12 and at the opposite end 74 to an edge of a respective panel to permit proper deployment of its panels 20 or 22 to a position at right angles to the vehicle axis with the solar cells 32 on the outboard surface of the same oriented towards the source of solar energy. In the illustrated embodiment, in FIG. 3, the solar cells 32 face to the left and lie generally coplanar to the left hand end wall 26 of the spacecraft 12. Mounted within the center of the upper and lower walls 14 and 16 of spacecraft 12 is a deployment arm drive motor 52. The motor, in FIG. 6, is mounted within a circular opening 54 within the top wall 14, the motor 52 being provided with a flange 56 which is bolted to the top wall 14 of the spacecraft by suitable bolts 58. Extending upwardly, FIG. 6, from the motor 52 is a rotatable bracket 60 including a base plate 62 supporting laterally spaced ears 64 through which extends a pivot pin 66 mounted for rotation therein, the pin being rigidly coupled to the lower or radially inboard end 68 of the deployment arm 50 forming a spring biased hinge 70. A coil spring 65 is concentrically mounted on pin 66 and has one end 67 fixed thereto and the other end 69 fixed to ear 64 and is tensioned to pivot the deployment arm 50 from the position shown in FIG. 4 to the position shown in FIGS. 3, 5 and 6. Bracket 60 includes a recessed portion 59 between ears 64 defining stops 61 and 63 for deployment arm 50, limiting rotation of arm 50 about pin 66 to an angle θ of somewhat less than 90°, FIG. 8. Further, on the opposite side of the pin 66 from spring 65 is a switch member 72 responsive to rotation of the arm and deployment of the panel to provide an electrical signal indicative of pivoting of the deployment arm 50 from a position essentially parallel to the surface of the top wall 14 of the spacecraft to a position at right angles thereto. A similar spring biased hinge 76 is provided between the outboard end 74 of the deployment arm 50 and side edge 78 of panel 20. In this respect, the outboard end 74 of each deployment arm 50 terminates in a generally right angle projection portion 75 fixedly supporting pivot pin 77. A bifurcated hinge element 79 straddles projection 75 and a spring assembly 80 identical to that at the inboard end of arm 50 biases the panel to its radially extended position as shown in FIG. 3. In FIG. 9, face 82 of hinge element 79 defines a stop which abuts edge 84 of projection 75 when the panel 20 fixed thereto overlies upper wall 14 of the spacecraft, FIG. 4, and which abuts edge 86 of the projection 75 when the panel 20 is fully extended radially of the spacecraft, FIG. 5. The spring loaded hinges 70 and 76 automatically bias the panels 20 and 22 to the positions of FIG. 3 upon release of the panel ends by rotation of latches 42. The hinge 76 further preferably carries a second switch 90 responsive to pivoting of the panel 20 approximately 180° relative to said arm from a position where the panel overlies the arm 50 and is coplanar therewith as seen in FIG. 4 to a position where it extends outwardly therefrom as an axial extension thereof and also generally coplanar therewith, the extent of this movement being seen by comparison of FIGS. 4 and 5. Further, since the spring loaded hinges 70 and 76 are provided with latches, they retain the deployment arms in the radial position shown in FIGS. 3, 5 and 6, and the panels in their outboard position with respect to the deployment arm 50 as seen in FIG. 5. Alternatively, and in a more sophisticated type of control system, pivoting of the inboard end 68 of the deployment arms 50 may be accomplished by a drive motor, and a Selysen motor system may be employed for effecting rotation of the panel 20 about the hinge joint 76 at edge 78 proportional to pivoting of the inboard end to radial position relative to the spacecraft 12.
Further, while the invention has been described in conjunction with the use of the lattice supports 18 as curved guide surfaces for facilitating the elastic deformation of panels 20 and 22, such supports may not be necessary to control and maintain prescribed curvature of the individual panels 20 partially due to the additional stiffness developed by curving of the substrates 30 to the extent of an adequate natural frequency as determined by launch requirements.
By elastically deforming and wrapping a single panel or multiple panels about the spacecraft body, the continuous substrate permits the broadest lattitude in solar cell configuration, substrate area is more efficiently used because there is a minimum of area prohibited to solar cell placement. As the substrate's perimeter length is markedly reduced, there is no mechanical infringing on the substrate face and all launch supports and restraints can be accommodated on the reverse side of the substrate. The panel or panels when elastically deformed for launch may have a radius of curvature equal to that of the dynamic envelope of the launch vehicle shroud, and this maximizes and therefore substantially increases the possible substrate area available for power production prior to array deployment in contrast to the previously described concepts which stow the substrate as chordal planes within the cylindrical envelope. The stowed configuration of the invention of the panels of the present invention allows maximum spacecraft volume to be achieved as an intrustion on the spacecraft design envelope is negligible when compared to that of the conventional concepts described in the description of the prior art. The curvature induced in the substrate 30 of each panel when stowed for launch enhances the structural stiffness of the substrate. This allows a thinner substrate to be used with consequent weight savings. The invention further eliminates the need for hinges between substrate sections or panel sections, thus increasing reliability and producing further weight savings.
Further, while the solar array panel support structure above the north and south equipment panels (upper and lower spacecraft body walls 14-16) comprises an open framework or lattice structure 18 composed of rectangular tubular members and the solar array supports structure on the east and west sides 24 of the spacecraft, because each panel is stowed with a constant radius of curvature, uniform moment is induced and this moment is reacted at the panel ends by way of the multiple rotatable latches 42, the forces acting through the elongated heads 44 on the edges of respective panels. Further, the stress produced in the solar cells 32 and their covers (not shown) due to curving of the panels 20 and 22 for storage must be resolved, it is preferred that the cell cover and cell-substrate interface bond be formed or RTV, a flexible material with the induced stresses being lower than if the elements were rigidly bonded.
While the solar array panels are illustrated in rectangular configuration, the present invention permits relatively broad design lattitude both in terms of area selection, size and configuraton. The array therefore with its area defined by a particular spacecraft's power system need, may be optimized at that size. Reductions or increase in area requirements can be accommodated by reducing or increasing the panel size by whatever actual area increment is necessary without influence on the array's weight efficiency and negligible impact on the spacecraft design as compared to the prior rigid panel structures. Alternatively, rather than employing a honeycomb substrate, the panels may be formed of a matrix type structure with a thin overlay of Kapton sheeting to which the individual solar cells 32 may be affixed.
While the invention has been particularly shown and described with reference to a preferred embodiment thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. | A pair of semi-rigid solar cell panels are curved under stress and latched in arcuate edge abutting fashion about the exterior of a spacecraft body, and upon release of the latched ends flatten into tangency at opposite sides of the spacecraft body. Spring hinges at the ends of a deployment arm cause each panel to automatically move radially outward of the spacecraft body, and a motor mounted to the spacecraft body and to one end of the deployment arm rotates the panel to orient the solar cells relative to the source of solar energy. | 1 |
FIELD OF THE INVENTION
This invention relates to a coating tool for correcting wrong letters or a writing tool such as ball-point pen or the like, and more particularly, a writing tool constructed such that air in the cap is pressurized and compressed when the cap is pushed and loaded in respect to the tool tip, a rotary member projecting from the tool tip is retracted inwardly against a spring, and the compressed air in the cap is fed into the tool's liquid tank to increase the inner pressure.
BACKGROUND OF THE INVENTION
In general, this kind of writing tool, for example, a coating tool for correcting wrong letters by coating correction liquid, is constructed such that e.g., a rotary member held within the extremity end of the tip is biased by a spring and closely contacts the inward extremity edge of the tool tip closing the extremity end of the tip and preventing correction liquid from being discharged. In turn, the rotary member projecting from the extremity end of the tool tip maybe retracted and spaced apart from the inward extremity edge of the tip, against the spring to open the extremity end of the tip, whereupon the correction liquid in the liquid tank is discharged from the extremity end.
In the prior art, this kind of writing tool, as shown in FIG. 16, an inner cylinder 32 for pressurizing and compressing air is arranged within a cap 30 to closely contact an outer periphery of an extremity end 31, The cap 30 is pushed and loaded against the extremity end 31, air is pressurized and compressed in the inner cylinder 32, and the rotary member 34 held in the extremity end of the tip 33 is retracted inwardly toward the tip. The rotary member 34 is thereby moved away from the inward extremity edge of the tip 33, and the compressed air in the inner cylinder 32 is fed into the liquid tank 35 so as to increase an inner pressure in the liquid tank 35 (e.g., Japanese Utility Model Laid-Open publication No. Hei 6-39169).
Thus, as described in the paragraphs 13 through the 15 of page 7 of the laid-open specification, the prior art writing tool is constructed such that when the cap 30 is loaded in respect to the extremity end 31, the inner cylinder 32 of the cap 30 closely contacts the outer periphery of the extremity end 31 to make a sealed space preventing air leakage within the inner cylinder 32, and the air in the inner cylinder 32 is pressurized and compressed under the reduced volume of the sealed and closed space. Then, when the air in the inner cylinder 32 is pressurized and compressed, the rotary member 34 projecting from the tip 33 abuts a tongue 37 of a resilient valve opening member 36 arranged in The cap, the rotary member is then is retracted against the spring by the force of the tongue 37, in such a manner that the rotary member 34 is moved away from the inward extremity edge of the contacted tip 33, thereby feeding the compressed air in the inner cylinder 32 from the clearance formed between the rotary member 34 and the inward extremity edge into the liquid tank 35, pressurizing the liquid tank 35.
However, the tongue 37 of the valve opening member in the cap is cantilevered, this structure achieved by cutting and raising the cylindrical part of the valve opening member 36 inwardly. Accordingly, when the cap is loaded in respect to the extremity end, the rotary member projecting from the tip extremity end is retracted by means of the pushing force of the tongue against the spring. Accordingly, the pushing force of the tongue becomes attenuated within a short period of time when the cap is repeatedly fixed and removed and eventually, the rotary member is not retracted inwardly toward the tip against a the spring under the attenuated pushing force of the weakened tongue. Disadvantages of poor positive operation and poor stability result.
In order to cut and raise the tongue from the valve opening member, machining is required. Further when air in the inner cylinder is pressurized and compressed, the valve opening member must be assembled and arranged within the cap in a positional relation where the rotary member abuts the tongue. The assembling operation is there troublesome and expensive.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a writing tool in which inner pressure in a liquid tank is increased by feeding compressed air in the cap into the liquid tank during cap loading, and in which machining and assembling operations are easily carried out.
It is another object of the present invention to enable a valve opening operation in which the rotary member is moved away from the inward extremity edge of the tip for feeding the compressed air to the liquid tank, and in which the valve opening operation is maintained positively and stably for a long period of time under utilization of the inner bottom part of the cap.
Further, another object of the present invention is to provide the writing tool allowing an effective gripping action.
The writing tool of the present invention described above is constructed such that the rotary member is held within the extremity end of the tip to be held at the extremity end of the liquid tank while being resiliently sprung by a spring, contacted with the inward extremity edge of the tip and partially projected, the cap is pushed and loaded at the extremity end while closely contacted with an outer periphery of the extremity end holding the tip so as to make a sealingly closed tip, wherein the length of the cap is formed into a length ranging from the extremity end of the tip to a part near the cap loading base end, and in turn there is provided a resilient member in which the cap is pushed to the cap loading base end at the extremity end or a part near the cap loading base end in the cap, the pushing operation is released to cause the cap to be pushed back to the normal loading position.
In addition, the aforesaid resilient member is made of O-ring or leaf spring or spring.
Further, in accordance with the present invention, writing tool in which a rotary member is held within an extremity end of a tip held at an extremity end of a liquid tank under a state in which it is resiliently sprung by a spring, contacted with an inward extremity end of a tip and its part is projected, a cap is pushed onto and loaded on said extremity end under a state in which it is closely contacted with an outer periphery of the extremity end holding the tip so as to sealingly close the tip, the writing tool is characterized in that: a length ranging from an opening end surface of said cap to its inner bottom part is formed into a length ranging from an extremity end of the tip to a part near a cap loading base end of the extremity end and in turn there is installed a resilient member comprising O-ring or leaf spring for pushing back the cap to the normal loading position in respect to the extremity end by releasing the pushing operation after the cap is pushed onto an outer periphery of the cap loading base end of the extremity end to a part near the cap loading base end, thereafter the pushing operation is released. According to this, when the cap is pushed into and loaded up to a part near the cap loading base end at the extremity end and the opening end surface is abutted against the O-ring at the cap loading base end and further pushed into it, the O-ring is resiliently deformed between the opening end surface of the cap and the cap loading base end, the inner bottom part of the cap is abutted against the rotary member projected out of the extremity end of the tip, the rotary member is retracted inwardly toward the tip in such a manner that it is moved away from the inner extremity end edge of the tip against a spring to open the extremity end of the tip and in turn, after the O-ring is resiliently deformed, thereafter the cap pushing operation is released, resulting in that the cap is automatically pushed back to the normal loading position at the extremity end by a recovering force (a resilient force) when it is returned to its original state before deformation, and at the same time the inner bottom part is moved away from the rotary member, the rotary member is contacted with the inner extremity end edge of the tip by a spring to close the extremity end of the tip. Thereafter the pushing operation is released, resulting in that the cap is automatically pushed back to the normal inserting and loading position at the extremity end by a spring force when the leaf spring is returned back to its original state before its deformation.
In addition, according to the present invention, the cap is pushed and loaded at the extremity end while closely contacted with an outer periphery of the extremity end holding the tip so as to make a sealingly closed tip, the writing tool is characterized in that: a length of said cap is formed into a length ranging from an extremity end of the tip to a part near a cap loading base end of the extremity end and in turn there is installed at the cap loading base end at the extremity end a resilient member for pushing back the cap to the normal loading position in respect to the extremity end by releasing the pushing operation after the cap is pushed to a part near the cap loading base end. Accordingly, as aforementioned, during a case in which the cap is pushed into and loaded up to a part near the cap loading base end at the extremity end, the inner bottom part of the cap is abutted against the rotary member projected out of the extremity end of the tip, the rotary member is retracted inwardly in a tip in such a manner that it may be moved away from the inner extremity end edge of the tip against the spring so as to open the extremity end of the tip, and in turn, the opening end surface of the cap is abutted against the resilient member at the cap loading base end and in a state in which the resilient member is being deformed, the cap pushing operation is released, resulting in that the cap is pushed back automatically by the resilient member to the normal loading position at the extremity end and concurrently the inner bottom part is moved away from the rotary member, the rotary member is contacted with the inner extremity end edge of the tip so as to close the extremity end of the tip.
In addition, according to the present invention, the cap is pushed and loaded at the extremity end while closely contacted with an outer periphery of the extremity end holding the tip so as to make a sealingly closed tip, the writing tool is characterized in that: a length ranging from an opening end surface of said cap to its inner bottom part is formed into a length as one ranging from an extremity end of the tip to a part near a cap loading base end of the extremity end, and there is installed a resilient member at an outer periphery of the extremity end for pushing back the cap to the normal loading position in respect to the extremity end by releasing the pushing operation after the cap is pushed to the cap loading base end of said extremity end, the resilient member is provided with a cap returning resilient part formed into a cylindrical shape extending from the cap loading base end of said extremity end toward the extremity part and projected in annular form in a circumferential direction along one end opening edge of the cylinder abutted against the cap loading base end. Accordingly, during the loading process of the cap against the extremity end, the cap returning resilient part of the resilient member is pushed by the opening end surface of the cap and resiliently deformed and concurrently as its resilient deformation, the inner bottom part of the cap is abutted against the rotary member projected out of the extremity end of the tip to cause the rotary member to be retracted inwardly into the tip against the spring and to feed the compressed air in the cap pressurized and compressed into the liquid tank and then the valve structure at the tip extremity end is opened. In turn, as the cap pushing operation is released, the cap is pushed back to the normal loading position of the extremity end by a recovering force of the cap returning resilient part and concurrently, the inner bottom part is moved away from the rotary member, the rotary member is contacted with the inner extremity end of the tip to close the valve structure of the tip extremity end. In addition, the cylinder part of the resilient member may perform a gripping action for preventing a slippage at the time of correcting wrong letters.
Further, another feature of this invention is that an annular end surface of at least the cap returning resilient part is provided with an indent recess for assuring and forming a deformed space augmenting resilient action of the cap returning resilient part therebetween and the cap loading base end of the extremity end. According to this, during the cap loading action against the extremity end, the cap returning resilient part of the resilient member is, as described in the above, is pushed by the opening end surface of the abutted cap and resiliently deformed in such a manner that it may be set toward the deformed space between it and the cap loading base end and in turn as the cap pushing operation is released, the cap is pushed back to the normal loading position for the extremity end by a recovering force of the cap returning resilient part augmented by the compressed air in the deformed space.
Further, another feature of this invention is that the aforementioned cap includes a transparent cap main body formed in an inner diameter larger about twice than an outer diameter of the extremity end, and a colored cylindrical inner cap with a bottom which is coaxially assembled at a tail end of the cap main body, internally installed there, closely contacted with an outer periphery of the extremity end to sealingly close the tip during loading of the extremity end, the inner bottom part being abutted against the rotating member projected from the extremity end of the tip to retract said rotary member inwardly into the tip, and a loading and moving amount of the rotary member in respect to the extremity end when the rotary member is spaced apart from the inward extremity edge of the tip is restricted under abutment of the extremity end against the extremity end surface. According to this, the colored inner cap acting as one for sealingly enclose the tip at the outer periphery of the extremity end and for pressuring and compressing the inner air during the cap loading process against the extremity end, and acting as one for moving the rotary member away from the inner extremity end edge of the tip so as to feed the pressurized and compressed air into the liquid tank so as to open the valve structure at the tip extremity end is installed inside the cap main body, resulting in that an ornamental effect of the cap can be realized. In addition, the inner cap is abutted against the extremity end surface of the extremity end when the valve structure at the tip extremity end is opened so as to restrict a loading and moving amount of the cap in respect to the extremity end abutted against the extremity end surface of the extremity end, resulting in that the compressed air in the inner cap is positively fed into the liquid tank. Namely, when the valve structure at the tip extremity end is opened, movement of the cap is received so that the tip extremity end may not be closed by the inner bottom of inner cap for making the rotary member receded and thus that compressed air in the inner cap may be surely fed into the liquid tank.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a longitudinal section for showing an embodiment of the writing tool of the present invention;
FIG. 1B is an expanded view of IB portion of FIG. 1A;
FIG. 2 is a longitudinal section for showing a substantial part to indicate a cap loading step against an extremity end;
FIG. 3A is a longitudinal section for showing a state (a valve opened state) in which a cap is loaded up to a part near a cap loading base end at an extremity end and a rotary member projecting from an extremity end of a tip is retracted toward an inside of the tip with an inner bottom part of the cap;
FIG. 3B is an expanded view of portion IIIB of FIG. 3A;
FIG. 4 is a longitudinal section for showing another embodiment of the writing tool of the present invention;
FIG. 5A is a longitudinal section for showing an embodiment of the writing tool of the present invention;
FIG. 5B is an expanded view of VB portion of FIG. 5A;
FIG. 6A is a longitudinal section for showing a state (a valve opened state) in which a cap is loaded up to a part near a cap loading base end at an extremity end and a rotary member projecting from an extremity end of a tip is retracted toward an inside part of the tip with an inner bottom part of the cap;
FIG. 6B is an expanded view of VIB of FIG. 6A;
FIG. 7A is a longitudinal section for showing one example of an embodiment of the writing tool of the present invention;
FIG. 7B is an expanded view of VIIB portion of FIG. 7A;
FIG. 8A is a longitudinal section for showing a state (a valve opened state) in which a cap is loaded up to a part near a cap loading base end at an extremity end and a rotary member projecting from an extremity end of a tip is retracted toward an inside part of the tip with an inner bottom part of the cap;
FIG. 8B is an expanded view of VIIIB portion of FIG. 8A;
FIG. 9 is a partial enlarged view for showing another embodiment of a spring supporting state;
FIG. 10 is a longitudinal section for showing an embodiment of the writing tool of the present invention;
FIG. 11A is a longitudinal section for showing a state in which an inner cap is closely contacted with an outer circumference of the extremity end during a loading step against the extremity end;
FIG. 11B is an expanded sectional view of main point of FIG. 11A;
FIG. 12 is a longitudinal section for showing a state in which an opening end surface of a cap is abutted against a cap returning resilient part of a resilient member during a loading step against the extremity end;
FIG. 13A is a longitudinal section for showing a state (a valve opened state) in which a cap returning resilient part of a resilient member is resiliently deformed while being pushed by an opening end surface of the cap during a loading step against the extremity end;
FIG. 13B is an expanded view of main point of FIG. 13A;
FIG. 14A is a longitudinal section for showing an embodiment of the writing tool of the present invention;
FIG. 14B is a section taken along a line XIVB--XIVB of FIG. 14A;
FIG. 15A is a longitudinal section for showing another embodiment of the writing tool of the present invention;
FIG. 15B is a section taken along a line XVB--XVB of FIG. 15A; and
FIG. 16 is a longitudinal section for showing the prior art writing tool.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, preferred embodiments of the present invention will be described as follows.
FIGS. 1A to 3B illustrate an embodiment of the writing tool of the present invention on claims 1 and 2, wherein a liquid tank 1 is formed in either of a pen type or a bottle type, an extremity end 3 for holding a tip 2 is loaded at an extremity part of the liquid tank, a cap 4 is pushed and loaded up to a part near a cap loading base end 3-1 (circumferential step) of the extremity end 3 while being closely contacted with an outer (cylindrical) circumference of the extremity end 3, thereby an inner bottom part 4-1 (inner end surface) of the cap 4 is abutted against a rotary member 5 projecting from the extremity part of the tip 2 so as to cause the rotary member 5 to be retracted inwardly toward the tip 2 in such a manner that the rotary member is spaced apart from an inward extremity edge 2-1 (retaining rim) of the tip 2 against a spring 6, whereby the extremity end of the tip 2 is opened (unblocked), compressed air in the cap 4 pressurized and compressed during a pushing and loading step of the cap 4 is fed into the liquid tank 1 and then an inner pressure of the liquid tank 1 is increased.
Then, at the outer periphery of the cap loading base end 3-1 of the extremity end 3 is installed an O-ring 7 for automatically pushing back the cap 4 to the normal loading position of the extremity end 3 by releasing the pushing operation after the cap 4 is pushed and loaded up to a part near the cap loading base end 3-1.
In this case, the normal loading position of the cap 4 against the extremity end 3 is defined as a state in which an annular projection 9 at the inner surface of the cap 4 is engaged with an annular projection 8 at the outer periphery of the extremity end 3.
The tip 2 and the extremity end 3 are substantially of a well-known structure. That is, the tip 2 is formed into a pipe (channel) with proper metallic material, an opening edge at the extremity end formed narrow at its end is drawn by a press fitting and the like, an inward directed extremity is arranged at the extremity end and concurrently a radial longitudinal groove 10 formed by a broach machining operation is arranged inside the edge, the rotary member 5 is held at the inside extremity end between the longitudinal groove 10 and the inner extremity edge 2-1 under one state in which the rotary member is being resiliently urged and contacted with the inward directed extremity edge 2-1 and the other state in which its part is being projected from the inward directed extremity edge 2-1. The extremity end 3 has a straight large-diameter cylindrical part 3-2 ranging from the cap loading base end 3-1 to the midway part directed toward the extremity end for holding the tip 2, the extremity end is formed into a stepped cylindrical shape of narrow end formed substantially into a narrow straight toward its end and then the tip 2 is press fitted into and held at a small-diameter cylinder part 3--3 at the extremity end.
The cap 4 is formed into a stepped shape with a narrow end thereof in compliance with an outer shape of the extremity end 3, and a length LI ranging from an opening end surface 4-2 (rim) to an inner bottom part 4-1 is formed into a length L2 ranging from the extremity end of the tip 2 from which the rotary member 5 is projected to a part near the cap loading base end 3-1 of the extremity end 3. In other words, the length is formed into the length LI in which, when the cap 4 is loaded up to a part near the cap loading base end 3-1 of the extremity end 3, as shown in FIG. 3A and 3B the opening end surface 4-2 of the cap 4 is abutted against the O-ring 7 at the cap loading base end 3-1 so as to cause the O-ring 7 to be resiliently deformed and concurrently the inner bottom part 4-1 is abutted against the rotary member 5 projected from the extremity end of the tip 2, the rotary member 5 can be retracted inwardly toward the tip 2 against the spring 6 in such a manner that it is spaced apart from the inward extremity edge 2-1.
Reference numeral 11 in the figure denotes an annular projection arranged at the inner (circumferential) surface of the reduced diameter part 4-3 of the cap 4 and this projection may act to be closely contacted with the outer periphery of the reduced diameter part 3--3 of the extremity end 3 during a process in which the cap 4 is pushed and loaded against the extremity end 3 so as to compress the air in the cap 4.
In addition, the reduced diameter part 4-1 of the cap 4 is provided with a proper height step 12 directed from the inner bottom part 4-1 toward the opening end surface 4-1 so as to be operated such that when the cap 4 is loaded against the extremity end 3 to cause its inner bottom part 4-1 to abut against the rotary member 5 and further to cause the rotary member 5 to be retracted, it is abutted against the extremity end surface 3-4 of the extremity end 2 so as to restrict a loading and moving amount of the cap 4 in respect to the extremity end 3.
That is, it is constructed such that a motion of the cap 4 is received when the extremity end of the tip 2 is opened through abutment of the inner bottom part 4-1 against the rotary member 5 without being influenced by a force of a user when the cap 4 is loaded, the inner bottom part 4-1 is prevented from being abutted against the inward extremity edge 2-1 of the tip 2. That is, the compressed air within the cap 4 is fed positively from a clearance between the rotary member 5 and the inward-directed extremity edge 2-1 into the liquid tank 1 while the extremity end of the opened (unblocked) tip 2 is not clogged by the inner bottom part 4-1 of the cap 4 (a "pressurizing position" as shown in FIG. 3B).
The O-ring 7 is resiliently deformed during a step in which the cap 4 is pushed into and loaded to a part near the cap loading base end 3-1 of the extremity end 3 so as to push back the cap 4 automatically to the normal loading position in respect to the extremity end 3 when its pushing operation is released (a user's hand is removed from the cap 4). That is, during the aforesaid loading step of the cap 4, the O-ring 7 may act to release the pushing of the rotary member 5 in such a manner that the rotary member 5 retracted inwardly in the tip 2 against the spring 6 through abutment of the inner bottom part 4-1 is contacted again with the inner-directed extremity edge 2-1 with the spring 6 to cause the extremity end of the tip 2 to be closed (blocked), the O-ring 7 is made of resilient materials, such as silicone rubber or soft resin or foamed styrol or the like capable of realizing a recovering force (a resilient force) for pushing back the cap from its state resiliently deformed by the opening end surface 4-1 of the cap 4 to the normal loading position of the extremity end 3, and the O-ring 7 is installed at the engaging groove 13 arranged at the cap loading base end 3-1.
As illustrated in FIG. 4 in a second embodiment, the O-ring 7 may be formed into a hollow shape. In this case, enclosures such an air or gel-like substances may sometimes be enclosed in the hollow space in such a degree as one to enable a recovering force (a resilient force) to be attained for pushing back the cap 4 to the normal loading position of the extremity end 3.
An example of use of the writing tool of the present embodiment constructed as described above will be described as follows, wherein the cap 4 is pushed onto the extremity end 3 from a state (a "writing position" of the rotary member 5 in FIG. 2) in which the annular projection 11 at the inner surface of the cap 4 is closely contacted with the outer periphery of the extremity end 3, until the opening end surface 4-2 of the cap 4 is abutted against the O-ring 7 at the cap loading base end 3-1 to cause the O-ring 7 to be resiliently deformed. Then, during a step in which the inner stepped part 12 of the cap 4 is abutted against the extremity end surface 3-4 of the extremity end 3, the O-ring 7 is resiliently deformed, the inner bottom part 4-1 of the cap 4 is abutted against the rotary member 5 projected from the extremity end of the tip 2 to cause the rotary member 5 to be retracted inward in the tip 2 in such a manner that it is spaced apart from the inward extremity edge 2-1 of the tip 2 against the spring 6 and then the valve structure at the extremity end of the tip 2 is opened (unblocked, i.e., the "pressurizing position" of the rotary member 5 shown in FIGS. 3A & 3B).
That is, from the normal cap-loading position in respect to the extremity end 3 as shown in FIGS. 1A & 1B, the cap 4 is pushed against the extremity end 3 until the opening end surface 4-2 of the cap 4 is abutted against the O-ring 7 at the cap loading base end 3-1 to make a resilient deformation of the O-ring 7 in its push crushed state, the inner bottom part 4-1 of the cap 4 spaced apart from the extremity end of the tip 2 is abutted against the rotary member 5 projected from the extremity end of the tip 2 to cause the rotary member 5 to be retracted inward of the tip 2 in such a manner that the rotary member is spaced apart from the inner extremity edge 2-1. With such an arrangement as above, the valve structure at the extremity end of the tip 2 is opened, the compressed air within the cap 4 is fed positively from a clearance between the opened inner extremity edge 2-1 and the rotary member 5 into the liquid tank 1 so as to increase the inner pressure within the liquid tank 7.
In turn, after the cap 4 is pushed onto the extremity end 3 until the O-ring 7 at the cap loading base end 3-1 is resiliently deformed as described above, the pushing operation is released (the cap 4 is removed), resulting in that the cap 4 is pushed back to the normal loading position against the extremity end 3 with the recovering force when the O-ring 7 returns to its original state before its deformation and concurrently the inner bottom part 4-1 of the cap 4 is moved away from the rotary member 5 (returned back to the state shown in FIG. 1A).
With such an arrangement as above, the rotary member 5 is contacted with the inner extremity edge 2-1 of the tip 2 by the spring 6 and then the valve structure at the extremity end is closed. (refer to FIG. 1B)
FIGS. 5A to 6B illustrate a third embodiment of the writing tool of the present invention, wherein this embodiment is constructed such that, as the resilient member for use in pushing back the cap 4 from the part near the cap loading base end 3-1 of the extremity end 3 to its normal loading position, a ring-shaped leaf spring 14 is loaded at the cap loading base end 3-1 of the extremity end 3 in place of the O-ring 7 described in detail in the aforesaid embodiments and then the cap 4 is pushed back from the part near the cap loading base end 3-1 of the extremity end 3 to its normal loading position with the spring force of the leaf spring 14. Otherwise, since remaining portions the aforesaid third embodiment are substantially similar to those of the detailed first embodiment described above expecting features directed to the leaf spring 14, the same reference numerals are applied to the same elements and the description thereof is omitted.
The leaf spring 14 is of a ring-shape freely fitted to the engaging groove 15 arranged at the cap loading base end 3-l of the extremity end 3, and formed into a substantial disk-shape having its inside part of the ring expanded to be deformable.
In this way, in the case of the writing tool of the third embodiment, the opening end surface 4-2 of the cap 4 is abutted against the leaf spring 14, the cap 4 is pushed further up to a part near the cap loading base end 3-1 for deforming the leaf spring 14 (a state in FIG. 6A), the inner bottom part 41 of the cap 4 causes the rotary member 5 projected from the extremity end of the tip 2 to be retracted inwardly toward the tip 2 against the spring 6 as described in detail in the above embodiment and then the valve structure at the extremity end of the tip 2 is opened (refer to FIG. 6A). Then, the pushing operation of the cap 4 is released, the cap 4 is pushed back to the normal loading position of the extremity end 3 with the spring force of the leaf spring 14 and the valve structure at the extremity end of the tip 2 is closed.
FIGS. 7A to 8B illustrate a fourth embodiment of the writing tool of the present invention, wherein a spring 16 is loaded in the reduced diameter part 4-3 of the cap 4 and the cap 4 is pushed from the cap loading base end 3-1 of the extremity end 3 to the normal position of the extremity end 3 with a force of the spring 16. In the fourth embodiment features that are substantially similar to those of the first embodiment described above, e.g., generally excepting the length of the cap 4 itself and the arrangement of the spring 16, are identified by the same reference numerals and the description thereof is omitted.
The cap 4 is constructed such that a length L3 ranging from the opening end surface 4-2 to the inner bottom part 4-1 is formed into a length L4 ranging from the extremity end of the tip 2 from which the rotary member 5 projects to the cap insertion and loading base end 3-1 of the extremity end 3, the cap 4 is pushed onto the extremity end 3 and loaded there until the opening end surface 4-2 is abutted against the cap insertion and loading base end 3-1, thereby the inner bottom part 4-1 is abutted against the rotary member 5 projected from the extremity end of the tip 2, the rotary member 5 is retracted inwardly toward the tip 2 in such a manner that the rotary member 5 is spaced apart from the inner extremity edge 2-1 against the spring 6 and the valve structure at the extremity end of the tip 2 is opened.
That is, a loading and moving amount of the cap 4 in respect to the extremity end 3 is restricted under an abutment between the opening end surface 4-2 of the cap 4 and the cap loading base end 3-1 (a state in FIG. 8A), and the opened valve structure at the extremity end of the tip 2 (the inward extremity edge 2-1) is not prevented from being clogged by the inner bottom part 4-1 of the cap 4. (a state in FIG. 8B)
The spring 16 is formed to have a proper length with such an outer diameter as one capable of being freely inserted into the reduced diameter part 4-3 of the cap 4, its one end is supported by a press fitting at a supporting stepped part 17 formed slightly smaller than the outer diameter of the spring 16 at the inner bottom part 4-1 of the reduced diameter part 4-3 and the spring is coaxially installed within the reduced diameter part 4-3 while being projected from the reduced diameter part 4-3 toward the opening end of the cap 4.
In addition, as means for supporting one end of the spring 16 at the supporting step 17 of the reduced diameter part 4-3, this is not limited to the press fitting, but various means can be optionally attained such as supporting through screw thread by arranging a helical groove le at the inner surface of the reduced diameter part 4-3 as shown in FIG. 9 to enable several turns at one end of the spring 16 to be supported.
Thus, in accordance with the writing tool of the embodiment described above, when the cap 4 is pushed and loaded onto the extremity end 3 until the opening end surface 4-1 of the cap 4 is abutted against the cap loading base end 3-1, the spring 16 is gradually compressed from the time when the other end of the spring is abutted against the extremity end surface 3-4 of the extremity end 3 during that operation, the inner bottom surface 4-1 of the cap 4 is abutted against the rotary member 5 projected out of the extremity end of the tip 2, the rotary member 5 is retracted inwardly toward the tip 2 so as to open the valve structure at the extremity end of the tip 2. In turn, after the cap 4 is pushed onto the extremity end 3 until the opening end surface 4-2 of the cap 4 is abutted against the cap loading base end 3-1 (a state in FIG. 8A), the pushing operation of the cap 4 is released, the cap 4 is pushed back to the normal loading position of the extremity end 3 by the spring 16 expanded with the other end of the spring being abutted against the extremity end surface 3-4 of the extremity end 3 (returned back the state shown in FIG. 7A). With such an arrangement as above, the inner bottom part 4-1 of the cap 4 is spaced apart from the rotary member 5, the rotary member 5 is contacted with the inward extremity edge 2-1 of the tip 2 by the spring 6 to close the valve structure at the extremity end. (a state in FIG. 7B)
Accordingly, in accordance with the writing tool of the present invention constructed as above, the fact that an inner pressure in the liquid tank is increased by feeding compressed air into the liquid tank as well as the fact that O-ring, leaf spring or spring of which machining and fixing can be easily carried out are utilized as a resilient member for pushing back the cap to the normal loading position in respect to the extremity end after feeding the compressed air into the liquid tank to pressurize an inside part of the liquid tank during a loading process of the cap in respect to the extremity end enable its machining and assembling to be substantially simplified as compared with that of the prior art writing tool and further enable its manufacturing cost to be reduced. The valve opening operation for retracting the rotary member projected out of the extremity end of the tip inwardly toward the tip so as to feed the compressed air into the liquid tank is performed in such a manner that the rotary member is abutted against the inner bottom part of the cap, so that the valve opening operation can be maintained positively and stably for a long period of time without being damaged in a short period of time as found in the prior art writing tool.
FIGS. 10 to 13B illustrate a fifth embodiment of the writing tool of the present invention, wherein a cylindrical resilient member 19 is loaded at an outer periphery of the extremity end 3, a cap 21 is pushed and loaded up to a cap loading base end 3-1 (circumferential step) in respect to the extremity end 3 with a cap returning resilient part 20 (resilient circumferential ring) arranged at an outer periphery of the cylindrical part 19-1 of the resilient member 19 to be described later, thereafter the pushing operation is released to cause the cap 21 to be automatically pushed back to the normal loading position of the extremity end 3. Then, the cap 21 is comprised of a cap main body 21-2 and an inner cap 21-3, and during a process in which the cap 21 is loaded in respect to the extremity end 3, the (inner circumferential surface of the) inner cap 21-3 is closely contacted with the outer periphery (outer cylindrical surface) of the extremity end 3 to compress the air within the inner cap 21-3 contacted with the rotary member 5 projected out of the extremity end of the tip 2, the rotary member 5 is spaced apart from the inward extremity edge 2-1 retaining rim of the tip 2 against a spring 6 as to open (unblock) the valve structure at the extremity end of the tip 2 comprised of the rotary member 5 and the inward extremity edge 2-1. Elements of this embodiment that are substantially similar to the first embodiment described above generally excepting the form of the resilient member 19 for use in returning the cap 21 and the form of the cap 21 are identified by the same reference numerals, and the description thereof is omitted.
The normal loading position of the cap 21 the respect to the extremity end 3 in such an embodiment as above is defined as a state in which the cap 21 is retracted and returned back in a direction where the cap is pulled out of the extremity end 3 by the resilient member 19, and the inner bottom part 21-1 (inner end surface) of the inner cap 21-3 is spaced apart from the rotary member 5. That is, the inner bottom part 21-1 of the inner cap 21-3 is spaced apart to cause the rotary member 5 to be resiliently sprung by the spring 6 and contacted with the inward extremity edge 2-1 of the tip 2 and the valve structure at the extremity end of the tip 2 is closed (block).
The extremity end 3 comprises a large diameter cylindrical part 3-2 having a straight segment ranging from the cap loading base end 3-1 toward the midway part of extremity end side holding the tip 2, as described in detail in reference to the aforesaid embodiment, this is formed into a fine narrow end stepped cylindrical shape (outer circumferential surface) formed substantially straight, and the tip 2 is held by being press fitted to the reduced diameter cylindrical part 3--3 at the extremity end. Then, in the embodiment, an outer periphery of the large diameter cylindrical part 3-2 of the extremity end 3 is provided with an indent part 22 so as to enable the resilient member 19 to be strictly loaded in flush with the outer periphery of the large diameter cylindrical part 3-2.
The indent part 22 is formed in compliance with a thickness of a cylindrical wall of the cylindrical part 19-1 of the resilient member 19 within a range over an entire length from the cap loading base end 3-1 to the substantial full length of the large diameter cylindrical part 3-2. Then, an annular groove 23 having an appropriate width and depth is arranged along an opening edge at the bottom part of the indent part 22 located at the reduced diameter cylindrical part 3--3, and an annular projection 24 of the resilient member 19 to be described later is formed to be engaged through a fastening action.
The cap 21 includes a cap main body 21-2; and an inner cap 21-3 which is coaxially assembled at a tail end of the cap main body 21-2, installed internally thereof, sealingly contacted with an outer periphery of the reduced diameter cylindrical part 3--3 of the extremity end 3 during a step in which the cap main body 21-2 is loaded at the extremity end 3, and for sealingly closing the tip 2 projected from the reduced diameter cylindrical part 3--3.
The cap main body 21-2 is made of transparent synthetic resin material to be formed into a cylindrical shape having an inner diameter which is larger about twice than an outer diameter of the large diameter cylindrical part 3-2 of the extremity end 3r and the cap main body 21-2 covers the extremity end 3 under a state in which a clearance 25 to cause inner air to be naturally retracted is kept between it and the outer periphery of the large diameter cylindrical part 3-2 of the extremity end 3 during its loading step in respect to the extremity end 3. Then, a length L5 ranging from the opening end surface 21-20 to the inner bottom part 21-1 of the inner cap 21-3 is formed to be about a length L6 ranging from the extremity end of the tip 2 from which the rotary member 5 projects to a part near the cap loading base end 3-1 of the extremity end 3.
The inner cap 21-3 is formed of colored synthetic resin material and made into a cylindrical shape having a bottom part with an inner diameter closely contacted with an outer periphery of the reduced diameter cylindrical part 3--3 of the extremity end 3 and a proper length, the inner surface directed inwardly from the opening edge is formed with a stepped part 26 abutted against the extremity end surface 3-4 of the reduced diameter cylindrical part 3--3 during the loading step in respect to the extremity end 3 so as to restrict a loading and moving amount of the cap 21 in respect to the extremity end 3, and the inner cap 21-3 is coaxially assembled and internally arranged at the tail end under a fixed state in which it is fitted and engaged with an installing port 27 opened coaxially at the tail end of the cap main body 21-1.
In this case, the cap 21 sealingly closes the tip 2, pressurizes the inner air, retracts the rotary member 5 inwardly into the tip 2 so as to move the rotary member apart from the inward extremity edge 2-1 for feeding the compressed air into the liquid tank 1, assembles the colored inner cap 21-3 acting to open the valve structure located at the extremity end of the tip 2 into the transparent cap main body 21-2 and internally installing the inner cap in the cap main body,. Then, the inner cap 21-3 causes the stepped part 26 to be abutted against the extremity end surface 3-4 of the reduced diameter cylindrical part 3--3 of the extremity end 3 when the valve structure located at the extremity end of the tip 2 is opened with the inner bottom part 21-1 during its loading step in respect to the extremity end 3, so as to restrict a loading and moving amount of the cap 21 in respect to the cap 21. That is, as described in detail in the aforesaid embodiment, it may accept the motion of the cap 21 to prevent the inward extremity edge 2-1 of the tip 2 from being closed with the inner bottom part 21-1 of the inner cap 21-3 without being influenced by a degree of force applied by a user in case of loading the cap 21 when the valve structure is opened through abutment with the rotary member 5. That is, the compressed air within the inner cap 21-3 is positively fed from the clearance between the rotary member 5 of which valve is opened and the inward extremity edge 2-1 into the liquid tank 1 (the "pressurizing position" of the rotary member 5 shown in FIG. 13B).
A resilient member 19 is formed into a cylindrical shape having such a thickness, length and outer diameter to be flush with an outer periphery of the large diameter cylindrical part 3-2 within the indent part 22 arranged in the large diameter cylindrical part 3-2 of the extremity end 3, and the opening edge at one end of the cylindrical part 19-1 is provided with a cap returning resilient part 20 projected in an annular form in a peripheral direction.
The cylindrical part 19-1 may provide a gripping action to prevent a holding part from being slid during use of the writing tool to correct written wrong letters, an annular projection 24 fitted to and engaged with the annular groove 23 arranged at the bottom part of the indent part 22 is get at an inner periphery of the other end opening edge of the cylindrical part, and then the cylindrical part 19-1 can be fixed and held in the indent part 22 without being removed from it and flush with the outer periphery of the large diameter cylindrical part 3-2 under a fastening action worked on the annular projection 24 like a rubber band.
The cap returning resilient part 20 is resiliently deformed while being pushed by the opening end surface 21-20 of the cap 21 during a loading step in respect to the extremity end 3, recovered and deformed when its pushing operation is released (the hand is moved away from the cap 21) so as to act to push back the cap 21 automatically to the normal loading position in respect to the extremity end 3. That is, after the inner bottom part 21-1 of the inner cap 21-3 abuts against the rotary member 5 and retracts it inwardly toward the tip 2 against the spring 6 during the aforesaid loading process, it may act to release the pushed state of the rotary member 5 in such a manner that the rotary member 5 is contacted again with the inward extremity edge 21-1 by the spring 6 to close the valve structure located at the extremity end of the tip 2, wherein at a state in which one end opening edge of the cylindrical part 19-1, more particularly the cylindrical part 19-1 is being loaded at the indent part 22 of the extremity end 3, it may be arranged in a rectangular annular form in a circumferential direction along an opening edge of the opening end abutted against the cap loading base end 3-1 at a projecting height having a substantial same diameter as an outer diameter of the cap main body 21-2 (on outer diameter of the opening of the opening end surface 21-20).
Then, an example of usage of the writing tool of the present embodiment constructed as described above will be described as follows, wherein the inner cap 21-3, under its close contacted state with an outer periphery of the reduced diameter cylindrical part 3--3 of the extremity end 3 (a state shown in FIG. 11A), is pushed until the opening end surface 21-20 of the cap 21 is abutted against the cap returning resilient part 20 of the resilient member 19 which is present under its state abutted against the cap loading base end 3-1 (a state shown in FIG. 12). At this time, the air in the inner cap 21-3 is pressurized and compressed, passes through a clearance 25 in respect to the cylindrical part 19-1 of the resilient member 19 without being remained in the cap main body 21-2 and then the air is automatically discharged into the surrounding air (refer to FIG. 11A). Accordingly, during the loading step against the extremity end 3, it is possible to load the cap 21 without being applied by a load resistance caused by remained air in the cap main body 21-2. That is, it is possible to load the cap 21 only with a low force of a close contacting force of the inner cap 21-3 in respect to the extremity end (the "writing position" of the rotary member 5 is shown in FIGS. 11A-12).
Then, the opening end surface 21-20 of the cap 21 is abutted against the cap returning resilient part 20 and further pushed. Then, during a step in which the stepped part 26 of the inner cap 21-3 is abutted against the extremity end surface 3-4 of its reduced diameter cylindrical part 3--3 of the extremity end 3 so as to restrict a loading and moving amount in respect to the extremity end 3, the cap returning resilient part 20 is resiliently deformed and concurrently, the inner bottom part 21-1 of the inner cap 21-3 is abutted against the rotary member 5 projected out of the extremity end of the tip 2, the rotary member 5 is retracted inwardly toward the tip 2 in such a manner that it may be moved away from the inward extremity edge 2-1 of the tip 2 against the spring 6 so as to open the valve structure located at the extremity end of the tip 2 (a state shown in FIG. 13A & 13B). That is, as shown in FIG. 10, at the normal loading position in respect to the extremity end 3, the inner bottom part 21-1 of the inner cap 21-3 spaced apart from the extremity end of the tip 2 is abutted against the rotary member 5 projected out of the extremity end of the tip 2 by a method wherein the cap 21 is pushed in respect to the extremity end 3 until the opening end surface 21-20 of the cap 21 is abutted against the cap returning resilient part 20 at the cap loading base end 3-1 and the cap returning resilient part 20 is resiliently deformed, and the rotary member 5 is retracted inwardly toward the tip 2. With such an operation as above, the valve structure located at the extremity end of the tip 2 is opened, the compressed air in the inner cap 21-3 is fed into the liquid tank 1 through the clearance between the valve opened inward extremity edge 2-1 and the rotary member 5 so as to increase an inner pressure in the liquid tank 1.
In turn, as the pushing operation for the cap 21 is released (the cap 21 is released), the cap 21 is pushed back to the normal loading position in respect to the extremity end 3 by a recovering force (a resilient force) where the cap returning resilient part 20 returns to its original state before deformation and concurrently the inner bottom part 21-1 of the inner cap 21-3 is moved away from the rotary member 5 (returned back to the state shown in FIG. 10). With such an operation as above, the rotary member 5 is contacted with the inward extremity edge 2-1 of the tip 2 by the spring 6 so as to close the valve structure located at the extremity end.
FIGS. 14A to 15B illustrate sixth embodiment of the writing tool of the present invention.
FIGS. 14A and 14B show a sixth embodiment, a system in which an annular end surface of the cap returning resilient part 20 in a general structure similar to the fifth embodiment, is provided with an (annular) indent recess 29 for keeping a deformed space 28 of the cap returning resilient part 20 in respect to the cap loading base end 3-1, the cap 21 is pushed onto the extremity end 3, its opening end surface 21-20 is abutted against the cap returning resilient part 20, then as it is pushed, the cap returning resilient part 20 is resiliently deformed in such a manner that the cap returning resilient part 20 is released into the deformation space 28, then as the pushing operation is released, the recovering force of the cap returning resilient part 20 is augmented by the compressed air within the compressed and deformed space as the cap returning resilient part 20 is resiliently deformed. In the sixth embodiment, the same reference numerals are applied to the elements substantially similar to those of the fifth embodiment and the description thereof is omitted.
The indent recess 29 is formed into a groove having a proper depth and an opening width at the annular end surface of the cap returning resilient part 20 abutted against the cap loading base end 3-1, the cylindrical part 19-1 is loaded in the indent part 22 of the extremity end 3, thereby an annular deformed space 28 is assured in respect to the cap loading base end 3-1 (refer to FIG. 14B).
Thus, according to the writing tool of the sixth embodiment, the cap 21 is pushed onto the extremity end 3 to cause its opening end surface 21-20 to be abutted against the cap returning resilient part 20 of the resilient member 19 and further pushed. Then, the cap returning resilient part 20 is pushed by the opening end surface 21-20 of the abutting cap 21 and resiliently deformed in such a manner that it is released into the deforming space 28 assured in respect to the cap loading base end 3-1 and concurrently as it is resiliently deformed, the inner bottom part 21-1 of the inner cap 21-3 is abutted against the rotary member 5 projected out of the extremity end of the tip 2 so as to open the valve structure located at the extremity end of the tip 2 as described in detail in the aforesaid embodiment.
In turn, when the pushing operation is released after the stepped part 26 of the inner cap 21-3 is abutted against the extremity end surface 3-4 of the reduced diameter cylindrical part 3--3 of the extremity end 3 and pushed until a loading and moving amount in respect to the extremity end 3 is restricted, the cap 21 is pushed back to the normal loading position in respect to the extremity end 3 with the recovering force of the cap returning resilient part 20 augmented by the compressed air in the deformed space 28 compressed during the pushing operation of the cap 21 so as to close the valve structure located at the extremity end of the tip 2 as described in detail in the aforesaid embodiment.
FIGS. 15A and 15B illustrate a seventh embodiment in which the shape of the opening of the indent recess 29 in the (annular) aforesaid embodiment described in detail is changed, wherein, the indent recess 29 is formed into a substantial L-shaped section opened from the annular end surface of the cap returning resilient part 20 abutted against the cap loading base end 3-1 toward the inner surface of the cylindrical part 19-1, and a deformed space 28 is kept between the cap loading base end 3-1 of the extremity end 3 and its outer circumference, so-called bottom part of the indent 22.
Accordingly, in accordance with the writing tool of the seventh embodiment of the present invention constructed as described above, the valve opening operation in which the rotary member 5 projected out of the tip 2 is retracted inwardly toward the tip 2 in order to feed the compressed air in the compressed cap 21 into the liquid tank 1 during the cap 4 loading step in respect to the extremity end 3 is performed by the inner bottom part 21-1 of the cap 4 in the same manner as that of the sixth embodiment described in detail, so that it can be kept positively and stably for a long period of time.
In addition, the cap returning resilient part 20 is pushed to be released toward its deformed space 28 and resiliently deformed. In other words, since a high pushing force is not required when the cap 21 pushing operation in respect to the extremity end 3 is carried out, children or ladies can handle the writing tool easily and this is substantially convenient in operation.
Further, since the recovering force of the cap returning resilient part 20 for pushing back the cap 4 up to the normal loading position of the extremity end 3 is augmented by the compressed air in the compressed and deformed space 28 during pushing operation of the cap 4, its positive characteristic can be attained. In addition, the cylindrical part 19-1 of the resilient member 19 may act to grip for preventing a slippage of the writing tool when it is used for correcting the wrong letters.
Further, the colored inner cap 21-3 which may act to be closely contacted with an outer periphery of the extremity end 3 to sealingly close the tip 2 and to compress inner air and act to keep the rotary member 5 spaced apart from the inward extremity edge 2-1 of the tip 2 in order to feed compressed air into the liquid tank 1 and to open the valve structure located at the extremity end 3 of the tip 2 is stored within the transparent cap main body 21-2. The ornamental effect of the cap 21 is improved. In addition, since the inner cap 21-3 may act to abut against the extremity end surface of the extremity end 3 when the valve structure located at the extremity end 3 of the tip 2 is opened so as to restrict the loading and moving amount of the cap 21 in respect to the extremity end 3, the compressed air in the inner cap 21-3 which is pressurized and compressed is positively fed into the liquid tank 1.
As writing tool of the present invention is constructed as described above, the valve opening operation in which the rotary member projected out of the tip is retracted inwardly toward the tip in order to feed the compressed air in the compressed cap into the liquid tank during the cap loading step in respect to the extremity end is performed by the inner bottom part of the cap, so that the operation for opening valve when the compressed air in the cap is fed into liquid tank can be kept positively and stably for a long period of time. Accordingly, the writing tool of the present invention is preferable as a writing tool in which an inner pressure in the liquid tank is increased by feeding compressed air of the cap into the liquid tank during the cap loading step and also that the liquid in the tank is fed into writing portion of the extremity end of the tip by utilizing said inner pressure. For example, it is useful as a tool for coating correcting fluid and so on that correcting fluid filled in liquid tank is fed into writing portion of the extremity end of the tip by increasing internal pressure of the tank during the writing step and thus the correcting fluid is applied to mistakenly written letters. | This invention relates to a writing tool for correction of misspelled words or a writing utensil such as a ball-point pen, in which air in a cap is pressurized in a process of pushing the cap onto and mounting the cap on an extremity end and the compressed air is forced into a liquid tank through an end of a tip to provide pressurization within the liquid tank. A distance from an opening end surface of a cap to an inner bottom portion of the cap is defined with respect to a distance from an end of a tip to near a cap loading base end of an extremity end. A resilient member is mounted on an outer periphery of the extremity end or in the cap for pushing back the cap to a normal mount position relative to the extremity end by releasing a pushing operation after the cap is pushed near the cap mounting base end. The cap can be automatically pushed back from the cap mounting base end to the normal mount position of the extremity end by means of the elastic member. | 1 |
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